CN113731136A - 一种避免二噁英生成的炉内控制方法 - Google Patents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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Abstract
二噁英是焚烧行为产生的污染物质,二噁英生成的前提是有卤族元素和有机物存在。本发明是在焚烧过程中,在高温条件下(800℃‑1200℃)在烟气出口处喷射卤族元素反应活性剂,反应活性剂与卤族元素的质量比为(10‑50):1,该活性试剂为碱性微粉,碱性微粉依靠自身活性吸附卤族元素后与卤族元素反应生成稳定的卤化物,有效消耗卤族元素,使二噁英因缺乏卤族元素而无法生成。
Description
技术领域
本发明主要属于焚烧烟气处理领域,具体是涉及一种焚烧烟气中二噁英类物质的炉内控制方法。
背景技术
固体废物焚烧处理具有适用面广、减量效果好、削减毒性、可回收热量等优点,已成为国内外处理生活垃圾、电子垃圾、危险废物与污泥等固体废物的重要手段。根据《中国统计年鉴》,2018年中国生活垃圾焚烧处理量已达无害化处理量的45.1%,此外医疗废物等危险废物也主要以焚烧为处理方式。但是焚烧过程中会产生SO2、NOX以及二噁英等气相污染物,其中二噁英毒性强,具有致癌性、致畸性等性质,二噁英的控制是烟气净化的重点与难点。
二噁英的生成机制主要包括原生二噁英的释放、高温与缺氧条件下CO等碳氧化物与HCl酸性卤素气体作用释放、含卤素前驱物分子反应生成二噁英、200-500℃时C、O、H、Cl等元素发生基元反应从头合成二噁英等(陈帅帅.电子垃圾处理过程中二噁英检测与减排研究[D])。目前二噁英的处理方法主要是通过控制炉膛焚烧温度在850℃以上,分解破坏二噁英以控制排放量,但是烟气在降温过程中卤素与碳、氢、氧等元素在催化剂的作用下会产生二噁英前驱物进而合成二噁英,或者发生氧化与缩合等基元反应从头合成二噁英,二噁英不能完全得到控制。氯化氢、溴化氢、氯气、溴与含卤素有机物气体的含量是二噁英从头合成的重要影响因素。国内针对固体废物焚烧的高温烟气普遍采取急冷处理,在极短时间内将烟气温度降至200℃以下,最大限度削减烟气在从头生成最适温度区间的停留时间,但采用水冷骤降温度进行急冷处理时降温速率往往很难达到要求,而且急冷后无法回收焚烧产生的热能,造成了资源的浪费。因此有必要探索固定气体中卤化物进而控制降温过程中二噁英合成的方法。中国专利CN105316480A公布了一种减少在烧结过程中二噁英生成的抑制剂添加方法与装置。其抑制剂通过两级混合法添加,一级混合为将尿素配制成20%-30%的溶液作为抑制剂输送至烧结小球***与焚烧原料混合,通过流量控制计控制抑制剂添加量在0.005%-0.01%之间,二级混合为将抑制剂混合烧结球与混合料再次进入烧结机烧结,最后将混合物料进入烧结机烧结。该发明通过添加尿素与燃料烧结小球混合进而抑制二噁英的产生,抑制剂用量少。但是抑制效果一般,为50%左右,且尿素的加入可能会增加烧结过程中氮氧化物的排放,大面积推广使用有一定的难度。
中国专利CN101368121B公布了一种垃圾焚烧二噁英控制的添加剂及其生产工艺。其采用特殊配制的混合添加剂(80-88%的含硫量0.5-1%的煤,2.3-8.1%的氧化钙或碳酸钙,0.8%-2.5%的氢氧化钠,2.5%-4.5%的碳酸铵以及2.3%-7.6%的碳酸钴、碳酸钾、高锰酸盐)来固定氯化物,降低二噁英的低温生成,以此降低二噁英的排放。但是生产此添加剂只是将各添加物料混合,并未明确混合剂的加入方式以及各配料的作用效果,亦未明确此混合添加剂的整体控制效果,且多种物料加入的同时也增加了处理成本,不利于推广使用。
焚烧烟气降温过程中二噁英的合成是烟气中卤化物的作用过程,大量的研究表明含氯或溴物质提供的氯源或溴源是影响二噁英合成的重要因素。(郑玉峰,祁国恕.固体废物焚烧二恶英的生成机制及其控制技术[J].环境保护科学,2008,34(3):16-18,46)。相关研究表明,在催化过程中烟气中的大分子有机碳以及氯化氢等无机氯经过飞灰中一些有催化作用的成分(Cu、Fe等过渡金属或它的金属氧化物)催化反应会生成二噁英及包括氯代苯、五氯苯酚等二噁英的前驱物,这些前驱物在金属的催化作用下,通过分子重排或自由基缩合或脱卤等与其他分子反应形成二噁英。而碱性添加剂能与HBr等酸性气体反应,且能使芳烃脱卤,从而可控制二噁英的前驱物合成与从头合成。可见在炉内烟气降温前喷射碱性微粉可有效地依靠其活性吸附卤族元素,与酸性卤化气体等卤化物反应,进而与卤族元素反应生成稳定的卤化无机盐,使卤族元素缺乏而无法生成二噁英。
发明内容
本发明针对固体废物焚烧烟气降温时二噁英形成的过程,提供一种利用卤族元素反应活性剂(碱性微粉)炉内喷射避免二噁英形成的方法,可有效的在避免二噁英低温重合成。
本发明可通过以下技术方案实现:
在焚烧过程中,温度为800℃-1200℃的区间,二噁英在高温条件下被分解后分散进入烟气通道,将碱性微粉抑制剂通过微粉喷枪喷入炉膛烟气出口前端,使烟气中酸性卤化气体等卤化物与碱性微粉混合进而被吸附与反应。
所述碱性微粉抑制剂为碱性碳酸盐,包括K2CO3、KHCO3、Na2CO3、NaHCO3,进一步优选Na2CO3。此类碱性碳酸盐成本较低,便于操作。以燃料中卤族元素质量为基准,使用时以卤族元素反应活性剂与卤族元素质量比为(10-50):1的比例从烟道前端喷入。
碱性微粉依靠自身活性吸附卤族元素后与卤族元素反应生成稳定的卤化物。碳酸钠可以通过以下作用过程将卤化物转化为氯化钠等卤化无机盐固定在活性剂内,从而使二噁英由于缺乏卤族元素而无法合成。
Na2CO3+2HX=2NaX+CO2↑+H2O
同时碱性碳酸盐可使卤代芳烃脱卤,碱性微粉可与部分有机卤化物反应固定在活性剂内。
上述固定卤素反应均在炉膛内800℃-1200℃高温条件下发生,可满足在烟气降温前避免二噁英形成的应用要求。
优选地,所述碳酸钠为无水碳酸钠微粉,粒径优选100-300目,活性剂的比表面积大,保证活性剂与烟气的充分作用。在烟道前端将碱性微粉以微粉状喷入,活性剂被高速经过的烟气作用分散混合,有利于活性剂与烟气中卤化物充分吸附反应,会显著提升活性剂的固卤反应效率。
所述炉内反应活性剂反应装置由计量投料机1、气动微粉喷射器2、微粉喷枪3、收集斗5、卸灰口6组成。所述微粉喷射器喷嘴为圆柱状,用于喷射活性剂微粉;计量投料机用于控制活性剂加入量;收集斗与卸灰口用于收集与定期排出反应后的活性剂。
与现有技术相比,本发明有以下优点
1)本发明优选卤素反应活性剂,同时在主流固体废物焚烧的温度条件下进行反应,可实现在不改变原有工作温度的条件下对烟气降温过程中二噁英产生的有效控制。
2)本发明使用碳酸钠作为反应活性剂,二噁英控制效果好、成本低;活性剂喷入***不需要改变原有工艺条件、易操作,具有技术可行性。
3)本发明不需要对烟气采用骤冷的方式控制二噁英,后续可继续利用固体废物焚烧产生的热量。
附图说明
图1为炉内卤族元素反应活性剂反应装置示意图。
具体实施方式
下面通过叙述实施例结合附图对本发明做进一步的说明。
本发明提供了一种避免二噁英生成的炉内控制方法,包括卤族元素反应活性剂的预处理与活性剂喷射装置,装置如图1所示。
固体废物焚烧产生的二噁英在800-1200℃高温下分解进入烟气中,在烟道前端炉内侧壁喷入卤族元素反应活性剂微粉,通过活性剂吸附高温烟气中卤化物并与其反应,实现卤素固定反应。
卤族元素反应活性剂采用碳酸钠微粉,将碳酸钠微粉研磨至100-300目,以反应活性剂与卤族元素(10-50):1的质量比喷入炉膛烟道前端。
整个焚烧***包括固体废物焚烧炉膛、烟气通道、活性剂反应装置,其中活性剂反应装置包括喷射器与收集器,安装在炉膛内烟气通道前端。喷射装置采用气体扰动喷射器,碱性微粉被持续搅动,避免发生架料现象。喷射器前端采用计量投料机控制反应剂的加入剂量。喷射器安装于炉膛内烟道前端,高温烟气自下而上与活性剂充分混合,烟气与活性剂持续作用,使烟气中酸性卤化气体等卤化物转化成卤化钠等卤化无机盐固定在活性剂中。收集斗采用耐高温材质制成对反应后活性剂进行收集,收集斗末端设置卸料口,可定期排出反应活性剂。
实施案例:
1)将电路板去除元器件,破碎后,采用氧弹+离子色谱法对其进行有机卤素与无机卤素含量分析;
2)研磨碳酸钠至200目大小的微粉,加入进料机。碳酸钠投加量按与卤族元素质量比35:1的比例计算。
3)将电路板微粉送入高温炉中焚烧,焚烧炉温控制在850℃。通过计量投料机控制碳酸钠微粉投入量,碳酸钠微粉通过气动微粉喷射器喷入炉膛烟道前端;碳酸钠与无机与有机卤化气体反应,被固定成卤化无机盐,落入收集斗中被收集,削减了促进二噁英产生的卤素源,在炉内避免二噁英的降温再生成。
4)经试验测定,碱性微粉碳酸钠固定的卤素达电路板卤素含量的80%以上,烟气中二噁英的降温再合成得到有效的控制。
Claims (6)
1.一种避免二噁英生成的炉内控制方法,其特征在于,在800-1200℃的焚烧炉膛内,在卤素反应活性剂反应装置内,卤素反应活性剂(碱性微粉)通过微粉喷射装置喷入炉膛内烟气出口前端,烟气中酸性卤化气体等卤化物被活性剂吸附反应生成稳定的卤化无机盐被收集,在烟气降温前大幅削减二噁英合成的卤素源,避免二噁英的降温重生成。
2.根据权利要求1所述的一种避免二噁英生成的炉内控制方法,其特征在于,所述卤素反应活性剂为碱性碳酸盐,包括碳酸钾、碳酸氢钾、碳酸钠、碳酸氢钠的一种或多种,优选为碳酸钠,粒径大小为100-300目,使用时以反应活性剂与卤族元素的质量比为(10-50):1的比例以微粉状通过喷枪喷入炉膛内。
3.根据权利要求1与权利要求2所述的一种避免二噁英生成的炉内控制方法,其特征在于,在炉膛内800-1200℃的温度区间二噁英被分解后产生的酸性卤化气体,有机卤化物等被所述的碱性碳酸盐吸附反应,卤素被碱性碳酸盐固定为稳定的卤化无机盐,从而在烟气降温前使二噁英缺乏卤素而无法生成。
4.根据权利要求1所述的一种避免二噁英生成的炉内控制方法,其特征在于,所述的卤素反应活性剂反应装置,安装在焚烧炉膛侧壁,具***置在炉膛内烟气通道出口前端。
5.根据权利要求1与权利要求4所述的一种避免二噁英生成的炉内控制方法,其特征在于,所述的卤素反应活性剂反应装置中喷射装置由气动微粉喷射器、计量投料机组成,避免活性剂发生架料现象控制投加量与烟气充分混合。
6.根据权利要求1与权利要求4所述的一种避免二噁英生成的炉内控制方法,其特征在于,所述的卤素反应活性剂反应装置中收集装置位于喷枪下方,由耐高温材质制成的收集斗与卸料口组成,对反应后活性剂进行收集与排出。
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