垃圾焚烧飞灰理化特性研究

应用能谱分析、灰熔点炉、XRD、压汞仪等仪器手段对国内外8种垃圾焚烧飞灰的成分、熔点、晶相结构、颗粒特性等物理化学性质进行了系统研究。研究表明,飞灰成分因为受原料、炉型、取样位置等因素影响而差异很大。由于飞灰的成分差异导致垃圾焚烧飞灰比煤灰更易于熔融,对熔融处理有利,这主要归因于飞灰中SiO2含量以及SiO2/Al2O3差异,熔点与SiO2含量存在正比关系；添加CaO实现助熔是有条件的,不同飞灰由于焚烧条件和飞灰成分不同导致晶相组成有一定差异；飞灰内部孔径主要分布于0.3 μm～1.5 μm范围内,飞灰的比表面积为20.5 m2/g。     

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。     

大型电站煤粉炉自身固硫灰渣的微观晶相分析

研究了电站1 025 t/h煤粉炉燃用Ca/S(摩尔比)=2.02的神木煤自身固硫灰渣的晶相组成，XRD分析表明,入炉煤中无定形的非晶相质量分数高达91.2%，CaCO3晶相质量分数为2.1%。满负荷下飞灰中因高温熔融形成的玻璃态非晶相质量分数高达70.5%，煤灰自身固硫产物CaSO4质量分数为3.4%，CaCO3和CaO质量分数为6.9%，使其仍具有进一步固硫的能力。满负荷下炉底渣中钠长石质量分数高达59.2%，非晶相质量分数为25.7%，未发现CaSO4、CaCO3或CaO晶相。当锅炉负荷降低时，飞灰中非晶相质量分数相应降低，炉底渣中非晶相质量分数升高。     

垃圾焚烧飞灰基本特性研究

以三个正在运行的垃圾发电厂的除尘器飞灰为研究对象，实验测出它们的化学组成、热灼减率、灰熔点等物化特性和浸出毒性、腐蚀性等有害特性，对三种灰样的特性进行了对比、分析。结果表明，飞灰的物化特性主要受飞灰中MgO、CaO、SiO2和CaCl2等几种主要成分质量分数的影响。MgO和Al2O3质量分数较高而CaCl2质量分数较低的飞灰其灰熔点相对较高；CaO和CaCl2质量分数较高的飞灰其水分和热灼减率也相对较高；SiO2质量分数较高的飞灰其重金属的浸出率相对较低；CaO和Al2O3等碱性氧化物质量分数较高的飞灰其浸出液的pH值相对较高。     

弱还原气氛下水稻秸秆对晋城无烟煤的助熔机理

以高灰熔点的晋城无烟煤和水稻秸秆为研究对象,通过CaO-Al_2O_3-SiO_2三元相图、X射线衍射分析(XRD)和扫描电镜耦合X射线能谱分析(SEM-EDX)研究了弱还原气氛下水稻秸秆对晋城无烟煤的助熔机理。随着水稻秸秆添加比例的增加,灰熔融特征温度呈下降趋势,灰中碱性氧化物CaO、Na_2O和K_2O含量增多,结渣指数Rb/a值在0.20-0.69;当水稻秸秆添加量为20%(质量分数)时,流动温度(FT)降低至1 369℃,可满足气化炉液态排渣的要求;水稻秸秆的添加降低了灰中液相出现的温度,增加了液相物质出现的比例和几率,使灰更易发生熔融;混合灰中所形成的钠长石等低熔点矿物质以及钙长石、石英和莫来石所形成的低温共熔物导致灰熔点降低。     

TiO2选择性富集的物理化学行为

创造合适的物理化学条件,可使富钛还原性熔渣体系(CaO SiO2 TiOx MgO Al2O3)中的钛组分在化学位梯度的驱使下,选择性地富集于钙钛矿相中,从而便于分离与提取.促进钛组分选择性富集的物理化学成因可归结为:将熔渣在高温下氧化,可使渣中低价钛转变为四价钛而增加TiO2活度;此外,提高熔渣碱度可增加渣中CaO活度,这些均增强了钙钛矿析出反应 TiO2＋CaO = CaTiO3(s)的热力学趋势,促使渣中的TiO2尽可能与CaO结合生成钙钛矿并随之析出.实验结果表明,将碱度调整在1.3的熔渣彻底氧化,可使其中80％左右的TiO2富集于钙钛矿相中,其富集程度相对于调质与氧化前增加约一倍.     

钙铁助剂对粉煤灰熔融性和结晶行为的影响机理

利用粉煤灰制备高强度无机纤维是实现其高值化利用的重要路径,由于粉煤灰硅铝含量较高,可通过添加钙铁助剂降低均质化过程中原料熔融温度,避免降温拉丝过程中结晶行为。本工作研究了空气气氛下不同含量及比例钙铁助剂对煤灰熔融性及结晶行为的影响机理。结果表明,空气气氛下氧化钙(CaO)与氧化铁(Fe₂O₃)不存在协同助熔效果,CaO的助熔效果优于Fe₂O₃。高温下Fe₂O₃未与硅铝组分生成低熔点矿物,而添加CaO有利于将难熔的莫来石转化为钙长石,使得粉煤灰熔点大幅度降低;然而,当CaO添加量超过30%时,生成了大量的钙黄长石,使得粉煤灰熔点迅速升高。降温过程中,铁元素以赤铁矿形式析出,析晶温度相对较低;而钙元素以钙长石形式析出,析晶温度相对较高,不利于无机纤维制备过程中纺丝操作。当CaO含量为32.46%时,粉煤灰熔点最低,且降温过程中无晶体析出,因此,在粉煤灰基无机纤维制备过程中应选择钙基助剂调控熔融性和结晶行为。     

熔融制样X射线荧光光谱法测定水泥及水泥熟料中成分

采用波长色散X射线荧光光谱仪测定水泥和水泥熟料中的Na2O、MgO、A12O3、SiO2、P2Os、SO3、K2O、CaO、TiO2、MnO、Fe2O3等成分。采用熔融玻璃片方法制样，采用Li2B4O7为熔剂，较混合熔剂的制样效果好；硫在1050℃熔融制样过程中的挥发较慢，对测定结果无明显影响。方法测定准确度、精密度较好，所得结果与湿法化学分析结果相符。     

Mg2+和Na+对高熔点煤灰熔融性的影响

以山西阳泉固庄高熔点煤灰为研究对象,通过向煤灰中添加不同量的MgO与Na₂CO₃,研究了Mg²⁺与Na⁺在高温下对煤灰熔融性的影响。研究结果表明,煤灰熔融温度随氧化镁的添加(5%~25%)单调下降;而随氧化钠添加(5%~25%)出现先降后升现象,在氧化钠添加量为15% 时,灰熔点达到最低。XRD分析表明,阳泉固庄煤灰熔融温度高(大于1 750℃)的原因是高温条件下耐熔矿物莫来石、方英石的存在。添加外加剂后,高温时外加剂与硅酸盐矿物反应,生成了更多的低共熔矿物霞石、堇青石等。同时,Mg²⁺和Na⁺的加入会使得非桥氧数量增多,高温煤灰低聚物增多,降低了煤灰的熔融温度。通过三元相图以及SEM分析,高温条件下煤灰中部分元素的富集以及团聚现象是导致Mg²⁺和Na⁺对煤灰熔融温度影响不同的原因。     

碱熔-电感耦合等离子体原子发射光谱(ICP-AES)-内标法测定水泥标准物质中的氧化物含量

电感耦合等离子体原子发射光谱(ICP-AES)法与内标法的结合扩展了ICP-AES的分析范围。采用氢氧化钠熔融样品，ICP-AES-内标法测定各类水泥标准物质样品中SiO2、Al2O3、TFe2O3、MgO、TiO2等氧化物的含量。实验结果表明，标准物质测定值与标准值吻合，6次平行样品测定相对标准偏差小于1.4%。方法一次熔样，纵向测定主常量元素，操作简单，快速，准确，为水泥标准物质的研制提供了另一种定值方式。     

Characteristics of major dioxin/furan congeners in melted slag of ash from municipal solid waste incinerators

Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in slag of fly ash from three municipal solid waste (MSW) incinerators were analyzed to observe any changes in characteristics and distribution of their congeners by melting process. Actual concentration and Toxic Equivalent (TEQ) concentration profiles of 17 major congeners of PCDDs/PCDFs for gas, fly ash and melted slag were compared. The distributions of PCDDs/PCDFs in different streams macroscopically showed similarities with the generally known profiles for emission gas from a municipal waste incinerator. The total concentrations of PCDDs/PCDFs in off-gas and fly ash have been known to be a function of incineration conditions and of air pollution control device utilization; however, their normalized distributions were independent of such conditions. The concentrations of PCDDs/PCDFs in the melted slag of fly ash were not related to the concentrations of PCDDs/PCDFs congeners in fly ash but were rather a function of the melting furnace type and operation. The total amount of PCDDs/PCDFs in the melted slag of fly ash contained almost 150–27,000 times less dioxin than that in fly ash, however, the TEQ of dioxin in the slag was reduced by 435–43,500 times, which could enable them to be utilized as recycled construction materials. In normalized TEQ concentration profiles of 17 congeners of PCDDs/PCDFs, the ratio of PCDFs to PCDDs changed from 1.32 to 2.19 by melting, which showed relatively higher portion of furans left in melted slag than those in fly ash. By comparing reduction ratios of different congeners, PCDDs (dioxins) were relatively easier to destruct than PCDFs (furans) during melting process. The most difficult congener to destruct could be octa-chlorinated dibenzofuran (OCDF) among major congeners. For slag cooling methods, dioxin concentration in TEQ of slow cooled slag by air was four times higher than that of fast cooled slag by water. Thus cooling by water is more appropriate with the added beneficial effect of producing granules/particles, which can be utilized as roadbed materials.     

灰中焦对煤灰熔融特性的影响

采用连有电脑－摄像头的煤灰熔融特性测定装置，在Ar气氛下研究了灰中焦对煤灰熔融特性的影响。结果表明，灰中焦对灰熔融特征温度和灰熔融动态特征具有显著影响，影响程度与煤种以及煤焦的质量分数有关。掺焦的灰熔融温度高于不掺焦的熔融温度；掺焦量增加，其灰熔融温度升高。当掺焦量提高至20%时，在接近或高于煤灰熔融温度时由于焦与焦之间通过熔融煤灰的黏结作用形成了不熔骨架，使灰锥高度不再随温度的提高而发生变化，这也是灰锥很难出现或者根本不出现软化温度和流动温度的原因。     

燃烧福建无烟煤的循环流化床锅炉飞灰及其未燃炭分析

以三个燃烧福建无烟煤的商业CFB锅炉电厂飞灰为研究对象，分析飞灰的粒径和含碳量分布；观察并区分了飞灰中煤炭、烟怠、半焦和灰渣等颗粒的表面形貌；测定了飞灰炭的反应活性并与入炉煤作比较；并研究了飞灰炭的来源。结果表明，采用单级分离装置的CFB锅炉，粒径在0.0385mm～0.0500mm的飞灰质量最多，未燃炭份额也最高；而采用双级分离装置的CFB锅炉，飞灰质量分布和飞灰炭份额的峰值则出现在粒径为0.0500mm~0.0750mm处。飞灰主要由三种形貌的颗粒组成，颗粒状的未燃炭、絮团状的灰渣、和介于两者之间的半焦。与入炉煤相比，飞灰炭的反应活性较高，主要来源于入炉煤中的细粉和燃烧早期因破碎和磨蚀而产生的、来不及在炉膛中燃尽的细小含炭颗粒。入炉煤中易破碎、反应性较高的亮煤是构成电厂CFB锅炉飞灰炭的主要成分。     

Comparative investigation of reactivity of different kinds of fly ash in alkaline media

Comparison of the influence of temperature and different alkali activators on the reactivity of two types of fly ash (conventional, fluidized) was presented. The main emphasis was put on fluidized fly ash as potential component of binding mixtures containing low amount of cement. Conventional fly ash was used as a reference. It was found that for these materials the key differences affecting products of activation are: availability of calcium and sulfate ions as well as structure of fly ash grains influencing dissolution of aluminate and silicate species. Fluidized fly ash, contrary to conventional fly ash, undergoes reaction in 0.1 M solutions of hydroxides forming mainly ettringite. In the case of 4 M hydroxides, both fly ashes undergo hydration processes. Conventional fly ash formed mainly amorphous aluminosilicate gel, while fluidized fly ash may create zeolitic products especially in the case of elevated temperature of early hydration. Sulfate and alkali ions can be incorporated into aluminosilicate structure of new formed products; however, this process depends strictly on the type of used hydroxide and its concentration. The presence of Ca(OH)₂, carbonates and alkali sulfates was also registered in the case of hydrated fluidized fly ash.

     

垃圾焚烧炉飞灰熔融特性及重金属的分布

对垃圾焚烧炉飞灰进行了差热分析及熔融实验，探讨了不同熔融温度对试样的灼烧减量及重金属分布特性的影响。结果表明，飞灰试样在1132℃时熔融，在1252℃～1290℃发生二次熔融。灼烧减量在1200℃达到最低值27.5％； Cr、Ni、Cu在熔融体中的固溶率随着沸点的升高而依次升高。重金属Pb、Cd、As、Hg挥发率均超过95％，挥发性依次为Pb>Cd>As>Hg；飞灰中Zn的氧化物熔融后转化为Zn2SiO4、ZnSiO3和ZnAl2O4等不易挥发的化合物，且Zn在1200℃时挥发率最低仅有66.7％。     

山西“两高”煤灰分对石灰石助熔机制影响的研究

以山西"两高"煤为研究对象,考察了洗选改变灰分对添加助熔剂Ca CO3的影响。研究发现,随着洗煤灰分的降低,煤灰中二氧化硅含量及硅铝比(Si/Al)降低,煤灰流动温度降低至液态排渣气流床气化所需温度时,Ca CO3的添加比例与洗煤高温下生成的矿物质种类及其含量相关,经过洗选降低灰分后的FH与SH洗煤,通过添加一定比例的助熔剂Ca CO3,高温下煤灰渣类型由结晶渣变为玻璃体渣,排渣温度范围宽,能够很好地满足气流床气化液态排渣的要求,洗选与添加Ca CO3助熔剂配合使用的方式,可以有效调控山西"两高"煤灰流动性质。     

Kinetics of thermal decomposition of PVC/fly ash composites

In this study, the kinetics and mechanisms of thermal degradation of Poly Vinyl Chloride (PVC) composites reinforced with class-F fly ash are studied experimentally and numerically using Flynn–Wall model. The addition of fly ash to the polymer matrix results in a decrease in the primary degradation temperature and an increase in the secondary degradation temperature. The metal oxides in the fly ash act as acid absorbers, which results in the destabilization of PVC during its dehydrochlorination process. However, they also react with the chlorine free radicals, which prevents the formation of HCl during degradation. In addition, it is observed that calcium and iron oxides, present in fly ash, are more reactive to the chlorine radicals rather than the silicon and aluminum oxides. The effect of fly ash chemical composition on the degradation of PVC composites was studied by comparing the thermal properties of composites containing two different classes of fly ashes, class-F and class-C, at similar levels. Thermal stability of the composites is found to be dependent on the chemical composition of fly ash. Higher dehydrochlorination rate is observed in the case of composites filled with class-F fly ash than those reinforced with class-C fly ash.     

煤催化气化条件下不同煤种煤灰烧结行为研究

选取9类典型煤种,利用压差法测定烧结温度的实验装置,结合灰渣的XRD分析结果,考察了添加K基碱金属催化剂、不同煤种灰成分对烧结温度的影响。结果表明,碳酸钾催化剂的添加,明显降低高铁钙含量的WJT煤的灰熔点及烧结温度,碱金属K化合物极易同煤中Fe、Ca的矿物质反应生成低温共融物进而加剧煤灰的熔融结渣。不同煤种烧结温度的差异与煤灰中硅、铝、铁、钙含量密切相关。铝、硅含量高的煤灰烧结温度较高,而铁、钙含量高的煤灰烧结温度相对较低。碱金属K催化剂的添加加剧了煤灰的烧结结渣,而钙、铁的存在会加速硅铝酸盐间的反应生成低温共融物进而加速灰熔融。各煤种烧结温度的变化与其灰成分在CaO-SiO₂-Al₂O₃、FeO-SiO₂-Al₂O₃三元相图上的位置相吻合。     

造纸污泥添加剂对麦秆灰烧结熔融特性的影响

利用灰熔点测试仪、XRD及XRF等仪器,对比研究了造纸污泥(脱墨污泥、造纸废水污泥)、城市废水污泥作为添加剂对麦秆灰熔融特性的影响,考察了烧结和熔融过程中的组分变化,分析了污泥添加剂对麦秆灰的作用机理;进一步将污泥添加剂与常规添加剂进行灰熔融特性对比研究。研究发现,添加比例控制为3%-10%,造纸污泥(脱墨污泥、造纸废水污泥)软化温度提升效果均优于城市废水污泥;在添加比例控制为5%时,造纸废水污泥对麦秆灰软化温度提升效果最好;增大添加比例过程中,造纸废水污泥Al_2O_3修饰骨架作用明显,但灰中长石类物质逐渐增多使得软化温度提升效果下降;在不同温度下,脱墨污泥主要是通过形成硅铝榴石使得灰熔点提升,造纸废水污泥则主要是通过生成高熔点物质CaSiO_3抑制低熔点硅酸盐形成,城市废水污泥升温中存在明显SiO_2晶态转变过程;使用污泥添加剂作为抗结渣添加剂具有良好应用前景。