添加剂对垃圾焚烧飞灰熔融过程二不断噁英分解的影响

为了研究添加剂对垃圾飞灰熔融处理过程中二噁英分解特性的影响，选择碱性氧化物CaO和液体陶瓷(LC)2种添加剂，改变温度、气氛和熔融时间研究2种添加剂对二噁英分解率的影响．研究表明CaO对二噁英分解影响随气氛不同而改变，氧化气氛下，加入CaO使二噁英的分解率略微降低，而在还原气氛下则会使二噁英分解率升高．液体陶瓷添加剂对熔融过程二噁英分解有显著影响．1400℃时，随着LC添加比例由0增加到10％，二噁英分解率则从99．997％升高到100％．同时加入10％的LC可以使二噁英的完全分解温度由无添加剂时的1460℃降低至1100℃．     

焦煤、塑料和粉尘共热解失重分析

在以N₂载气,其流量为30mL/min、升温速率为5℃/min、热解终温为1000℃的条件下,运用Setaram Lab-sysYM热重分析仪系统分析了塑料、冶金粉尘和焦煤的热解过程以及它们之间的相互影响.不同配比的塑料、冶金粉尘和焦煤混合热解过程分析表明:在低温段,煤和塑料热解产生大量活泼自由基,然后通过自由基内部重排或自由基间相互结合的方式稳定化,其中的硫元素主要形成气态硫化物(如H₂S、COS等),并与粉尘中的金属氧化物作用生成固态金属硫化物而固硫;高温段产生的H₂、CO及粉尘中所含有的C等增强了反应体系的还原性,加剧了粉尘中金属氧化物的还原气化,从而更有利于实现焦炭的有效脱硫可见,运用添加塑料、冶金粉尘到焦煤中的方法可以实现炼焦过程中的焦炭和煤气同时脱硫的双重效果.     

垃圾焚烧与二■■

多氯二苯并-对-二■■(PCDDs)和多氯二苯并呋喃(PCDFs)是毒性极强的环境污染物质,垃圾焚烧又是大城市中引起二■■污染的主要来源。文中介绍了如何加强垃圾焚烧厂的运行管理,严格控制二■■的产生和排放等问题。      

Hydrothermal treatment of MSWI fly ash for simultaneous dioxins decomposition and heavy metal stabilization

Researches on the hydrothermal treatment of municipal solid waste incineration (MSWI) fly ash were conducted to eliminate dioxins and stabilize heavy metals. In order to enhance decomposing polychlorinated dibenzodioxins (PCDDs) and polychlorinated dibenzo-furans (PCDFs) during hydrothermal process, a strong reductant carbohydrazide (CHZ) is introduced. A hydrothermal reactor was set up by mixing raw MSWI fly ash or the pre-treated fly ash with water and then heated to a pre-set temperature; CHZ was spiked into solution according to specially defined dosage. Experimental results showed that under the temperatures of 518 K and 533 K, the decomposition rates of PCDDs/PCDFs were over 80% and 90%, respectively, by total concentration. However, their toxic equivalent (TEQ) decreased only slightly or even increased due to the rising in concentration of congeners 2, 3, 7, 8-TCDD/TCDF, which might be resulted from the highly chlorinated congeners losing their chlorine atoms and being degraded during the hydrothermal process. Better results of TEQ reduction were also obtained under the higher tested temperature of 533 K and reactor with addition of 0.1%wt CHZ was corresponded to the best results. Good stabilization of heavy metals was also obtained in the same hydrothermal process especially when ferrous sulphate was added as auxiliary agent.     

Distribution of PCDDs,PCDFs and PCBs in the atmosphere

Air samples were collected through the summer season using quartz fiber filter (QMF) and polyurethane foam plugs (PUF) with high volume air sampler. The QMF and PUF samples were analyzed for polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), polychlorinated biphenyls (PCBs), chlordanes and DDE by high resolution gas chromatography with mass spectrometry (HRGC-MS). We have previously reported the concentrations of these compounds in urban air. In this study we present: (1) daily variability; (2) vapor/particulate ratio of these compounds. Daily variability of these compounds in ambient air was discussed with meteorological factors. The major parts of PCDDs and PCDFs exist in the particulate phase. Chlordanes, PCBs, and DDE exist in the vapor phase at 98%,96% and 95%, respectively.     

鲫鱼肝脏中CYP1A1的诱导作为沉积物中二的毒理学指标的研究

在实验室内用鲫鱼分别暴露于含有PCDD/Fs和PCBs严重污染的沉积物和未受污染的沉积物中,测定鱼肝脏中细胞色素P4501A1（CYP1A1）依赖的7－乙氧基－3－异吩唑酮－脱乙基酶（EROD）的活性。结果表明,鲫鱼暴露于受二类化合物污染沉积物中1周后,肝脏中EROD的活性是对照组的83倍,而未被污染的沉积物暴露试验中EROD的活性和对照组没有明显差别。在此沉积物－水实验系统中二类污染物的TCDD等当量浓度（TEQ/L）与肝脏EROD的活性有较好的相关性。较长时间暴露,得到肝脏EROD的活性随时间的变化关系。还获得了试验温度对EROD活性诱导的影响。此实验表明,用实验室鲫鱼暴露于沉积物－水系统中,鱼肝脏EROD活性诱导可作为沉积物毒性评价指标,用于受二类化合物污染的沉积物样品的筛选,并有希望成为此类污染物的半定量检测方法。     

PVC热解过程中HCl的生成及其影响因素

采用热重分析仪(TG)对聚氯乙烯(PVC)的热解特性进行研究.在不同条件下进行PVC热解制取氯化氢(HCl)实验,研究载气流量、入料量、热解时间和热解温度对氯化氢产率的影响,得出最佳热解条件;采用离子色谱(IC)、气相色谱(GC)、气质联用仪(GC-MS)对热解产物进行化学分析,揭示PVC热解制取HCl过程的反应机理.结果表明:PVC热解制取氯化氢的最佳热解条件为载气流量100mL/min、热解时间30min、入料量1.2g和热解温度400℃;PVC热解存在2个失重阶段,即260~320 ℃和390~600 ℃;随热解温度升高,焦油产率由0.95%升高到20.29%、HCl产率由25.69%升高到53.76%,而半焦产率则由54.39%下降到11.27%、气体产率变化范围为9.09%~18.97%;当热解温度低于400 ℃时,气体组分仅检测到H2、C2H4、C3H6;当热解温度高于400 ℃时,检测到的气体组分为H2、CH4、C2H4、C2H6、C3H6、C3H8;随着热解温度的升高,焦油组分中不稳定组分逐渐转化为稳定组分.PVC热解制取HCl的第1反应阶段主要是脱除HCl的链式反应,同时生成少量的苯等芳香族化合物及环烷烃等有机化合物;第2反应阶段主要为少量HCl生成、焦油的结构重整、分子重排、脱苯环和同分异构化等.     

污泥中潜在的二■■污染物质

依据国内外最近的检测结果对污泥中二■■类物质的研究进行论述,探讨其来源、组成分布、环境行为及潜在危害。研究表明,焚烧过程排放?成了环境中二■■的本底来源,除此之外的二■■主要来源于废水处理(包括生活污水与工业污水)形成的污泥,并且污泥中二■■的含量较高。鉴于二■■的毒理特性、以往的二■■污染事件及我国对污泥的处理方式,急需查明堆肥与填埋处理的污泥中的二■■现状,并以此为依据制定二■■毒物的排放标准及其在环境中的限额。      

城市生活垃圾气化熔融焚烧技术

近年来,新开发的气化熔融焚烧技术实现了垃圾处理能源化目标和与环境的协调发展,该技术被认为是解决垃圾处理和能源问题最有效的方法。文章结合传统焚烧+灰渣熔融技术、阐述了两步法气化熔融和直接气化熔融两种气化熔融焚烧技术工艺流程的特点。气化熔融焚烧技术能遏制二英的产生和排放,降低焚烧过程产生酸性气体(SOx,HCl,HF,NOx等)、挥发性有机物尤其是芳香烃类、多氯化联苯类和二英、呋喃类、以及重金属和危害性灰渣的排放。叶恶叶恶     

灰分对高硫煤热解部分气化硫变迁的影响

采用分步脱除矿物质方法,对义马原煤及HCl,HCl-HF,HCl-HNO₃处理后煤样,分别在固定床反应器中考察了热解部分气化下硫的脱除规律.结果表明:一方面在热解过程中原煤及酸处理煤样H₂S和COS的析出均呈双峰趋势,其析出值主要受温度、原煤中灰分和HNO₃氧化作用;另一方面,在部分气化和酸处理后煤样热解半焦在600℃～900℃范围内硫脱除率可达50%～80%,800℃时,无机硫可完全脱除.而原煤热解半焦总硫,无机硫的脱除率在700℃时最大.气化温度的升高,加强了碱性矿物质的固硫作用,其结果是900℃气化时,总硫和无机硫脱除率降低.酸处理后有机硫含量基本保持不变,其噻吩结构只随碳骨架的气化而析出.     

Characterization of mechanochemical treated fly ash from a medical waste incinerator

The mechanochemical treatment of fly ash generated from a medical waste incinerator was subjected to grinding for 2 hr at 400 r/min in a planetary ball mill. The treated fly ash was characterized by a suite of analytical methods including High Resolution Gas Chromatograph/High Resolution Mass Spectrometer, Mastersizer 2000 Particle Size Analyzer, QUADRASORBTM SI Surface Area Analyzer, Scanning Electron Microscopy and X-ray di raction. Results showed that abatement e ciency of polychlorinated dibenzop- dioxins and polychlorinated dibenzofurans (PCDDs/Fs) in terms of total concentration averagely amount to 76% which was relatively higher than that of I-TEQ concentration averagely amount to 56%; the most concentration of toxic congeners as well as isomers of PCDDs/Fs decreased after mechanochemical treatment. The treated fly ash was characterized by a more homogeneous distribution of concaves as well as the significant decreasing in overall particle size and great enlargement in surface area. The major crystallization phases or intensities were considerably changed by mechanochemical treatment, of which a new phase containing chlorine formed may be a possible factor suggesting chlorination reaction occurring on the crystalline surface.     

温度对城市有机垃圾热解焦油成分的影响

以城市有机垃圾热解焦油为对象,研究了不同热解终温下(600~800℃)焦油的特性及其随温度的变化规律.结果表明:随着热解终温从600℃升高至800℃,焦油中C含量从74.49%增至83.42%;焦油的芳香化程度高于原料而低于热解炭,焦油的极性低于原料和热解炭,随着热解终温的升高,焦油的H/C和O/C逐渐降低;多环芳烃(PAHs)是焦油的主要成分,随着热解终温从600℃升高至800℃,其含量从54.06%增至83.45%;萘及其衍生物是焦油PAHs的主要成分,其含量在热解终温600、700、800℃时分别占PAHs的50.72%、46.80%、39.26%.研究结果证明了垃圾热解焦油可用作碳基复合材料和作为制备染料、树脂、溶剂、驱虫剂等的原料.     

生活垃圾焚烧发电厂二噁英近零排放技术研究

随着生活垃圾焚烧发电厂的逐渐增多,二噁英首当其冲成为反对呼声的靶子,因此探讨二噁英的防治对策进展显得更为重要.二噁英近零排放控制技术目前主要有两种:选择性催化还原法和热解气化技术.选择性催化还原(SCR)系统一般是用来去除NOx,实际上采用合适的催化剂后,二噁英去除效率能高于90%.热解气化技术被称为第三代焚烧技术,一方面一燃室里垃圾热分解,削弱了二噁英的生成环境;另一方面,二燃室里气体燃烧,温度在1000℃以上,烟气停留时间2 s以上,保证了二噁英的充分分解.     

废旧锂电池电极活性材料真空热解固氟研究

以废旧锂离子电池电极活性材料为研究对象,在真空热解过程中加入CaO作为固氟剂,用以吸收电极活性材料在真空热解的回收工艺中产生的氟磷化合物,能有效减轻二次污染。研究了温度、CaO添加量、停留时间等热解条件对真空热解固氟效果的影响。结果表明固氟效果随温度的增加而增加,在温度500℃以上变化不大,并略有下降;CaO添加量对固氟效果有促进作用,30%可达到很高的固氟效果;30 min的停留时间对于含氟化合物的分解已经足够。得到CaO固氟工序的最佳操作参数:CaO添加量30%左右,温度500~600℃,停留时间30 min。     

Heavy metal removal from aqueous solution using carbonaceous K2S-impregnated adsorbent

A novel carbonaceous adsorbent for heavy metal removal was prepared from raw coal by one-step simple sulfur impregnation using K2S. Raw coal was mixed with K2S powder and then heated at 800°C for 30 min in nitrogen to produce K2S char. The sulfur content and form in K2S char were determined, and the ability of K2S char to adsorb Zn2+, Cd2+ and Pb2+ was examined. The K2S impregnation was e ective at impregnating sulfur into coal, especially in the form of elemental, thiophenic and sulfatic sulfur. The sulfur content of K2S char was higher than those of raw coal and pyrolysis char. The Zn2+ removal in 2.4 mmol/L of Zn2+ solution by K2S char was higher than raw coal with the removal rate of 100%. K2S char adsorbed Pb2+ and Cd2+ in 24 mmol/L of Pb2+ and Cd2+ solution with the removal rate of 97% and 35%, respectively. The elution extents of adsorbed Pb2+ and Cd2+ were zero in distilled water and 27% in 0.1 mol/L HCl solution. These results indicated that an e ective adsorbent for heavy metal ions was prepared from coal using K2S sulfur impregnation, and that the adsorbed metals were strongly retained in K2S char.     

产乙烯脱卤拟球菌195脱卤反应途径的理论探针

运用密度泛函理论在B3LYP/6-31G(d)水平下对多氯二苯并-对-二 (PCDDs)、多氯二苯并呋喃(PCDFs)、多氯联苯(PCBs)、多溴联苯醚(PBDEs)和氯苯分子进行计算,找到了一个可指示产乙烯脱卤拟球菌(Dehalococcoides ethenogenes)195降解转化这些芳香卤化物脱卤反应途径和中间产物的参数—结构上可能的脱卤产物的分子总能量(ET).以ET作为理论探针可指示PCDD/Fs、PCBs、PBDEs和氯苯被菌株195转化的主要脱卤中间产物,脱卤反应倾向于生成具有较低ET值的中间产物.另外可以利用结构上可能的脱卤中间产物与具有最低ET值脱卤中间产物间的分子总能量差(?ET)作为理论探针,推断存在第2种脱卤中间产物的可能性,?ET越小,则同时存在多种脱卤中间产物的可能性越大.     

城市垃圾焚烧飞灰熔融DSC-DTA实验研究

利用高温DSC-DTA热分析仪对国内外2种城市垃圾焚烧飞灰在惰性气氛(N2)和氧化气氛(O₂)下的熔融特性进行了研究.在20℃～1450℃的温度范围内采用3种温升速率进行实验.飞灰熔融过程包含多晶转变和熔融相变2种反应,多晶转变发生在480℃～670℃范围内,吸热量20kJ/kg;熔融约发生在1136℃～1231℃,在1174℃达到峰值,熔融相变潜热约700 KJ/kg,整个过程总吸热量约1800 kJ/kg.研究了CaO添加剂对飞灰熔融的影响.最后提出飞灰熔融吸热量的预测模型,模型     

新型干法水泥生产中二恶英减排的环境技术经济研究

分析了水泥生产过程中多氯二苯并对二恶英和多氯二苯并呋喃(以下简称“二恶英”)的产生机理和国内外排放情况,针对我国部分新型干法水泥窑生产工艺二恶英排放偏高和窑炉能效偏低的问题,选择典型的新型干法水泥窑,开展了二恶英、常规污染物排放情况监测和能效检测及诊断,提出了二恶英协同减排措施,实施了有针对性的技术改造,并对改造后的排放和能效改进情况、环境和经济效益进行了系统评估. 结果表明:采用提高能效、充分燃烧、快速冷却废气及确保进入除尘器的废气温度低于200 ℃等二恶英减排最佳可行技术,烟气中二恶英的量降低了91.8%,单位熟料的能耗水平降低了2.08%;同时,颗粒物等常规污染物和二氧化碳等温室气体也实现了协同减排. 企业通过节能和余热利用获取了经济效益.      

Pyrolysis of EVA and its application in recycling of photovoltaic modules

The basic pyrolysis behaviour of ethylene vinyl acetate(EVA) copolymer, which is often used as a lamination agent in solar modules, was investigated in thermogravimetry, differential thermal analysis(DTA) and thermovolumetry. The TG analysis showed that the EVA pyrolysis can be accelerated under the partial oxidizing atmosphere but the end pyrolysis temperature must be higher than in nitrogen, to eliminate the coke formed. Meanwhile, a strong exothermal peak occurs at about 450% under the air condition and gets weaker obviously at the oxygen content lower than 10 vol. %. The mass balance of EVA pyrolysis was given through the thermovolumetry with the output of l0 wt. % permanent gas, 89.9 wt. % condensate and 0.1% residual coke. Besides, the composition of the permanent gas and condensate at different pyrolysis stages were analysed and interpreted on the known pyrolysis mechanism.     

微电解-电/Fenton-曝气池工艺预处理高浓度亚麻废水

高浓度亚麻废水不宜直接进行生化处理。试验采用"Fe-C柱微电解-电/Fenton-曝气池"工艺对其进行预处理,即先采用Fe/C微电解,然后基于Fe2+的生成几乎同步引入电/Fenton反应,之后再调节流出液pH至碱性并鼓入空气以除去部分NH3-N。相应优化工艺条件为:Fe/C柱微电解时mFe/mC为2:1,废水停留时间为1.5 h;电/Fenton时双氧水(30%)滴加速度为0.025 mL/min;调节水样pH10并在空气流速为1.5 L/min的条件下空气吹脱1.5 h。采用该工艺预处理高浓度亚麻废水后,出水几乎为无色;固体悬浮物的去除率可达94.2%,NH3-N去除率可达71.4%,COD去除率可达51.8%,BOD5去除率可达28.3%,为后续生化深度处理创造了有利条件;BOD5/COD值由原来的0.12上升至0.19,废水的可生化性得到较明显的改善。电/Fenton反应的处理效果好于普通的Fenton反应,其原因可能是由于电/Fenton既有"原位"的均相/非均相Fenton反应发生,又有在微电解电场协助下的"电催化Fenton"反应发生。