CN113332844A - 一种催化分解二噁英处理垃圾的方法 - Google Patents
一种催化分解二噁英处理垃圾的方法 Download PDFInfo
- Publication number
- CN113332844A CN113332844A CN202110723331.8A CN202110723331A CN113332844A CN 113332844 A CN113332844 A CN 113332844A CN 202110723331 A CN202110723331 A CN 202110723331A CN 113332844 A CN113332844 A CN 113332844A
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- Prior art keywords
- flue gas
- garbage
- dioxin
- catalyst
- catalytic
- Prior art date
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Images
Classifications
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- F23G5/00—Incineration of waste; Incinerator constructions; Details, accessories or control therefor
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Abstract
本发明涉及一种催化分解二噁英处理垃圾的方法,更具体地,属于一种将垃圾进行焚烧、焚烧后的烟气依次的进行二次燃烧、脱硫、催化分解有机高分子烃和焦油、固定床催化分解二噁英,以及进一步进行烟气净化达标处理的垃圾处理方法;本发明公开了分解二噁英的高活性催化剂的制取方法;本发明中烟气排放的二噁英浓度低于国标(GB18485‑2014)《生活垃圾焚烧污染控制标准》规定的0.1ngTEQ/m3指标;本发明所采用的设备属于工业上公知的设备,运行可靠,技术成熟,结构简单,维修方便,造价低廉,本发明具备好的新颖性、创造性和工业实用性。
Description
技术领域
本发明涉及垃圾焚烧的方法,具体地涉及采用催化分解烟气中的二噁英处理垃圾的方法,属于环保技术领域。
背景技术
生活垃圾(包含废塑料、废橡胶、纸屑、木、布、根、叶、草)和有机废弃物在焚烧中不可避免的产生二噁英有害气体物质;二噁英属于氯代三环芳烃类化合物,是多氯化二苯并二恶英(PCDD)和氯化二苯并呋喃 (PCDF)的统称,是由200多种异构体、同系物等组成的混合体;二噁英在标准状态下是无色无味固态物质,熔点为303~305℃,化学性质稳定,在水中溶解度很低,难溶于水,常温下不挥发,难氧化、分解或水解,二噁英的毒性又很强,是一级致癌、致畸物质,对人体损害极大;二噁英是垃圾焚烧中产生的主要污染有毒物质;目前,500吨/日以上经济规模的垃圾焚烧广泛采用3T+E技术以控制二噁英(PCDD/F)在炉膛内生成,由于我国垃圾原料的多样性,以及炉膛内焚烧温度不均匀性,3T+E技术只能减少二嗯英的生成;目前,垃圾焚烧除去二噁英主要采用活性炭吸附烟气中的二噁英,最后通过袋式收尘器收集去除二噁英,吸附了二噁英和尘埃的活性炭也称为生活垃圾焚烧飞灰,属于《国家危险废物名录》口中的HW18类危险废物,对环境和人体健康有极大的伤害;根据《生活垃圾焚烧控制标准》 (GB18485-2014)规定:“生活垃圾焚烧飞灰应该按危险废弃物管理”,通常采用固化或热熔融的高成本处理方法对飞灰进行无害化处理;利用 3T+E高温分解二噁英或采用活性炭吸附处理二噁英的工艺流程长,处理设备复杂,成本高,极大地增加了垃圾处理的综合运行成本;
特别地,采用3T+E高温分解二噁英的方法,具有工程投资大,工艺流程长、温度高达750-1000℃,能耗大和操作复杂的严重问题,不适合国家振兴乡村中广泛推广的急需的小型(如一个村的垃圾一般在是3-10吨/ 日,一个乡镇的垃圾一般在100吨/日以下)垃圾焚烧系统;
现有技术已公开了一些解决这方面问题的技术方案,例如:本发明申请人在授权的USP6,133,491《一种从生活垃圾和/或有机废弃物制取烃类的方法和设备》,在授权的ZL200710130127.5《一种连续化处理生活垃圾的方法》和在授权的ZL98117823.5《用生活垃圾和或有机废弃物制取烃类的方法和设备》中,都公开了采用无氧条件下的非焚烧法的干馏方式处理生活垃圾,有不产生二噁英的优点,存在的问题是:以上方法属于垃圾的间接加热方式,间接加热的传热效果差,垃圾干馏的耗能高,通常的需要额外补充燃料给干馏设备加热才能使使垃圾完全分解,极大的增加了垃圾处理的运行成本;
有关催化剂分解烟气中二噁英的方法已有报导,在CN112191267A《一种催化氧化脱除烟气中二噁英的蜂窝式催化剂及其制备方法》,以及在 CN111151263A《一种脱除烟气中二噁英的催化剂及其制备方法和应用》中,是将活性组分、载体和粘合剂先混合在一起,然后进行混炼、陈化成泥料、成型、干燥和煅烧而成;催化剂孔隙的表层成分与其内部成分是一致,即催化剂表面含有大量的非活性的载体成分和催化剂内部含有大量的昂贵的活性组分,催化反应主要发生在催化剂孔隙表层,由于催化剂孔隙表层含有大量的非活性的载体成分,其孔隙表层的活性组分含量低、活性组分分布量小,导致催化剂的催化效果差,催化剂活性组分利用率低;烟气中的二噁英只能与蜂窝状或颗粒状催化剂孔隙表层的活性组分接触而发生催化分解,而催化剂内部含有的大量昂贵的活性组分无法起到催化作用;通常地,一旦催化剂表面“中毒”失效,整体催化剂将被丢弃,包含在催化剂内部的昂贵的活性组分也被丢弃掉,造成很大的催化剂资源浪费,增大了垃圾处理中气体净化达标处理的综合成本,这是现有公开的颗粒状或蜂窝状二噁英分解催化剂的缺陷。
通常地,中小型垃圾焚烧装置大多属于缺氧焚烧炉,垃圾在焚烧中供氧不足,垃圾燃烧不均匀,导致烟气中含有大量的高沸点有机高分子焦油和重烃物质,在烟气后工序降温过程中,烟气中的气相焦油分子和重烃分子易冷凝成粘稠液体和焦油,粘稠液体和焦油易堵塞设备、管道,以及易堵塞后工序的二噁英分解催化剂的表面孔隙,导致催化剂“中毒”失效,极大地影响垃圾焚烧烟气净化处理;对于垃圾焚烧中的烟气治理,现有公开的催化燃烧废气净化装置、UV光解废气净化器和等离子废气净化器只能分解室温下易挥发性有机物(VOCs),即在常温下处于气相的小分子非甲烷碳氢化合物(简称NMHCs)、气相含氧有机化合物、气相卤代烃、气相含氮有机化合物和气相含硫有机化合物,很难彻底分解室温下的粘稠液体和焦油,导致烟囱排放的气体中含有发臭气体严重污染大气,影响破坏周围居民的生存环境。
发明内容
本发明的目的就是要弥补现有技术的缺乏,提供在较低温度和催化剂的作用下将烟气中的二噁英彻底分解变成二氧化碳、水和氯化氢,再通过碱液喷淋除去氯化氢的垃圾处理方法。
本发明一种催化分解二噁英处理垃圾的方法,包括以下步骤:
(1)将所述垃圾经加料装置1装入焚烧炉2内并密闭焚烧炉2;
(2)将空气送入焚烧炉2内,对垃圾进行焚烧,焚烧炉2内的温度控制在180-500℃,压力为常压,将垃圾进行焚烧至烬;
(3)垃圾焚烧后产生的灰渣靠重力落入焚烧炉2底部的灰渣箱9内后排出;将垃圾焚烧产生的烟气从焚烧炉2烟气出口排出;
(4)将焚烧炉2排出的烟气引入二次燃烧室3内,对烟气中的焦油、高分子有机气体和其它有害气体进行焚烧,消除焦油对催化固定床5内催化剂孔隙的堵塞,二次燃烧室3内的烟气出口温度控制在300-600℃;
(5)将二次焚烧室3排出的烟气引入装有蜂窝状或颗粒状脱硫剂的脱硫装置4内,用脱硫剂除去烟气中的含硫物质;
(6)将脱硫装置4排出的烟气引入催化固定床5内,催化固定床5内配置有进一步分解有机物和焦油的蜂窝状催化剂,以及装有分解二噁英的蜂窝状的MH-1助催化剂和/或HM-2催化剂,以及公知的分解二噁英催化剂,催化固定床5内的催化反应温度控制在240-390℃,烟气的空速为 1000-20000/h,烟气中的二噁英在催化剂作用下被分解成为二氧化碳,水和氯化氢,烟气中的高分子有机物和焦油被催化裂解成小分子的有机物 (VOCS);
(7)将催化固定床5内的烟气排出,输送到常规的废气净化处理装置6 中,对烟气中的尘埃和有害气体进行进一步净化处理;如采用碱液喷淋塔,利用酸碱中和反应,除去烟气中的酸性气,以及除去二噁英分解产生的氯化氢;采用布袋除尘器对烟气中夹带的尘埃和颗粒物进行拦截去除,采用公知的脱硝技术设备,对烟气中的氮氧化物(NOx)进行催化(SCR)或非催化处理(SNCR)将氮氧化物转化成N2;采用催化燃烧废气处理装置,进一步除去烟气中微量的小分子有机物(VOCS);
(8)将废气净化处理装置6排出的达标气体通过引风机7和烟囱8排入大气。
所述的脱硫装置4内的脱硫剂,是颗粒状或蜂窝状的氧化铁脱硫剂、颗粒状或蜂窝状的氧化锌脱硫剂或其它公知的烟气脱硫剂;
所述的催化固定床5内的裂解有机烃、焦油的颗粒状或蜂窝状催化剂,属于常规的烃类热裂解催化剂商品,SR-1催化剂属于本发明所采用的其中之一的催化剂;
所述的催化固定床5内装有分解二噁英的颗粒状或蜂窝状催化剂,所述的二噁英的颗粒状或蜂窝状催化剂,包括:MH-2催化剂和/或HM-1助催化剂,以及公知的分解二噁英催化剂;
实施本发明一种催化分解二噁英处理垃圾的方法所采用的设备,主要由加料装置1、焚烧炉2、灰渣箱(9)、二次燃烧室3、脱硫装置4、催化固定床5、气体净化处理装置6,引风机7和烟囱8组成;
所述的加料装置1,属于公知的螺旋进料机、往复式推料机,以及带密封盖的料仓,该料仓与焚烧炉炉膛之间设置卸料阀门;
所述的焚烧炉2,可以选用立式焚烧炉、卧式焚烧炉、回转窑式焚烧炉,炉排式焚烧炉、流化床式焚烧炉、CAO焚烧炉或缺氧燃烧的热解干馏气化炉;
所述的二次燃烧室3,属于常规的燃烧炉,配置有燃油燃烧器或燃气燃烧器和燃烧空气的进口;
所述的脱硫装置4,属于常规的工业气体脱硫塔、固定床脱硫设备或干法脱硫设备,脱硫剂属于颗粒状、条状或蜂窝状的固体,如氧化锌脱硫剂、氧化铁脱硫剂和氧化镁脱硫剂......,将固体脱硫剂放入脱硫设备内的筛孔板上,如氧化锌脱硫剂发生下列化学反应:
H2S+ZnO=ZnS+H2O;
SO3+ZnO=ZnSO4
所述的催化固定床5,属于公知的工业上使用的“气体--固体”催化反应固定床(见图2),是圆柱形或方体的壳体10,壳体10上配置有气体进口13和气体出口11,壳体10内部配置带孔的隔板12,隔板12上面放置颗粒状或蜂窝状催化剂,烟气经过气体进口12,穿过催化剂(14、15、 16)发生催化反应,发生催化反应后的气体经气体出口11从催化固定床5 排出;
所述的气体净化处理装置6,属于常规的烟气净化处理设备,包括:碱液喷淋塔、布袋除尘器、公知的脱硝催化(SCR)或非催化(SNCR)技术设备,将氮氧化物(NOX)转化成N2,和催化燃烧废气处理装置;
本发明中所述的垃圾,包括生活垃圾、医疗垃圾,厨余垃圾、农林有机垃圾、废塑料、废橡胶、废弃电子产品、废弃服装、电路板、皮革、废药材、其它有机废弃物和工业有机废料。
本发明烟气中的二噁英在催化剂作用下被分解成为二氧化碳,水和氯化氢,其化学反应原理如下:
采用碱液(烧碱、石灰乳....)喷淋塔,将烟气中的酸性气体(NO2、H2S、 SO3......)除去,如二噁英分解产生的氯化氢,用碱液除去,发生如下酸碱中和反应;
HCL+Ca(OH)2→CaCL2+H2O
H2S+Ca(OH)2→CaS+H2O
NO2+Ca(OH)2→Ca(NO3)2+H2O
SO3++Ca(OH)2→CaSO4+H2O
SO2++Ca(OH)2→CaSO3+H2O
在本发明的催化固定床5中,装有蜂窝状或颗粒状分解二噁英的MH-1 助催化剂和/或MH-2催化剂,以及装有进一步分解有机烃和焦油的SR-1 催化剂,SR-1催化剂已在本申请人授权的ZL 98117823.5《用生活垃圾和 /或有机废弃物制取烃类的方法和设备》和U.S.Pat.No.6,133,491 《Process and apparatus for producing hydrocarbons fromresidential trash or waste and/or organic waste materials》中公开;
在本发明的催化固定床5中,同时地发生下列二种类型的催化反应:
第一种类型:在SR-1催化剂作用下,烟气中的有机烃类、焦油能够裂解变成为小分子的烃类(H2、C1-C5)气体,SR-1催化剂对焦油、高分子烃类的裂解具有好的选择活性,属于吸热反应,提高反应温度,能加速有机高分子烃类、焦油的分解;
第二种类型:烟气中的二噁英在MH-1助催化剂和/或MH-2催化剂作用下,二噁英被氧化变成二氧化碳(CO2)、氯化氢(HCL)和水(H2O),属于放热反应,降低反应温度,有利于二噁英的分解;
本发明中,利用SR-1型催化剂先将烟气中的高分子烃类或焦油分解成室温下易挥发性小分子有机物(VOCs),防止烟气中的焦油堵塞在二噁英分解催化剂表面,遏制二噁英分解催化剂“中毒”和失效,确保催化固定床5内的烟气进出流畅,这是本发明的特征之一;
化学反应平衡原理,在上述催化固定床5中,二噁英被氧化变成二氧化碳(CO2)、氯化氢(HCL)和水(H2O),属于放热反应,降低温度,有利于化学反应平衡向着生成物二氧化碳(CO2)、水和氯化氢(HCL)的方向进行,而高分子烃类、重油变成为小分子烃(H2、C1-C5)的裂解属于吸热反应,提高反应温度有利于高分子烃类、重油的快速热解;因此,在催化固定床5内,二噁英被氧化变成二氧化碳(CO2)、氯化氢(HCL)和水 (H2O)放出的热量及时的供给高分子烃类、焦油发生催化裂解所需的热量,上述二种催化反应具有好的热量优势相补利用,具有相互加速催化反应速度的优点,这,是本发明的基本特征之一。
本发明的MH-1助催化剂主要由活性组分、载体骨架和粘结剂构成,其制备方法包括以下步骤:
(1)将40-60%(wt%)活性氧化铝(a-AL2O3)粉末(商品),60-40(wt%) 酸化处理后的精制硅藻土粉末(商品),按照100%重量百分比例(wt%) 进行分别的称重配料、搅拌混合均匀,得到载体;
(2)将摩尔比为2∶3的Fe(NO3)3(40mmol/L-Mn(NO3)2(60mmol/L)混合液在330K下用氨水(9%)调节PH=9,得到棕黑色沉淀物,将沉淀物洗涤后, 330K下干燥2h,420K下烘干24h,粉粹成80目以上细度,得到铁锰复合氧化物(FeO/MnO),属于一种分解二噁英的催化剂活性组分;
(3)将上述(1)制取的30-35%(wt%)载体,上述(2)制取的35-45% (wt%)铁锰复合氧化物(FeO/MnO),10-15%硫酸镁(MgSO4),以及加入3-5% (wt%)硅或铝粘合剂如水玻璃(商品)混合在一起,搅拌均匀,依照公知的蜂窝状或颗粒状催化剂成型方法,经混合、成型、干燥、在600-650℃煅烧24h,得到蜂窝状或颗粒状的MH-1助催化剂;
本发明的MH-2催化剂主要由活性组分、载体骨架和粘结剂构成,其制备方法包括以下步骤:
(1)将40-60%(wt%)活性氧化铝(a-AL2O3)粉末(商品),60-40(wt%) 酸化处理后的精制硅藻土粉末(商品),按照100%重量百分比例(wt%) 进行分别的称重配料、搅拌混合均匀,得到载体;
(2)将上述(1)制取的90-92%(wt%)载体,以及加入5-8%(wt%)硅或铝粘合剂如水玻璃(商品)混合在一起,搅拌均匀,依照公知的蜂窝状或颗粒状催化剂成型方法,经混合、成型、干燥、在600-650℃煅烧24h,得到蜂窝状或颗粒状的载体;
(3)将偏钒酸铵(NH4VO3)溶于60℃的水中,用氨水调节PH=9,配成10%(wt%)偏钒酸铵溶液,将钨酸铵(NH4)10W12O41)溶液于水中配成10%(wt%) 的钨酸铵溶液,然后,将钨酸铵溶液与偏钒酸铵溶液按照摩尔比为1∶3的比例进行混合,搅拌均匀成为混合液体;将上述(2)制得的蜂窝状或颗粒状载体放入所述的混合液体内进行浸渍,让蜂窝状或颗粒状载体在偏钒酸铵和钨酸铵的溶液吸附至饱和,然后将所述的蜂窝状或颗粒状载体在 80℃下脱水干燥,在600-650℃煅烧炉内下进行真空或负压抽风加热12h,负载在蜂窝状或颗粒状载体孔隙额表面的偏钒酸铵和钨酸铵受热后发生如下分解反应:
2NH4VO3=V2O5+H2O+2NH3
(NH4)10W12O41=12WO3+10NH3+5H2O
煅烧炉内产生的氨气和水分受热后挥发,热分解最后产生固态的V2O5和WO3被均匀的高密度的粘结在所述的蜂窝状或颗粒状载体孔隙的表层,最后得到MH-2型催化剂;
可以多次的重复的将所述的蜂窝状或颗粒状载体放入偏钒酸铵溶液和钨酸铵溶液内浸渍、然后进行干燥和煅烧,增大催化剂活性组分V2O5和 WO3吸附和粘结分布在所述蜂窝状或颗粒状载体孔隙表层的厚度,提高活性组分V2O5和WO3的催化时间和催化效益;
在本发明中,FeO/MnO和MgSO4是MH-1助催化剂中的活性组分,起分解二噁英的助催化作用;在MH-2催化剂中的V2O5和WO3是活性组分,起到分解二噁英的作用;活性氧化铝(a-AL2O3)和精制硅藻土是催化剂载体(或称活性组分的骨架载体),硅或铝粘合剂如水玻璃(商品)是粘结剂;
本发明蜂窝状MH-1助催化剂和MH-2催化剂的物理性质:根据需要可以制成的正方体或长方体的外形尺寸:150mm×150mm×150mm、100mm× 100mm×150mm、100mm×100mm×100mm或50mm×50mm×100mm;蜂窝状催化剂的孔数按照7孔/cm2至25孔/cm2,孔径在3-5mm选用,1.0-1.3mm壁厚,容重0.6-0.8g/cm3,比表面积100-180m2/g,轴向抗压强度≥0.65MPa,工作温度为160--350℃;蜂窝状催化剂单位表面积的孔数少或孔径大、风量就大,风阻就小,反之亦然;根据设计的风量和风阻力要求,去选择合适的催化剂孔径和固定床中配置的蜂窝状催化剂的数量;
本发明中,将MH-1助催化剂和/或MH-2催化剂和SR-1催化剂配置在催化固定床5内的方式,采用常规的固定床内配置催化剂的方法,见附图 2;
烟气中的二氧化硫(SO2)与二噁英分解催化剂的活性组分V2O5接触后发生如下氧化--还原反应,即SO2+V2O5=SO3+2VO2,V2O5属于强氧化剂,V2O5与SO2后被还原变成VO2,二噁英分解催化剂的活性组分(V2O5)被“中毒”失效,在二噁英催化分解反应发生之前,将烟气中的硫化物(如H2S、SO2) 除去,是确保二噁英催化分解成二氧化碳、水和氯化氢的关键;
本发明中,二次燃烧室3燃烧后的烟气,采用脱硫装置4除去烟气中的含硫物质,遏制了含硫物质(如H2S、SO2)使固定床5内的催化剂活性组分(V2O5)被“中毒”失效,确保后工序二噁英在催化固定床5内的催化分解反应的正常进行,这是本发明的特征之一;
在催化固定床5中,让烟气分别穿过叠层配置的蜂窝状MH-1助催化剂和/或MH-2催化剂,增加了二噁英接触催化剂活性组分的面积,提高了二噁英在单位时间内的分解效果;特别地,MH-1助催化剂和MH-2催化剂的孔隙表层材料成分是浸渍、煅烧粘结后形成的催化活性组分,不含非活性的载体成分,极大地提高了催化剂比表面积的活性组分的量,加快了二噁英催化分解速度效果,载体中不含昂贵的活性组分成分,极大地降低了催化剂的制造成本,这是本发明的特征之一;
本发明对分解二噁英的MH-1助催化剂和MH-2催化剂,做如下催化活性评价测试:
按照本发明实施例同样的操作方法,在垃圾焚烧生产状况(如温度、压力,烟气空速和垃圾焚烧量)一致的情况下,对烟气进行二次采样和测试:
1.在催化固定床5内不放置催化剂情况下,在垃圾焚烧过程中,利用众瑞ZR-3720型二噁英烟气采样器,对烟囱排放的烟气进行120分钟的连续采样,经过分析测得烟气中二噁英的浓度为3.2ngTEQ/m3;
2.在催化固定床5内放置MH-1助催化剂和MH-2催化剂情况下(详见图 2),在垃圾焚烧过程中,利用众瑞ZR-3720型二噁英烟气采样器,对烟囱排放的烟气进行120分钟的连续采样,分析测得烟气中二噁英的浓度为 0.051ngTEQ/m3(见实施例);
结论:MH-1助催化剂和MH-2催化剂分解二噁英的催化活性为99.98% (即0.051/3.2)。
本发明方法的先进性和优点是:
1.本发明制取的二噁英分解催化剂,其成分不含贵重金属,不易“中毒”失效,原料来源广泛,制造成本低;特别地,催化剂表面不含非活性组分的载体成分,催化剂表面的催化活性成分含量高,活性组分密度大,催化活性好,极大地降低了生活垃圾焚烧去除二噁英的综合成本;
2.本发明在二噁英催化分解之前,对烟气进行了脱焦油和脱硫,解决和消除了烟气中的高分子烃和焦油使二噁英催化剂孔隙“中毒”失效的问题;
3.本发明制取的MH-1助催化剂和MH-2催化剂,能将烟气中的二噁英浓度降低到0.051ngTEQ/m3,低于国标0.1ngTEQ/m3的指标,催化活性达到 99.98%,具备好的工业实用性;
4.本发明所采用的设备属于工业上公知的设备,运行可靠,技术成熟,结构简单,维修方便,造价低廉;
5.本发明能使垃圾焚烧中烟气排放的二噁英浓度达到国家规定的标准,能将垃圾完全焚烧至烬,实行垃圾的无害化,具有好的工业实用性。
附图说明
图1是本发明的方法工艺流程图;
图2是本发明催化固定床内催化剂配置结构示意图;
在图1和图2中,1-加料装置,2-焚烧炉,3-二次燃烧室,4-脱硫装置, 5-催化固定床,6-废气净化处理装置,7-引风机,8-烟囱,9-灰渣箱,10- 催化固定床的壳体,11-催化固定床的气体出口,12-筛孔板,13-催化固定床的气体进口,14-SR-1催化剂,15-MH-1助催化剂,16-MH-2催化剂;
具体实施方式
下面结合附图和实施例对本发明作进一步说明,在本发明的一个实施例中,但本发明不受其限制。
实施例
如图1和图2所示,将1500Kg生活垃圾经加料装置1装入焚烧炉2 (立式焚烧炉,圆柱形炉体,炉堂内直径1800mm,高2500mm,装料容积为 5.89m3)内,并密闭焚烧炉2的加料口;启动2300m3/h引风机7,用PLC 调节通风量,焚烧炉2烟气出口管上配置氧气含量显示报警器,控制烟气中的氧含量在6-7%,将适量的空气送入垃圾焚烧炉2内,对垃圾进行焚烧,焚烧炉2内的温度控制在240-400℃,压力为常压或微负压,在此温度压力范围内,经过152分钟,焚烧炉2内的垃圾被焚烧至烬,垃圾焚烧后的灰渣落入焚烧炉2底部的灰渣箱9内定期排出;垃圾焚烧的烟气从焚烧炉 2中排出后引入二次燃烧室3内进行二次焚烧,采用甲醇燃烧机对烟气进行二次焚烧,将烟气排出的温度控制在390-520℃,烧掉烟气中的大部分焦油和有机烃,防止烟气中的焦油对后工序设备和固体催化剂的阻塞;将二次燃烧室3排出的烟气引入装有颗粒状氧化铁脱硫剂的脱硫装置4内,用脱硫剂除去烟气中的H2S、SO3和SO2,防止硫化物对催化固定床5内催化剂的中毒危害,将脱硫装置4排出的烟气引入催化固定床5内,催化固定床5内配置有SR-1催化剂、MH-1助催化剂和MH-2催化剂,参见图2;催化固定床5内的催化反应温度控制在300-390℃,烟气空速为 1800-2000/h,烟气先与SR-1催化剂接触,将烟气中的有机高分子烃类、焦油被SR-1催化剂裂解,然后,烟气流动穿过MH-1助催化剂和MH-2催化剂,在MH-1助催化剂和MH-2催化剂作用下,烟气中的二噁英被分解成为二氧化碳,水和氯化氢,将催化固定床5内的气体引入到气体净化处理装置6内进行进一步处理:包括:先将催化固定床5内的气体输送到石灰乳喷淋塔(10%的氧化钙乳液)内进行气体脱酸处理,除去烟气中的HCL、 CO2、NO2、SO2、H2S和尘埃;从碱液喷淋塔排出的气体经过“气--液”分离器脱水后,气体引入催化燃烧废气净化装置内,将烟气中易挥发性有机物 (VOCs)低温氧化燃烧变成为二氧化碳和水,将催化燃烧废气净化装置排出的气体输送到脉冲布袋除尘器中拦截微细的颗粒物和尘埃,将脉冲布袋除尘器排出的气体通过引风机7和烟囱8排入大气,将垃圾焚烧后的无机残渣从灰渣箱9中排出,此灰渣经过磁选机回收金属、粉粹、配料、模压制砖;
在垃圾焚烧的152分钟过程中,利用众瑞ZR-3720型二噁英烟气采样器,对烟囱排出的气体进行了连续的120分钟的二噁英生产实地采样,采用Thermo DFS磁式质谱仪(GC/MS)进行分析,根据《废气二噁英类的测定同位素稀释高分辨率气相色谱--高分辨质谱法》(HJ 77.-2008)规定进行二噁英的分析检测。
经过上述工艺过程得到如下主要数据和结果:
生活垃圾:1500KG:
垃圾物理性质(Wt%):水分36.6%,总固体类(包括碳水化合物、废塑料、废橡胶、、金属、无机物等)63.4%,PH值为8.1,垃圾容重为0.49吨/m3;
1500kg垃圾占有容积:3.06m3;
焚烧炉2的炉膛装料容积:5.89m3;
垃圾元素分析:H 7.43%(wt%);C 24.5%(wt%);050.27%(wt%); S 0.35%;N1.6%(wt%);金属及无机物15.85%(wt%);
焚烧炉2内:焚烧温度280-480℃,常压,空气通风量1500-2000m3/h;
垃圾焚烧处理时间:152分钟;
无机残渣及金属:237.8kg;
残渣及金属的平均密度:2.12吨/m3或0.47m3/吨;
237.8kg残渣及金属占体积:0.11m3[即0.47×0.2378];
垃圾炉渣残烧率(V%):3.65%[(0.11÷3.06)×100%];
垃圾减容率(V%):96.35%[100%-3.65%];
二次燃烧室3:
燃料:甲醇;
烟气排出温度:390-520℃
脱硫装置4内的脱硫剂参数:
颜色及外观:红褐色四边形柱形颗粒,配置在固定床内的筛孔板上;
脱硫剂成分:氧化铁和氧化锌的复合物;
规格(mm):Φ5X5~15mm;
强度(N/cm):≥50;
堆密度(kg/L):0.75-0.8;
穿透硫容:≥30%;
产品原粒度穿透硫容:≥30%,按HG/T4354-2012标准检测穿透硫容 31.5%;
硫化氢脱硫剂中以铁元素计,含量≥30%
以氧化铁计,含量≥50%;
催化固定床5内催化剂参数:
烃类和焦油裂解催化剂:SR-1,蜂窝状,外形尺寸15cm×15cm×15cm;二噁英分解催化剂:MH-1助催化剂和MH-2催化剂,孔密度:21孔/cm2,上述催化剂在催化固定床中的配置见图2;
催化反应温度:300-390℃;
催化固定床5内压力:0.03-0.08MPa;
催化反应空速:1800-2000h-1;
烟囱排放口的烟气中的二噁英测试参数:
烟气中的平均含氧量:6.5%;
二噁英采样仪器:众瑞ZR-3720型二噁英烟气采样器;
二噁英分析仪器:Thermo DFS磁式质谱仪(GC/MS);
烟气采样时间:120分钟;
排出烟气中的二噁英测试结果:0.051ngTEQ/m3,低于国标(GB18485-2014) 《生活垃圾焚烧污染控制标准》中规定的二噁英类小于0.1ngTEQ/m3。
Claims (4)
1.一种催化分解二噁英处理垃圾的方法,包括以下步骤:
(1)将所述垃圾经加料装置1装入焚烧炉2内并密闭焚烧炉2;
(2)将空气送入焚烧炉2内,对垃圾进行焚烧,焚烧炉2内的温度控制在180-500℃,压力为常压,将垃圾进行焚烧至烬;
(3)垃圾焚烧后产生的灰渣靠重力落入焚烧炉2底部的灰渣箱9内后排出;将垃圾焚烧产生的烟气从焚烧炉2烟气出口排出;
(4)将焚烧炉2排出的烟气引入二次燃烧室3内,对烟气中的焦油、高分子有机气体和其它有害气体进行焚烧,消除焦油对催化固定床5内催化剂孔隙的堵塞,二次燃烧室3内的烟气出口温度控制在300-600℃;
(5)将二次焚烧室3排出的烟气引入装有蜂窝状或颗粒状脱硫剂的脱硫装置4内,用脱硫剂除去烟气中的含硫物质;
(6)将脱硫装置4排出的烟气引入催化固定床5内,催化固定床5内配置有进一步分解有机物和焦油的蜂窝状催化剂,以及装有分解二噁英的蜂窝状的MH-1助催化剂和/或HM-2催化剂,以及公知的分解二噁英催化剂,催化固定床5内的催化反应温度控制在240-390℃,烟气的空速为1000-20000/h,烟气中的二噁英在催化剂作用下被分解成为二氧化碳,水和氯化氢,烟气中的高分子有机物和焦油被催化裂解成小分子的有机物(VOCS);
(7)将催化固定床5内的烟气排出,输送到常规的废气净化处理装置6中,对烟气中的尘埃和有害气体进行进一步净化处理;如采用碱液喷淋塔,利用酸碱中和反应,除去烟气中的酸性气,以及除去二噁英分解产生的氯化氢;采用布袋除尘器对烟气中夹带的尘埃和颗粒物进行拦截去除,采用公知的脱硝技术设备,对烟气中的氮氧化物(NOx)进行催化(SCR)或非催化处理(SNCR)将氮氧化物转化成N2;采用催化燃烧废气处理装置,进一步除去烟气中微量的小分子有机物(VOCS);
(8)将废气净化处理装置6排出的达标气体通过引风机7和烟囱8排入大气。
2.根据权利要求1所述的一种催化分解二噁英处理垃圾的方法,其特征在于:所述的MH-1助催化剂主要由活性组分、载体骨架和粘结剂构成,其制备方法包括以下步骤:
(1)将40-60%(wt%)活性氧化铝(a-AL2O3)粉末(商品),60-40(wt%)酸化处理后的精制硅藻土粉末(商品),按照100%重量百分比例(wt%)进行分别的称重配料、搅拌混合均匀,得到载体;
(2)将摩尔比为2∶3的Fe(NO3)3(40mmol/L-Mn(NO3)2(60mmol/L)混合液在330K下用氨水(9%)调节PH=9,得到棕黑色沉淀物,将沉淀物洗涤后,330K下干燥2h,420K下烘干24h,粉粹成80目以上细度,得到铁锰复合氧化物(FeO/MnO),属于一种分解二噁英的催化剂活性组分;
(3)将上述(1)制取的30-35%(wt%)载体,上述(2)制取的35-45%(wt%)铁锰复合氧化物(FeO/MnO),10-15%硫酸镁(MgSO4),以及加入3-5%(wt%)硅或铝粘合剂如水玻璃(商品)混合在一起,搅拌均匀,依照公知的蜂窝状或颗粒状催化剂成型方法,经混合、成型、干燥、在600-650℃煅烧24h,得到蜂窝状或颗粒状的MH-1助催化剂。
3.根据权利要求1所述的一种催化分解二噁英处理垃圾的方法,其特征在于:所述的MH-2催化剂主要由活性组分、载体骨架和粘结剂构成,其制备方法包括以下步骤:
(1)将40-60%(wt%)活性氧化铝(a-AL2O3)粉末(商品),60-40(wt%)酸化处理后的精制硅藻土粉末(商品),按照100%重量百分比例(wt%)进行分别的称重配料、搅拌混合均匀,得到载体;
(2)将上述(1)制取的90-92%(wt%)载体,以及加入5-8%(wt%)硅或铝粘合剂如水玻璃(商品)混合在一起,搅拌均匀,依照公知的蜂窝状或颗粒状催化剂成型方法,经混合、成型、干燥、在600-650℃煅烧24h,得到蜂窝状或颗粒状的载体;
(3)将偏钒酸铵(NH4VO3)溶于60℃的水中,用氨水调节PH=9,配成10%(wt%)偏钒酸铵溶液,将钨酸铵(NH4)10W12O41)溶液于水中配成10%(wt%)的钨酸铵溶液,然后,将钨酸铵溶液与偏钒酸铵溶液按照摩尔比为1∶3的比例进行混合,搅拌均匀成为混合液体;将上述(2)制得的蜂窝状或颗粒状载体放入所述的混合液体内进行浸渍,让蜂窝状或颗粒状载体在偏钒酸铵和钨酸铵的溶液吸附至饱和,然后将所述的蜂窝状或颗粒状载体在80℃下脱水干燥,在600-650℃煅烧炉内下进行真空或负压抽风加热12h,煅烧炉内产生的氨气和水分受热后挥发,热分解最后产生固态的V2O5和WO3被均匀的高密度的粘结在所述的蜂窝状或颗粒状载体孔隙的表层,最后得到MH-2型催化剂。
4.根据权利要求1所述的一种催化分解二噁英处理垃圾的方法,其特征在于:所述的垃圾,包括生活垃圾、医疗垃圾,厨余垃圾、农林有机垃圾、废塑料、废橡胶、废弃电子产品、废弃服装、电路板、皮革、废药材、其它有机废弃物和工业有机废料。
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