飞灰和废大理石烟气脱硫的传质反应研究

在双搅拌釜上实验测定了飞灰和废大理石浆液的脱硫率η及pH值随过程时间t的变化关系,计算了不同t时的传质速率Nm、液膜传质系数kL、气相总传质系数KG、气膜传质系数kG、传质系数之比KG/kG以及反应增强因子E等,并分析了飞灰和废大理石脱硫的传质-反应过程.实验和计算结果表明,当进口SO2体积分数为4000×10-6时,飞灰和大理石浆液脱硫均受液相阻力控制;pH值越低,KG/kG就越小,液相阻力控制也就越明显,在pH＝4.5时,液相阻力占总阻力的90%; pH值越高,E就越大,化学反应对传质的影响也就越明显;pH＝6时飞灰浆液具有与大理石浆液相近的脱硫率,达70%左右.     

Vapor-phase elemental mercury adsorption by residual carbon separated from fly ash

Introduction The impact of mercury on the environment and thephysiological health of human is well documented(Laudal,2000; Poissant, 2002; Galbreath, 2000; Palusova, 1991).Mercury, especially methyl mercury, has high affinities forfatty tissue…     

壳聚糖吸附剂脱除燃煤模拟烟气中汞的试验研究

采用在线检测法检测了纯氮气气氛下及模拟烟气气氛下高分子化合物壳聚糖吸附剂对单质汞的吸附特性,结果表明,温度升高有利于脱汞反应的进行,纯氮气氛下脱除汞单质效率不高,60℃时为28.85%, 120℃时升为38.46%;氮氧化物、硫氧化物对汞的脱除有一定的促进作用,在模拟烟气气氛下120℃时吸附剂出口平衡吸附率为48.05%,平均吸附率约68%.红外光谱分析揭示了壳聚糖吸附剂吸附烟气中汞的机理为2个游离氨基与2个羟基鳌合1个汞原子或汞离子.     

工业燃煤锅炉烟气循环方式下飞灰的汞吸附特性

为探究燃煤锅炉烟气循环方式下飞灰汞的吸附特性,利用固定床汞吸附装置,对立式煤粉沉降炉不同模拟烟气循环工况条件下形成的飞灰汞吸附特性进行了研究,重点考察了烟气循环比例、煤种、关键燃烧气体组分等因素的影响.结果表明:①烟气循环工况条件下形成的飞灰汞吸附能力明显优于非烟气循环工况（空气燃烧）条件下形成的飞灰,并且随烟气循环比例的增加,飞灰汞吸附量呈逐渐增加趋势.褐煤在净烟气循环比例为60%、40%、20%的条件下形成的飞灰汞吸附量分别是非烟气循环条件下的3.0、2.3和1.6倍.②烟气循环引起燃烧气体氛围中ρ（SO₂）与ρ（NO）的变化会影响飞灰的物化特性及其汞吸附性能.随燃烧氛围中ρ（SO₂）的提高,飞灰汞吸附量先增后减.烟气循环比例为40%且燃烧气体氛围中ρ（NO）为803 mg/m3条件下,ρ（SO₂）为2 857 mg/m3时褐煤与烟煤燃烧形成的飞灰汞吸附量较高（分别为0.45和0.75 μg/g）,分别较ρ（SO₂）为1 428和4 286 mg/m3时提高了25%~300%和53%~78%.随燃烧氛围中ρ（NO）的提高,飞灰汞吸附量呈逐渐增加趋势.烟气循环比例为40%且燃烧气体氛围中ρ（SO₂）为2 857 mg/m3条件下,ρ（NO）为1 205 mg/m3时褐煤和烟煤燃烧形成的飞灰汞吸附量较高,分别较ρ（NO）为803和402 mg/m3时提高了1.2~3.6和1.1~1.6倍.③飞灰中UBC（未燃尽碳）、CaO、MgO及Fe₂O₃可促进飞灰对汞的吸附.与褐煤飞灰相比,烟煤飞灰表现出更优的汞吸附性能,与UBC、CaO、MgO及Fe₂O₃在飞灰中的含量存在一定的正相关性.研究显示,烟气循环方式下飞灰汞吸附特性发生明显变化,煤质的合理选择、烟气循环比例、循环气体成分及浓度参数的优化控制可显著改善燃煤锅炉烟气中汞的排放控制效果.      

粉煤灰陶粒对废水中磷酸盐的吸附试验研究

以粉煤灰为主要原料制成粉煤灰陶粒,研究其对废水中磷酸盐的去除情况.同时,考察了影响粉煤灰陶粒吸附磷酸盐的主要因素及平衡吸附量,并对其进行吸附等温模型拟合分析.结果表明,粉煤灰陶粒对磷酸盐的去除率随粉煤灰陶粒投加量的增大而增加,较高的磷酸盐初始浓度可以加快磷酸盐的吸附.在较宽pH(4～10)范围内,均能呈现较好的磷酸盐去...     

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.     

Mercury transportation in soil via using gypsum from flue gas desulfurization unit in coal-fired power plant

The mercury flux in soils was investigated, which were amended by gypsums from flue gas desulphurization (FGD) units of coal- fired power plants. Studies have been carried out in confined greenhouses using FGD gypsum treated soils. Major research focus is uptakes of mercury by plants, and emission of mercury into the atmosphere under varying application rates of FGD gypsum, simulating rainfall irrigations, soils, and plants types. Higher FGD gypsum application rates generally led to higher mercury concentrations in the soils, the increased mercury emissions into the atmosphere, and the increased mercury contents in plants (especially in roots and leaves). Soil properties and plant species can play important roles in mercury transports. Some plants, such as tall fescue, were able to prevent mercury from atmospheric emission and infiltration in the soil. Mercury concentration in the stem of plants was found to be increased and then leveled off upon increasing FGD gypsum application. However, mercury in roots and leaves was generally increased upon increasing FGD gypsum application rates. Some mercury was likely absorbed by leaves of plants from emitted mercury in the atmosphere.     

镧改性粉煤灰合成沸石的同步脱氨除磷研究

以火电厂固废粉煤灰为主要原料,采用改良水热法研制合成了低成本的P型沸石,对其进行了稀土镧改性处理,以强化其脱氮除磷能力.实验研究了改性镧离子浓度、投加量、pH值对同步去除氨氮和磷的影响;运用XRD和SEM分析技术对合成沸石进行了表征.结果表明,在改性镧离子浓度0.5%、pH值为4~8、投加量为10g/L时,改性后的合成沸石对氨氮和磷的去除率分别达到90%,95%以上.改性后的合成沸石对氨氮及磷的吸附动力学数据符合伪二级方程.Langmuir方程能更好地描述氨氮及磷在改性合成沸石上的等温吸附行为,氨氮和磷的Langmuir最大吸附量分别为3.94,1.65mg/g.     

Use of zeolitized coal fly ash in the simultaneous removal of ammonium and phosphate from aqueous solution

Discharge of wastewater containing nitrogen and phosphate can cause eutrophication. Therefore, the development of an efficient material for the immobilization of the nutrients is important. In this study, a low calcium fly ash and high calcium fly ash were converted into zeolite using the hydrothermal method. The removal of ammonium and phosphate that coexist in aqueous solution by the synthesized zeolites were studied. The results showed that zeolitized fly ash could efficiently eliminate ammonium and phosphate at the same time. Saturation of zeolite with Ca²⁺ rather than Na⁺ favored the removal of both ammonium and phosphate because the cation exchange reaction by the NH₄ ⁺ resulted in the release of Ca²⁺ into the solution and precipitation of Ca²⁺ with PO₄ ³⁻ followed. An increase in the temperature elevated the immobilization of phosphate whereas it abated the removal of ammonium. Nearly 60% removal efficiency for ammonium was achieved in the neutral pH range from 5.5 to 10.5, while the increase or decrease in pH out of the neutral range lowered the adsorption. In contrast, the removal of phosphate approached 100% at a pH lower than 5.0 or higher than 9.0, and less phosphate was immobilized at neutral pH. However, there was still a narrow pH range from 9.0 to 10.5 favoring the removal of both ammonium and phosphate. It was concluded that the removal of ammonium was caused by cation exchange; the contribution of NH₃ volatilization to immobilization at alkaline conditions (up to pH level of 11.4) was limited. With respect to phosphate immobilization, the mechanism was mainly the formation of precipitate as Ca₃(PO₄)₂ within the basic pH range or as FePO₄ and AlPO₄ within acidic pH range.     

湿式烟气脱硫系统同时脱汞研究

研究表明,湿法烟气脱硫装置（WFGD）可去除烟气中绝大部分Hg^2＋,但对单质汞的吸收效果不明显,因此研究提高湿法烟气脱硫系统中单质汞的氧化率的方法对控制汞的排放具有重要意义。综述了WFGD及在此系统中各种添加剂的脱汞性能,认为在添加剂中,气态的臭氧、液态的次氯酸和氯化钠稀溶液、黄磷乳浊液、氢硫化钠溶液及EDTA的汞去除效果较好,且不会被SO2大量消耗,可在WFGD系统实现同时脱硫脱汞;而气态的氯气,液态的K2S2O8溶液虽然也有较好的汞去除效果,但因易被SO2或亚硫酸盐溶液消耗,当在WFGD系统中用其氧化单质汞时,需要对脱硫塔进行分层或其他改造,使烟气中的SO2被吸收后再控制汞,提高经济性。     

氯化钙焙烧法提取粉煤灰中的氧化铝

研究了以CaCl2为配料对粉煤灰进行焙烧活化,焙烧熟料水洗后,用硫酸溶液浸取以回收粉煤灰中氧化铝的方法,并考察了焙烧温度和时间、CaCl2加量、硫酸浓度和浸取时间等因素对氧化铝回收率的影响.采用添加CaCl2焙烧的方法,可高效率破坏粉煤灰中的刚玉和莫来石,生成能被无机酸分解的物相,如钙铝黄长石、硅铝酸钙等.结果表明,按CaCl2:粉煤灰=0.8的比例加入CaCl2,于900℃焙烧30min,熟料经水洗涤后,按照每g粉煤灰~30mmol硫酸的量加入1~4mol/L的硫酸溶液,常温浸取30min,氧化铝浸出率可达95%以上.     

粉煤灰对烟气中CO2的吸收特性及矿物相演变机理研究

粉煤灰矿化CO₂是一种极具前景的减少燃煤电厂CO₂排放的技术.然而,目前还缺乏从矿物学角度对碳酸化反应机理的详细认识.本研究选取了3种粉煤灰开展碳酸化实验和矿物学研究,考察碳酸化过程中温度对碳酸化能力及粉煤灰矿物学变化的影响.结果表明,在任一温度下,BJ粉煤灰的碳酸化率均高于YA和LY粉煤灰,这是由于BJ粉煤灰中硬石膏、钙铁石和无定形相等活性矿物相含量较高,LY粉煤灰缺少高活性的钙、镁结晶相.对YA粉煤灰而言,升高温度可显著提高透辉石、尖晶石、黑钙铁矿和方镁石的转化率.在碳酸化YA粉煤灰中同时检测出碳酸钙和碳酸镁/铁,说明除含钙相其他活性元素(Mg和Fe)也参与了碳酸化过程.因此,需要对每个粉煤灰原始材料的矿物学和操作温度进行具体的个案优化,以最大限度地提高固定CO₂能力和碳酸化率.结果还表明温度对不同晶型碳酸钙的形成具有重要作用.方解石在低温(40和80℃)下形成,而文石在高温(180和220℃)下形成.     

烟气单质汞氧化去除过程络合反应机理

湿法氧化去除烟气Hg⁰过程中产物Hg²⁺易发生络合反应,络合产物可能改变氧化体系形成新反应机制,这一现象尚未被认识研究.为获得Hg²⁺络合物生成及其对烟气脱汞影响机理,研究了配体阳离子、配体浓度、反应pH值、反应温度和摩尔比等对Hg²⁺络合反应的影响和氧化去除烟气Hg⁰的络合反应机理.结果表明MgCl₂、KCl、NiCl₂和BaCl₂配体均能与HgCl₂形成络合物,而CuCl₂和SnCl₄则不能生成络合物.络合物生成量随配体浓度的增加先升高然后趋于平衡;络合反应在酸性环境下发生且不受pH值变化影响;碱性环境下络合反应不能进行;反应温度基本不影响络合反应效应;增加配体浓度可提高络合物产量,不同配体络合效应不同,但最大吸光度基本相同,为（4.20±0.03）A.配体对络合反应有响应区间,低于区间下限值时不能形成络合物,高于上限制值时络合物产量不随配体浓度而变化.HgCl₂络合反应累积稳定常数β₄=10^15.07;[HgCl₄]^2-可螯合Hg（aq）和O₂（aq）使其与ClO^-和Hg₂Cl₂反应,形成氧化-络合氧化反应新机理.     

粉煤灰提铝中间产物合成4A分子筛对氨氮的吸附行为研究

采用粉煤灰提铝中间产物合成4A分子筛,利用XRD、SEM、热重分析、化学成分分析、阳离子交换容量对4A分子筛进行表征.考察吸附时间、pH、分子筛投加量、氨氮初始浓度、共存阳离子对其吸附性能的影响,研究其对模拟废水中氨氮的吸附效果,并结合准二级动力学方程、吸附等温线研究吸附性能和机理.结果表明,初始浓度为50 mg·L~(-1)、4A分子筛投加量为5 g·L~(-1)、pH值为6~9、吸附时间为80 min时氨氮去除率可达71.34%;随着氨氮初始浓度升高,其去除率降低,吸附容量增加;共存阳离子Na~+、K~+、Ca~(2+)对NH_4~+有强烈的竞争吸附,Mg~(2+)无明显竞争作用.吸附过程符合准二级动力学方程和Freundlich模型.Langmuir吸附等温线显示最大吸附容量为20 mg·g~(-1).     

粉煤灰对单体直接染料脱色效果的研究

就粉煤灰的投加量、染料的初始浓度、pH值及脱色时间等因素对单体直接染料脱色效果进行了研究，结果表明：在加灰量为0.006g/ml、gH值为2－10、脱色时间为20－30min时，粉煤灰对单体直接染料具有良好的脱色效果。     

粉煤灰对渗沥液氨氮的吸附试验及其动力学研究

为有效提高生活垃圾填埋场渗沥液的C/N,增加渗沥液的可生化性,应用粉煤灰吸附处理实际渗沥液中的氨氮,分别研究投加量,温度,pH值对吸附效果的影响,并在最佳吸附条件下对吸附过程进行动力学分析.结果表明,反应180min时,吸附达到平衡,氨氮去除率达到63.44%,单位吸附量为8.7428mg/g,可有效地调节渗沥液的营养比例,有利于生物处理作用;动力学数据拟合吸附过程符合伪二级动力学方程;动边界模型推算表明,液膜扩散为吸附过程的速度控制步骤;采用Dünwald-Wagner公式,估算有效扩散系数(Dc)为3.058×10-9cm2/s.     

Simultaneous removal of ammonium and phosphate by zeolite synthesized from coal fly ash as influenced by acid treatment

Zeolite synthesized from fly ash （ZFA） without modification is not efficient for the purification of NH4＋ and phosphate at low concentrations that occur in real effluents, despite the high potential removal capacity. To develop an effective technique to enhance the removal efficiency of ammonium and phosphate at low concentrations, ZFA was modified with acid treatment and the simultaneous removal of ammonium and phosphate in a wide range of concentration was investigated. It was seen that when compared with untreated ZFA, only the treatment by 0.01 mol/L of H2SO4 significantly improved the removal efficiency of ammonium at low initial concentrations. The behavior was well explained by the pH effect. Treatment by more concentrated H2SO4 led to the deterioration of the ZFA structure and a decrease in the cation exchange capacity. Treatment by 0.01 mol/L H2SO4 improved the removal efficiency of phosphate by ZFA at all initial P concentrations, while the treatment by concentrated H2SO4 （≥0.9 mol/L） resulted in a limited maximum phosphate immobilization capacity （PIC）. It was concluded that through a previous mild acid treatment （e.g. 0.01 mol/L of H2SO4）, ZFA can be used in the simultaneous removal of NH4＋ and P at low concentrations simulating real effluent.     

Mercury adsorption characteristics of HBr-modified fly ash in an entrained-flow reactor

In this study, the mercury adsorption characteristics of HBr-modified fly ash in an entrained-flow reactor were investigated through thermal decomposition methods. The results show that the mercury adsorption performance of the HBr-modified fly ash was enhanced significantly. The mercury species adsorbed by unmodified fly ash were HgCl₂, HgS and HgO. The mercury adsorbed by HBr-modified fly ash, in the entrained-flow reactor, existed in two forms, HgBr₂ and HgO, and the HBr was the dominant factor promoting oxidation of elemental mercury in the entrained-flow reactor. In the current study, the concentration of HgBr₂ and HgO in ash from the fine ash vessel was 4.6 times greater than for ash from the coarse ash vessel. The fine ash had better mercury adsorption performance than coarse ash, which is most likely due to the higher specific surface area and longer residence time.     

Kinetics and equilibrium of adsorption of dissolved organic matter fractions from secondary effluent by fly ash

Fly ash was used as a low-cost adsorbent for removing dissolved organic matter (DOM) in secondary effluent. Batch experiments were conducted under various adsorbent dosages, pH, contact time, temperatures and DOM fractional characteristics. Under the optimum conditions of fly ash dosage of 15 g/L, temperature of 303 K and contact time of 180 min, a removal of 22.5% of the dissolved organic carbon (DOC), 23.7% of UV-254, 25.9% of the trihalomethanes precursors in secondary effluent was obtained. The adsorption of DOM fractions onto fly ash all followed the pseudo second-order kinetic model, and the hydrophilic fraction adsorption by fly ash also fitted the intraparticle diffusion model quite well. Freundlich and Langmuir models were applicable to the fly ash adsorption and their constants were evaluated. The maximum adsorption capacities of the adsorptions revealed that fly ash was more effective in adsorbing hydrophilic fraction than the acidic fractions. Structure changes of the DOM fractions after fly ash adsorption were also characterized via spectrum analyzing. Those mechanisms presented critical step toward improved efficiencies of fly ash adsorption via further surface-modification.     

生活垃圾焚烧飞灰水洗液中氯离子的去除研究

开展了生活垃圾焚烧飞灰水洗液处理的实验研究,先通过加入氢氧化钙(Ca(OH)_2)、偏铝酸钠(NaAlO_2)初步去除水洗液中的Cl~-,再利用反渗透膜分离技术,探究了浓淡比、操作压力、pH、Cl~-浓度对Cl~-去除效果的影响.结果表明,化学沉淀法初步处理能去除水洗液中约50%的Cl~-,膜分离对经初步处理水洗液中Cl~-的去除率高达93.5%.经过两级处理后,飞灰水洗液中Cl~-的去除率高达96.74%,Cl~-的含量满足排放标准的要求.