Dehalogenation potential of municipal waste incineration fly ash

BACKGROUND, AIMS AND SCOPE: It is well known that the fly ash from filters of municipal waste incinerators (MWI-FA) shows dehalogenation properties after heating it to 240-450 degrees C. However, this property is not general, and fly ash samples do not possess dehalogenation ability at all in many cases. Fly ash has a very variable composition, and the state of the fly ash matter therefore plays the decisive role. In the present paper, the function of important components responsible for the dehalogenation activity of MWI-FA is analysed and compared with the model fly ash. METHODS: With the aim of accounting for the dehalogenation activity of MWI-FA, the following studies of hexachlorobenzene (HCB) dechlorination were performed: The role of copper in dehalogenation experiments was evaluated for five types of metallic copper. The gasification of carbon in MWI-FA was studied in the 250-350 degrees C temperature range. Five different kinds of carbon were used, combined with conventional Cu(o) and activated nanosize copper powder. The dechlorination experiments were also carried out with Cu(II) compounds such as CuO, Cu(OH)2, CuCl2 and CuSO4. The results were discussed from the standpoint of thermodynamics of potential reactions. Based on these results, the model of fly ash was proposed, containing silica gel, metallic copper and carbon. The dechlorination ability of MWI-FA and the model fly ash are compared under oxygen-deficient atmosphere. CONCLUSIONS: The results show that, under given experimental conditions, copper acts in the dechlorination as a stoichiometric agent rather than as a catalyst. The increased surface activity of copper enhances its dechlorination activity. It was found further that the presence of copper leads to a decrease in the temperature of carbon gasification. The cyclic valence change from Cu(o) to Cu+ or Cu2+ is a prerequisite for the dehalogenation to take place. RECOMMENDATION AND OUTLOOK: Thermodynamic analysis of the dechlorination effect, as well as the comparison of dechlorination pathways on MWI-FA and model fly ash, can provide a deeper understanding of the studied reaction.     

Dechlorination ability of municipal waste incineration fly ash for polychlorinated phenols

Pathways of pentachlorophenol dechlorination have been investigated on municipal waste incineration fly ash at 200 degrees C under nitrogen atmosphere. Thermodynamic calculations have been carried out for these dechlorination conditions using the method of total Gibbs energy minimization for the whole system consisting of gaseous components, i.e., chlorinated phenols, phenol, hydrogen chloride and the Cu3Cl3 trimer and of solid Cu2O and CuCl2 components. The effects of water, temperature and of the amounts of the reaction components on the thermodynamic equilibrium have been discussed and the experimental results compared with the calculated thermodynamic data.     

Effects of selected metal oxides on the dechlorination and destruction of PCDD and PCDF

OCDD and OCDF spiked silica/graphite based model fly ash containing various copper compounds and metal oxides were thermally treated under oxygen deficient conditions. All copper compounds tested showed a considerable dechlorination/hydrogenation reaction at 260 °C. After 30 min at 340 °C, less than 1% of the spiked OCDD and OCDF was recovered as T₄CDD/F to OCDD/F. Other compounds tested demonstrated a lower rate of dechlorination compared to the copper compounds. However, all other metal oxides showed a small dechlorination effect at 260 °C, which was considerably increased at 340 °C.

The model fly ash containing the different copper compounds or metal oxides showed comparable PCDD and PCDF isomer patterns after thermal treatment. However, small differences were observed among the different tested compounds. The PCDD and PCDF isomer patterns on the model fly ashes were similar to patterns found during dechlorination experiments on fly ashes from waste incineration processes.

Model fly ash containing Ca(OH)₂ exhibited the highest destruction potential, but a low dechlorination potential. In contrast, model fly ash containing any of the remaining compounds tested, was found to predominantly dechlorinate the spiked OCDD and OCDF.     

Dechlorination and destruction of PCDD,PCDF and PCB on selected fly ash from municipal waste incineration

The potential of fly ash to dechlorinate and destroy PCDD, PCDF and PCB was tested under oxygen deficient conditions in the laboratory. Specifically, two types of fly ash were compared, originating either from a fluidized bed incinerator using Ca(OH)₂ spray (FA1), or a stoker incinerator without Ca(OH)₂ impact (FA2).

Results from the present study indicate that on FA2 type fly ash, the degradation processes of OCDD, OCDF and D₁₀CB occurred primarily via dechlorination/hydrogenation up to temperature settings of 340 °C. In contrast, FA1 type fly ash was found to effect both dechlorination and destruction of these compounds already at temperature settings of 260 °C.

The dechlorination velocity of PCDD and PCDF did not differ significantly. However, the first dechlorination step of OCDF in the 1,9-position occurred faster compared to the first dechlorination step of OCDD.

The isomer pattern resulting from the dechlorination processes was quite similar on both FA1 and FA2, indicating that differences in alkalinity or elemental composition of the two types of fly ashes do not have a significant influence on the position of dechlorination. PCDD and PCDF dechlorination of the 2,3,7,8-positions was not favoured over dechlorination of the 1,4,6,9-positions on either type of fly ash. In contrast, dechlorination of PCB occurred predominantly on the toxicological relevant 3- and 4-positions.

The dechlorination/destruction processes were completed on both types of fly ash at 380 °C within one hour, which correlates well with results obtained from actual plant operation practices.     

改性粉煤灰处理低浓度含磷废水的研究

以酸改性粉煤灰为吸附剂,处理低质量浓度(1 mg/L左右)磷酸盐溶液,探讨了改性剂的种类、改性剂用量、吸附剂用量、反应时间、pH以及温度对除磷效果的影响.结果表明:(1)经过酸改性后粉煤灰的磷去除率显著提高,而且硫酸改性粉煤灰的除磷效果更好,磷去除率最高可达97.68％.(2)最佳条件:选择硫酸用量为5 mL/g进行改性,硫酸改性粉煤灰投加量为2.0g,反应时间为60 min,pH为7.2～10.8,温度为25℃(即室温).(3)改性粉煤灰对磷的吸附更符合Freundlich吸附等温模型,既有物理吸附,也有化学吸附,并以Ca、Mg氧化物与磷形成磷的沉淀物为主.     

粉煤灰对水溶液中磷的吸附性能及机理

以粉煤灰为吸附剂去除溶液中的磷,考察了其吸附除P动力学特征、热力学特征以及溶液初始pH和粉煤灰投加量对吸附除P效果的影响,并对其吸附除P机理做了初步探讨。结果表明,在给定实验条件下,粉煤灰对P具有较好的去除效果,随着初始P浓度从10 mg/L升高到80 mg/L,平衡吸附量为0.46～2.44 mg P/g粉煤灰,吸附效率从92.2%降低至61.1%;对不同浓度的含P溶液,粉煤灰最适用量为0.6～1.5 g粉煤灰/mg P;相同反应条件下,当温度由25℃升高到45℃时,P初始吸附速率提高了3倍;粉煤灰对P的吸附过程能够较好地拟合Langmuir、Freundlich及D-R吸附等温模型,相关系数均在0.98以上。通过对吸附饱和的粉煤灰进行解析实验发现,初始P浓度较低(<50 mg/L)时,以化学吸附为主,而在初始P浓度较高(>80 mg/L)时,则以物理吸附为主。     

火力发电厂飞灰对抗生素磺胺的吸附性能

研究了吸附时间、飞灰用量、初始溶液pH和振荡频率等因素对飞灰吸附去除水溶液中磺胺的影响,并对其吸附机理进行了初步探讨。研究结果表明,飞灰用量增大有利于提高其对磺胺的吸附去除率。在25℃、振荡频率150 r/min、飞灰用量50 g/L、磺胺浓度4 mg/L条件下吸附10 min,磺胺的吸附去除率可达到92.8%。电厂飞灰对磺胺的吸附符合二级动力学模型,属于单分子层吸附。     

壳聚糖联合碱改性粉煤灰对重金属离子的吸附特性

采用浸渍法将壳聚糖负载在经NaOH改性的粉煤灰上,制备了联合改性的粉煤灰。随粉煤灰上壳聚糖负载量的增加,粉煤灰对Pb²⁺和Cd²⁺的吸附率均提高。当负载壳聚糖的质量分数为8%,吸附温度为30℃,吸附时间为120 min时,粉煤灰对Pb²⁺的吸附率最高（为98.9%）,对Cd²⁺的吸附率也最高（为91.5%）。其吸附行为符合Freundlich等温吸附模型,但表现为2个线性区。粉煤灰负载壳聚糖的改性机理是粉煤灰与带正电荷的壳聚糖的化学键合作用。     

粉煤灰及改性粉煤灰对邻甲酚吸附性能的研究

研究了水溶液中粉煤灰(FA)和浸渍粉煤灰(IFA)吸附有害的邻甲酚,试验了颗粒大小、浸渍条件、pH值和温度等因素对吸附量的影响.结果表明,在稀溶液中进行吸附时,提高温度、减小粒径和pH值,可增加粉煤灰对邻甲酚的吸附量;用Al3+离子浸渍的粉煤灰具有较大的吸附量;吸附过程机理主要是多孔物质和静电作用的共同结果所致.     

铁屑粉煤灰组合处理含磷废水

实验研究了铁屑粉煤灰组合处理含磷废水的除磷效果.通过单因素实验,考查了铁屑粉煤灰质量比、反应时间、pH值和投加量对除磷效果的影响.实验结果表明,该法除磷的最优条件为铁屑和粉煤灰的质量比为2∶1,反应时间为20 min,pH值为6,投加量为20 g/L.在最优实验条件下磷的去除率达到了97.5％.对比了该法和粉煤灰吸附法与传统铁屑法的除磷效果.与单一粉煤灰吸附法和传统铁屑法除磷的结果相比较,铁屑粉煤灰组合除磷的方法具有明显优势.     

以粉煤灰和电石渣为催化剂的聚丙烯裂解模型研究

对粉煤灰和电石渣为催化剂的聚丙烯裂解进行模型研究.通过模型计算了裂解反应的表观活化能、频率因子、反应级数等.模型计算表明随着反应温度的升高反应速率增加,达到相同转化率所需反应时间减少.当剂塑比从0增加到30%时,聚丙烯裂解的活化能呈现降低的趋势,特别当剂塑比为30%时,其活化能降低约50%.说明粉煤灰和电石渣对聚丙烯裂解具有一定的催化效果.     

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。     

垃圾焚烧飞灰熔融过程中重金属的固化机理以及熔渣浸出特性的研究

研究了中国垃圾焚烧飞灰中主要重金属在熔融过程的固定化机理,定义了固定率这个参数来表征此过程。采用了中国和美国的危险废物浸出毒性鉴别方法来判别飞灰及其熔融渣的浸出毒性。研究结果表明,固定率能够较好地表征重金属在熔融过程不同温度阶段的固定情况;按照中国和美国废物浸出毒性鉴别标准,飞灰熔融处理后的熔渣不属于危险废物,具备资源化利用的条件。     

粉煤灰和电石渣对聚丙烯塑料裂解的影响研究

研究了粉煤灰和电石渣对聚丙烯塑料裂解的影响,讨论了加入量对裂解速度和裂解产物的影响.结果表明:粉煤灰和电石渣都使裂解产物中的轻质部分(汽油和裂解气)增加、重油降低;粉煤灰比电石渣更能加快反应的进行,而且加入量越多,反应越快,需时越短;粉煤灰比电石渣对聚丙烯塑料的裂解具有明显的催化促进效果.     

超临界水无害化共处理PVC和医疗垃圾焚烧飞灰的可行性探讨

采用超临界水氧化降解PVC同时无害化处理医疗垃圾焚烧飞灰,利用PVC脱氯形成的中间产物盐酸提取医疗垃圾焚烧飞灰中的重金属,达到飞灰无害化的目的。结果显示,超临界水可以将飞灰颗粒打碎,从而提高盐酸提取重金属的速率和效果,但是在超临界水中还存在重金属的固定过程,过长的反应时间和过高的反应温度都会降低重金属的提取效率。在提取过程中,Cu和Zn优先于Pb被盐酸浸出,而Pb被浸出后很容易被超临界水进一步固定。综合考虑重金属在超临界水中的变化特性,总结出超临界水处理飞灰和PVC的最佳条件为:PVC与飞灰质量比0.5:1,温度400℃,提取时间90 min。处理后的飞灰再次经过水洗后,其重金属浸出浓度低于USEPA规定的限制值。本研究为飞灰的无害化处理提供一条新的思路。     

碱熔预处理对粉煤灰溶解规律的影响及其动力学

在用粉煤灰合成沸石分子筛的过程中,粉煤灰在碱液中的溶解影响到合成反应的速率以及合成分子筛的性能。采用碱熔的方法处理粉煤灰,研究了粉煤灰在碱液中的溶解机理以及碱熔预处理对粉煤灰溶解规律的影响,并采用Noyes-Whitney方程分析其溶解动力学。结果表明,经过碱熔预处理的粉煤灰有36．11％的SiO2和16．33％的Al2O3转化为水溶性成分,剩余的非水溶性部分在碱液中的溶解速率也有大幅提高,硅铝离子达到平衡浓度的时间缩短,铝离子的平衡浓度有较大提升。Noyes-Whitney方程对粉煤灰在碱液中的溶解规律适用,相关系数都达到0．979以上。     

粉煤灰砖块对磷酸盐的吸附特性

以建筑废料粉煤灰砖块为吸附剂材料,通过静态吸附实验研究其对磷酸盐的吸附特征,以及磷酸盐初始浓度、吸附剂投加量、pH等因素对吸附反应的影响。Langmuir、Freundlich和Temkin等温模型的分析发现,Langmuir等温式方程最适合描述吸附过程,对磷酸盐的理论饱和吸附容量为44.62 mg/g。利用伪一级动力学模型、伪二级动力学模型和颗粒内扩散模型考察了吸附过程特征,其中伪二级动力学模型为最适于描述粉煤灰砖块对磷酸盐的吸附过程的动力学模型。通过颗粒内扩散模型、Bangham方程及Boyd模型对吸附动力学机理进行的探讨表明,颗粒内扩散速率不是粉煤灰砖块吸附磷酸盐反应的惟一速率控制步,膜扩散速率和颗粒内扩散速率共同影响着吸附反应速率。磷酸盐浓度较低时主要是膜扩散限制吸附反应速率,而磷酸盐浓度较高时则颗粒内扩散成为速率控制步。研究证明,粉煤灰砖块粉末作为湿地基质具有对磷酸盐很强的吸附能力,在减少了固体废弃物的数量的同时又可以实现水污染控制的目的。     

添加粉煤灰对污泥比阻影响的研究

污泥脱水是污泥处理中重要的一环.本研究采用电厂废弃物粉煤灰对未脱水污泥改性,经过改性的污泥比阻降低,改善污泥脱水性能,并对产生这一现象的机制进行了探讨.     

添加粉煤灰对污泥比阻影响的研究

污泥脱水是污泥处理中重要的一环。本研究采用电厂废弃物粉煤灰对未脱水污泥改性，经过改性的污泥比阻降低，改善污泥脱水性能，并对产生这一现象的机制进行了探讨。     

粉煤灰技术在污水处理中的应用研究及存在问题讨论

对国内外污水处理中应用粉煤灰技术的现状进行了文献综述 ,并从环境保护与市场机制这个视角对粉煤灰在污水处理中的应用及存在问题进行了分析讨论。粉煤灰具有一定的吸附性能以及细微粒径特征 ,在污水处理中可以获得较好效果。但是同时会产生数倍的污泥增量 ,有些污泥甚至是有毒的 ,会产生二次污染。通过对历史事件的回顾认为以粉煤灰为原料制备混凝剂等 ,尽管在技术上可行 ,但是从市场经济角度看是不可取的