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生活垃圾焚烧厂中二恶英的产生和控制
二恶英(DIOXIN,简称为DXN)即Poly Chlorinated Dibenzo-P-Dioxins,略写为PCDDs。简单地说PCDDs是两个苯核由两个氧原子结合,而苯核中的一部分氢原子被氯原子取代后所产生,根据氯原子的数量和位置而异,共有75种物质。
  OFweek网讯 1. 前言  生活垃圾焚烧厂烟气中的二恶英是近几年来世界各国所普遍关心的问题,自1999年比利时发生动物饲料二恶英污染事件后,二恶英更是倍受世人所关注,一时成为全球范围的热点。经过这一事件,二恶英在我国也是家喻户晓,闻毒色变。可以这样说,在今天研究生活垃圾焚烧厂烟气中二恶英的产生机理和控制措施,比以往任何时候都显得必要和重要。要建设生活垃圾焚烧厂,我们就不能也无法回避二恶英。  2. 二恶英的结构和特性  2.1 二恶英的分子结构  二恶英(DIOXIN,简称为DXN)即Poly Chlorinated
Dibenzo-P-Dioxins,略写为PCDDs。简单地说PCDDs是两个苯核由两个氧原子结合,而苯核中的一部分氢原子被氯原子取代后所产生,根据氯原子的数量和位置而异,共有75种物质,其中毒性最大的为2,3,7,8&四氯二苯并二恶英TCDDs(2,3,7,8&TCDDs),计有22种;另外,和PCDDs一起产生的二苯呋喃PCDFs,共有135种物质。通常将上述两类物质统称为二恶英(或称戴奥辛),所以二恶英不是一种物质,而是多达210种物质(异构体)的统称。  2.2 二恶英的特性  二恶英在标准状态下呈固态,熔点约为303~305℃。二恶英极难解溶于水,在常温情况下其溶解度在水中仅为7.2&10-6mg/L。而同样在常温情况下,其在二氯苯中的溶解度高达1400
mg/L,这说明二恶英很容易溶解于脂肪,所以它容易在生物体内积累,并难以被排出。二恶英在705℃以下时是相当稳定的,高于此温度即开始分解。另外,二恶英的蒸汽压很低,在标准状态下低于1.33&10-8Pa,这么低的蒸汽压说明二恶英在一般环境温度下不易从表面挥发。这一特性加上热稳定性和在水中的低溶解度,是决定二恶英在环境中去向的重要特性。  3. 二恶英的毒性和评价  据报导,二恶英是目前发现的无意识合成的副产品中毒性最强的化合物,它的毒性相当于氰化钾(KCN)的1000倍以上。同时它是一种对人体非常有害的物质,即使在很微量的情况下,长期摄取时便可引起癌症等顽症,国际癌症研究中心已将它列为人类一级致癌物。此外二恶英对人体还会引起皮肤痤疮、头痛、失聪、忧郁、失眠、新生儿畸形等症,并可能具有长期效应,如导致染色体损伤、心力衰竭、内分泌失调等。据有关报道,只要1盎斯(28.35克)二恶英,就能将100万人置于死地。  但上述结论更多的是建立在定性分析和理论推测的基础上的,因为根据国外有关报道,采用不同的方法对动物进行二恶英的毒性试验时,所获得的数据非常分散,变化范围相当广。其主要原因可能是二恶英的测量值极其微量(十亿分之几甚至万亿分之几),在不同的实验条件下,其结果会产生重大差异。而研究二恶英对人体的影响,至今还没有试验数据,今后也不可能用人来作直接试验。虽然,过去曾有过人体偶然接触二恶英从而导致伤亡的记录,但就此来确定二恶英对人体健康的影响是远远不够的。  二恶英的毒性与异构体结构有很大关系,各异构体浓度的综合毒性评价方法一般以TCDDs为基准,利用TCDDs的毒性当量(TEQ)来表示各异构体的毒性,称之为毒性当量因子(TEF),其它异构体的毒性以相对毒性进行评价,其计量单位常采用ng-TEQ/Nm3,目前发达国家对二恶英的排放标准一般控制为0.1ng-TEQ/Nm3。  4. 二恶英的产生和排放  4.1 二恶英和垃圾焚烧厂  现在有一种观点认为,二恶英是生活垃圾焚烧厂特有的公害问题,这是一种偏面的认识,其实二恶英是有机物与氯一起加热就会产生的化合物,只要使用水的场所都有可能产生二恶英,它是一种普遍的化学现象。二恶英在空气、土壤、水和食物中都能发现,火山爆发及森林火灾是自然界中二恶英的主要来源。另外,除草剂、发电厂、木材燃烧、造纸业、水泥业、金属冶炼、纸桨加氯漂白及垃圾焚烧处理均会释放出二恶英。据有关报道,人体从生活垃圾焚烧厂排放烟气中接触二恶英的机率要比从其它途径(如食物、空气等)接触二恶英的机率小。综合有关资料,国外生活垃圾焚烧厂烟气中二恶英的浓度范围约为10-4~10-6mg/Nm3之间,对周围环境空气质量的影响非常微小。实际上世界各国曾经发生过的多次二恶英污染事件几乎都与生活垃圾焚烧厂的烟气排放无关,包括1999年发生在比利时引起世界范围恐慌的动物饲料二恶英污染事件。  但这并不是说在生活垃圾焚烧厂的设计和运行时就可以不重视二恶英了,实际上从生活垃圾焚烧厂排放出来的二恶英往往都占各国二恶英排放总量的相当大的比重,但现有的统计资料表现出相当大的离散性。例如,根据美国署1994年完成的评估报告,全美产生的二恶英中来自垃圾焚烧厂的约占3.5%,这是所见资料中的下限;又如,据1990年日本的统计资料,日本二恶英的排放总量中来自垃圾焚烧厂的占80%以上,这是所见资料中的上限。综合有关资料,在采用焚烧方法处理生活垃圾比例较高的国家中,由生活垃圾焚烧厂排放出来的二恶英约占该国二恶英排放总量的10%~40%,绝对是污染大户。这就是世界各国对生活垃圾焚烧厂排放出来的二恶英予以极大关注的原因所在。也充分说明了在建设生活垃圾焚烧厂或者在生活垃圾焚烧厂的运行管理中,要注意改善生活垃圾的燃烧条件,严格控制二恶英产生的重要性和必要性。  4.2 垃圾焚烧厂中二恶英的生成途径  生活垃圾在焚烧过程中,二恶英的生成机理相当复杂,至今为止国内外的研究成果还不足以完全说明问题,已知的生成途径可能有:  4.2.1生活垃圾中本身含有微量的二恶英,由于二恶英具有热稳定性,尽管大部分在高温燃烧时得以分解,但仍会有一部分在燃烧以后排放出来;  4.2.2在燃烧过程中由含氯前体物生成二恶英,前体物包括聚氯乙烯、氯代苯、五氯苯酚等,在燃烧中前体物分子通过重排、自由基缩合、脱氯或其他分子反应等过程会生成二恶英,这部分二恶英在高温燃烧条件下大部分也会被分解  4.2.3当因燃烧不充分而在烟气中产生过多的未燃烬物质,并遇适量的触媒物质(主要为重金属,特别是铜等)及300~500℃的温度环境,那么在高温燃烧中已经分解的二恶英将会重新生成。  5. 二恶英的控制对策和措施  5.1 二恶英的控制对策  1996年6月,日本厚生省成立了《过程中二恶英削减对策研讨委员会》,并以最近的二恶英削减技术为基础,把二恶英削减对策分为&紧急对策&和&永久对策&两部分进行了研究,以全面推动削减二恶英为目标,1997年1
月23日日本政府重新编写了《关于垃圾处理过程中的防治二恶英产生等问题的指南》(通常称之为&新指南&)。
所谓&紧急对策&是利用最新的技术,把二恶英浓度水平削减到最低水平。具体讲,即使是在最容易受到垃圾焚烧厂影响的最大落地浓度地点上也要采取措施,使其TDI(人日容许摄入量)不要超过10pg/kg.d(TEQ)值,而且规定需要采取紧急对策的判断标准为80
pg/Nm3(TEQ)。即若某一垃圾焚烧厂不能达到80
pg/Nm3(TEQ)以下的排放浓度,则应立即采取削减措施。即使排放浓度没有超过这一标准的垃圾焚烧厂也要继续实行永久对策,努力控制二恶英的排放量。在&新指南&中的&永久对策&规定,新建完全连续运行焚烧炉的二恶英排放浓度标准定为0.1
ng/Nm3(TEQ)。  5.2 二恶英的控制措施  国内外的研究和实践均表明,减少生活垃圾焚烧厂烟气中二恶英浓度的主要方法是采取有效措施控制二恶英的生成。这些控制措施主要包括:  5.2.1选用合适的炉膛和炉排结构,使垃圾在焚烧炉得以充分燃烧,而衡量垃圾是否充分燃烧的重要指标之一是烟气中CO的浓度,CO的浓度越低说明燃烧越充分,烟气中CO浓度比较理想的指标是低于60
mg/Nm3;  5.2.2控制炉膛及二次燃烧室内,或在进入前烟道内的的烟气温度不低于850℃,烟气在炉膛及二次燃烧室内的停留时间不小于2S,O2浓度不少于6%,并合理控制助燃空气的风量、温度和注入位置,也称&三T&控制法;  5.2.3缩短烟气在处理和排放过程中处于300~500℃温度域的时间,控制余热锅炉的排烟温度不超过250℃左右;  5.2.4选用新型袋式,控制除尘器入口处的烟气温度低于200℃,并在进入袋式除尘器的烟道上设置活性碳等反应剂的喷射装置,进一步吸附二恶英;  5.2.5 在生活垃圾焚烧厂中设置先进、完善和可靠的全套自动控制系统,使焚烧和净化工艺得以良好执行;  5.2.6通过分类收集或预分拣控制生活垃圾中氯和重金属含量高的物质进入垃圾焚烧厂;  5.2.7由于二恶英可以在飞灰上被吸附或生成,所以对飞灰应用专门容器收集后作为有毒有害物质送安全填埋场进行无害化处置,有条件时可以对飞灰进行低温(300~400℃)加热脱氯处理,或熔融固化处理后再送安全填埋场处置,以有效地减少飞灰中二恶英的排放。  6. 结语  综上所述,生活垃圾焚烧厂烟气中的二恶英是客观存在的,但对此产生盲目的恐慌则是完全没有必要的。由于我国生活垃圾中含氯化合物和重金属含量相对较少,只要生活垃圾在焚烧炉中能达到完全燃烧,保证烟气在较高的燃烧温度下有较长的停留时间,并在烟气的排放过程中尽量避开300~500℃温度域,加上其它喷射活性碳、设置袋式除尘器等辅助措施配合,生活垃圾焚烧厂中二恶英的排放浓度是可以有效控制的,一般不会超过环保标准。
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