湿法预处理对垃圾焚烧飞灰中重金属的形态及风险影响研究

以某典型城市生活垃圾焚烧飞灰为研究对象,采用X射线荧光光谱仪（XRF）、X射线衍射仪（XRD）和电感耦合等离子体光谱仪（ICP）测定了焚烧飞灰的主要成分、矿物学组成和重金属含量,探讨了湿法预处理工艺对飞灰的化学组成、矿物学形态、化学形态及风险水平的影响.结果表明,飞灰的主要化学组成为O、Ca、Cl、Na、K等,占飞灰总质量的93.54％,其次含有0.04％ ～0.68％的Zn、Pb、Cu、Cr等微量重金属元素;经过湿法预处理,飞灰中可溶性氯盐具有较好的去除效果,且几乎所有重金属元素的不稳定形态（弱酸提取态和可还原态）比例都有一定程度的减少,有效降低了重金属的毒性、生物有效性及环境风险水平.本研究有助于降低焚烧飞灰的环境风险和探寻其资源化的有效途径.     

氯化铜催化二噁英生成实验及指纹特性分析

氯化铜被认为是对二■英(PCDD/F)生成促进作用最强的金属催化剂,温度和氧气含量是影响其催化二■英生成的关键因素.本文选取250～550℃间8个不同温度点及0～20%间4种不同氧气含量,系统性地研究了温度和氧气含量对含氯化铜模拟飞灰(MFA)生成二■英的影响,并通过分析指纹特性探讨二■英的生成路径和机理.结果发现,290～350℃之间二■英生成量较高,且在290℃时二■英总量达到最大值;氧气含量为10%时二■英生成量达到最高.研究二■英同分异构体分布可从分子层面为研究其生成路径和机理提供重要信息,因此,本文分析了四至八氯代PCDD/F的全部异构体的分布.结果表明,在本文所选取的温度和氧含量范围内,温度对二■英生成路径的影响高于氧气含量.最后,重点讨论了2,3,7,8位氯取代的17种有毒异构体的分布随温度和氧气的变化情况及生成路径.利用主成分分析法(PCA)证实了氯化铜催化二■英从头合成过程中存在经由氯酚路径生成的异构体,并讨论了不同工况下氯酚路径对二■英生成的影响.     

垃圾焚烧飞灰中Pb及特征药剂稳定化处理

筛选几种重金属药剂用于稳定垃圾焚烧飞灰,以重金属Pb为处理目标,通过单一或复配形式研究药剂的稳定效果并采用红外光谱（FT-IR）和X射线衍射（XRD）分析重金属稳定机理.结果表明,有机药剂稳定后Pb的螯合率高于无机药剂,投加质量分数为2%二乙基DTC能使Pb的浸出满足危险废物填埋污染控制标准（GB 18598-2019）要求,然而5%的硫化钠和磷酸二氢钠稳定后Pb的浸出浓度仍不达标;药剂处理后,Pb的部分不稳定态被转化为稳定态,且相比于无机药剂,有机药剂稳定后Pb的残渣态占比更高,抗酸碱能力更强;无机药剂处理后Pb的浸出性与养护时间成负相关,而有机药剂则由于特征官能团的氧化等因素而成正相关.成本核算结果表明,0.9%二乙基DTC和3%磷酸二氢钠复合药剂稳定飞灰在满足GB 18598-2019要求的基础上,成本相比于单一二乙基DTC处理降低26.72%.复合药剂处理后,飞灰中出现了N、S、P的特征吸收峰,重金属主要以螯合、沉淀作用稳定,同时整个体系的矿物组成并未发生改变,但结晶相的吸收峰强度明显减弱.     

调理剂对磷镉富集土壤中两种元素交互作用的影响

以磷镉富集的农业土壤（总Cd：0.94mg·kg^-1和全P：0.86g·kg^-1）为研究对象,按照湖北地区中稻生育期及至下茬作物播种期的时长进行室内培养试验,探究生物质炭（BC）、钙镁磷肥（CMP）和粉煤灰（FA）影响下土壤磷与镉的生物有效性、二者形态变化及其耦合作用效应.结果表明：①培养至140d时,添加调理剂处理土壤有效磷含量与未添加调理剂的对照土壤相比均显著增加,有效磷水平可达22.47~37.81mg·kg^-1,在不额外施用磷肥条件下可满足水稻最适生长需求,且添加BC处理的效果最佳.②供试土壤中的磷主要为无机正磷酸盐,且不同形态无机磷含量在调理剂作用下均有所提高,并随着时间土壤中固定态的O-P和Ca₁₀-P逐渐向活性较高的Ca₂-P、Ca₈-P、Al-P和Fe-P形态转变.③添加调理剂处理土壤有效态Cd含量在对照处理基础上显著降低8.74%~17.48%,这与3种调理剂对土壤pH的提高作用相关联.与此同时,添加调理剂的处理与对照相比,可交换态Cd显著降低,碳酸盐结合态Cd和残渣态Cd均有所提高,这与土壤有机质在BC的促进效应下,其表面富含的活性基团能够与Cd²⁺吸附螯合有关.结果初步证明,3种调理剂均能实现供试磷镉富集土壤中磷活化和镉钝化的双重功能,并以生物质炭和钙镁磷肥效果为佳,其效果可覆盖整个水稻生长时段并可延续至其下茬作物播种期.     

Utilization of fly ash in adsorption of heavy metals from wastewater

The aim of this study was to assess the toxicity reduction of wastewaster after treatment with fly ash. Fly ash is a waste material which is formed as a result of coal burning in power plants, but has the potential to adsorb heavy metal ions. The present study examined the adsorption capacity of fly ash to adsorb Pb²⁺, Cu²⁺, and Zn²⁺ from waste water under different conditions of contact time, pH, and temperature. Uptake of metal ions by fly ash generally rose with increasing pH. At lower temperatures the uptake of heavy metal adsorption were enhanced. Significant reduction in Pb²⁺ (79%), Cu²⁺ (53%), and Zn²⁺ (80%) content was found after treatment with fly ash of waste water treatment. Using the microtox test toxicity of the effluent was reduced by 75% due to removal of Pb²⁺ ion by the fly ash. Data indicated that fly ash generated by power plants may be used beneficially to remove metals from waste water.     

Trace elemental characterization of fly ash

The purpose of this study was to determine heavy metal concentrations in ash samples taken from the filter of the gas cleaning system of biomass incinerators in Austria. Knowing the concentrations of heavy metals is important for the decision of further treatment or utilization of the ashes. The heavy metals contained in the ashes remain in the bottom ash of the incinerator or leave the incinerator with the off-gas and are collected in the off-gas filter. The amount of the metals in the collected fly ash depends on the composition of the input material. The aim of this study was to examine this influence and compare the results with literature data. For measurement, the fly ash samples were at first dissolved in a microwave digestion unit using nitric acid and hydrochloric acid. Afterwards, 20 metals were analyzed by inductively coupled plasma optical emission spectrometry. Al, Fe, Mg, Mn, and Zn were found in higher concentrations in the fly ash samples. The enrichment factor between the concentrations in the fly ash and the concentrations in the input material was on average in the range of 18.     

PCDD/DFs and coplanar PCBs in fly ash samples from various types of incinerators in Taiwan

Polychlorinated dibenzo‐p‐dioxins and dibenzofurans (PCDD/DFs) and coplanar polychlorinated biphenyls (Co‐PCBs) were determined in fly ash samples from municipal solid waste (MSW), medical waste (MW), and electricity power plant incinerators in Taiwan. The average concentrations of PCDD/DFs and Co‐PCBs are 7.02 ng‐TEQ/g and 1.06 ng‐TEQ/g, respectively. The contributions to total TEQ are 24% from PCDDs, 64% from PCDFs, and 12% from Co‐PCBs, indicating that PCDFs generate the highest environmental impact and MSW and MW incinerators are potential Co‐PCBs contaminating sources. The levels of PCDD/DFs and Co‐PCBs found in ash samples increase from petroleum‐fired, coal‐fired, large municipal solid waste, small medical waste, to small municipal solid waste incinerators, and are generally lower than those from incinerators built earlier. All fly ash samples analyzed in this study were considered hazardous materials. More research is suggested to establish the relationship between the amounts of PCDD/DFs and Co‐PCBs in fly ash and in flue gas.     

改性粉煤灰处理含Cr(Ⅵ)废水的研究

实验研究了工业废弃物改性粉煤灰对Cr(Ⅵ)吸附的影响因素,讨论了pH值、浓度、温度及时间对吸附量的影响。讨论了反应机理,计算反应热力学参数(焓、自由能、熵)。实验结果表明,当Cr(Ⅵ)初始质量浓度为10 mg/L,反应温度303 K,pH=1时,吸附量最大为0.47 mg/g。吸附过程符合兰格缪尔等温吸附。吸附过程为自发进行的放热反应。反应温度为303 K时,反应过程的焓值为-3.529 kJ/mol,自由能-4.664kJ/mol,熵3.746 J/(mol.K)。反应动力学过程表明反应符合准二级动力学反应。     

电炉铁合金飞灰中金属和二噁英分布特性研究

分别利用高分辨气相色谱-低分辨质谱(HRGC-LRMS)联用仪、原子吸收分光光度计对4个电炉铁合金飞灰中4-8氯取代PCDD/Fs和12种金属进行检测,结果表明,飞灰中金属元素浓度高,其中重金属以Zn浓度最高,为19835.918~36729.200mg/kg;Ni浓度最低,为9.000~43.627mg/kg.4个灰样中PCDD/Fs的浓度差别较大,总量在33.792~88.125ng/g范围内,该浓度水平与生活垃圾焚烧飞灰相当.4个灰样中PCDD/Fs的分布特征不尽相同,但是均以OCDD/F的浓度最高.飞灰中较高的二噁英浓度水平与高浓度的Fe、Cu、Ca和Ni等金属存在一定的相关性.