CN108160665B - 废集成线路板热质协同绿色资源化方法 - Google Patents
废集成线路板热质协同绿色资源化方法 Download PDFInfo
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Abstract
废集成线路板热质协同绿色资源化方法,包括炭化裂解系统、破碎分选系统、气化裂解系统和热值利用及综合回收系统。与现有技术相比,炭化裂解系统可实现废集成线路板中有机质的干馏裂解,将碳、氢等元素转化成燃料化的炭化裂解气和裂解油,本发明的炭化裂解气燃烧的热量供炭化裂解所需的能源,实现自热炭化裂解;炭化裂解产物进行破碎分选,解决传统线路板直接破碎分选带来的难以破碎及有机物包覆金属问题,提高破碎效果及分选效果;气化裂解系统实现剩碳的综合利用,产生的气化裂解气可作为后续有价金属回收所需的热源,进一步提高热值的利用率。本发明具有热值利用率高、能耗低、金属回收率高,可实现有价金属短流程回收及烟气无污染等特点。
Description
技术领域
本发明涉及废集成线路板综合回收技术,特别是涉及采用炭化热解、气化热解、破碎分选和热源利用等技术,对废集成线路板的热量和有价物质进行协同绿色资源化的技术。
背景技术
集成线路板是电器电子产品的重要组成部分,是现代电器电子产业的基础。集成电路板主要由电子元器件、玻璃纤维增强环氧树脂和包括贵金属在内的许多金属材料组成的覆铜箔层压板。废集成线路板(WPCB)中含有如金银钯等等大量有价金属,其含量远高于原生矿藏,极具回收价值。同时,WPCB组成成分复杂,含有重金属、溴化阻燃剂等多种有害物质,传统的填埋和焚烧等回收方法会对生态系统在场严重损害。因此,WPCB具有资源性和污染性的双重属性。
目前,国内废集成线路板主要采用如下方法进行处置:
(1)冲天炉焚烧:该方法属于国家明文禁止的处置方式,该处置方法将带来巨大的环境污染,其中二噁英的污染严重。
(2)王水酸解:该方法也是国家明文禁止的方法,酸解过程中的酸气及处置产生的废液将带来严重的二次污染。
(3)等离子体裂解:该处置方式处于试验阶段,以真空或者氮气保护环境下,采用等离子体加热方式,将废线路板进行裂解,有机物直接裂解气化,避免二噁英产生,同时玻璃纤维等非金属形成非金属熔块,得到的合金块直接送冶炼并回收。由于其能耗太高,无法实现工业化推广。
(4)破碎分选:该方法是目前国家推荐的处置方式,在破碎分选之前,将废集成线路板的电子元器件进行摘除,在摘除过程中,某些技术采用热脱锡工艺,同时回收部分的锡。脱除元器件的裸板,采用破碎分选的方式实现线路板中的金属和非金属的分离,以分离介质的差异,分为水力分选、风力分选和静电分选。由于废线路板有机-无机-金属特殊结构,在破碎过程中容易产生粘连、包覆和不完全剥离等情况,因此,其金属回收率大约95%,同时能得到金属含量为1%左右的非金属粉末(树脂与玻璃纤维复合的粉磨)。以裸板金属含量20%计,则1万吨废线路板将产生8000吨非金属粉末,该非金属粉末属于危废,需要付费送相关处置企业进行处理,且相关处置企业基本上采取填埋方式处理。该方法的缺陷是金属回收率不高,产生的非金属粉末无法高值化利用,还需后续的危废处置。
(5)协同冶炼:该处置方式是国外主流处置方法,将废集成线路板与含铜污泥等工业废料进行协同冶炼,金属富集形成合金,进行下一步的回收提取,树脂在冶炼过程中作为燃料,玻璃纤维等非金属作为造渣剂进行处置。该方法具有处理能力强,二次污染轻等优点,但对协同冶炼装备和烟气处理装备要求很高,目前国内缺乏大型装备,无法进行工业化生产。
为了解决废集成线路板有机物热值利用及破碎分选难题,本发明提出炭化裂解技术,实现线路板有机物的裂解及炭化,将有机物中碳、氢等元素转化为燃料化的炭化裂解油和炭化裂解气,燃烧后提供热源,实现自热炭化裂解,炭化后的物料,由于有机物的裂解,很容易破碎和分选,提高金属回收率,炭化裂解得到的剩碳,采用气化裂解技术,实现碳和氢的进一步能源化,为后续的多金属回收提供热源。本发明实现废集成线路板的热质协同,在提高金属回收率的同时,大大降低能耗,避免二次污染。
发明内容
本发明的目的主要解决废集成线路板的高热值有机物利用和有价金属综合回收问题,同时集成线路板中玻璃纤维等无机物纯净分离并可实现综合利用,具有回收附加值高、能耗低、尾气达标排放等特点。
本发明所述的废集成线路板热质协同绿色资源化技术,主要包括如下主体技术部分:
(1)炭化裂解系统:包括炭化裂解、油气分离和炭化燃烧;废集成线路板通过炭化裂解得到炭化裂解渣和炭化裂解尾气,炭化裂解尾气通过油气分离得到炭化裂解油和炭化裂解气,炭化裂解气通过炭化燃烧得到燃烧尾气和热量,产生的热量直接为炭化裂解提供热源;
(2)破碎分选系统:包括破碎风选、磁选、电选;炭化裂解得到的炭化裂解渣进行破碎风选得到破碎料和粉尘,破碎料进行磁选得到铁磁性物质和非铁磁性物质,非铁磁性物质进行电选得到金属和非金属,铁磁性物质和非金属分别进行综合利用;
(3)气化裂解系统:包括气化裂解和水气分离;破碎风选得到的粉尘进行气化裂解得到气化裂解渣和气化裂解尾气,气化裂解尾气通过水气分离得到水和气化裂解气;
(4)热值利用及综合回收系统:包括蒸汽发生、尾气净化和多金属回收;炭化裂解油、炭化裂解气和气化裂解气进入蒸汽锅炉燃烧得到燃烧尾气和水蒸气,燃烧尾气进行尾气净化达标后排空,水蒸气供气化裂解和多金属回收所需的热源,气化裂解得到的裂解渣和电选得到的金属进行多金属回收得到有价金属及其化合物。
进一步地,在炭化裂解系统的炭化裂解过程中,控制氧分压≤6%,采用氮气保护,(即气氛为空气和氮气,且其中氧分压≤6%),炭化裂解温度为400~700℃,炭化裂解时间为1~3小时;在破碎分选系统的破碎风选过程中,破碎粒度小于100目;在气化裂解系统的气化裂解过程中,气化裂解温度为700~950℃,水蒸气/物料质量流量比为0.5~1,气化裂解时间为0.5~2小时;在热值利用及综合回收系统中,产生的燃烧尾气进行二次燃烧和急冷措施,保证二噁英达标排放。
与现有技术相比,炭化裂解系统可实现废集成线路板中有机质的干馏裂解,将碳、氢等元素转化成燃料化的炭化裂解气和裂解油,本发明的炭化裂解气燃烧的热量供炭化裂解所需的能源,实现自热炭化裂解;炭化裂解产物进行破碎分选,解决传统线路板直接破碎分选带来的难以破碎及有机物包覆金属问题,提高破碎效果及分选效果;气化裂解系统实现剩碳的综合利用,产生的气化裂解气可作为后续有价金属回收所需的热源,进一步提高热值的利用率。
本发明具有热值利用率高、能耗低、金属回收率高,可实现有价金属短流程回收及烟气无污染等特点。
附图说明
图1表示废集成线路板热质协同绿色资源化技术流程图
具体实施方式
实施例1
按照如下步骤进行回收:
(1)将废集成线路板通过炭化裂解得到炭化裂解渣和炭化裂解尾气,炭化裂解过程中,控制氧分压为6%,采用氮气保护,炭化裂解温度为400℃,炭化裂解时间为1小时;炭化裂解尾气通过油气分离得到炭化裂解油和炭化裂解气,炭化裂解气通过炭化燃烧得到燃烧尾气和热量,产生的热量直接为炭化裂解提供热源;
(2)炭化裂解得到的炭化裂解渣进行破碎风选得到破碎料和粉尘,破碎风选过程中,破碎粒度小于100目;破碎料进行磁选得到铁磁性物质和非铁磁性物质,非铁磁性物质进行电选得到金属和非金属,铁磁性物质和非金属分别进行综合利用;
(3)破碎风选得到的粉尘进行气化裂解得到气化裂解渣和气化裂解尾气,气化裂解温度为700℃,水蒸气/物料质量流量比为0.5,气化裂解时间为0.5小时;气化裂解尾气通过水气分离得到水和气化裂解气;
(4)炭化裂解油、炭化裂解气和气化裂解气进入蒸汽锅炉燃烧得到燃烧尾气和水蒸气,燃烧尾气进行二次燃烧和急冷的尾气净化,达标后排空,产生的水蒸气为气化裂解和多金属回收提供热源,气化裂解得到的裂解渣和电选得到的金属进行多金属回收得到有价金属及其化合物。
金属回收率为99.2%,烟气二噁英浓度为0.08ngTEQ/m3。
实施例2
按照如下步骤进行回收:
(1)将废集成线路板通过炭化裂解得到炭化裂解渣和炭化裂解尾气,炭化裂解过程中,控制氧分压为5%,采用氮气保护,炭化裂解温度为700℃,炭化裂解时间为3小时;炭化裂解尾气通过油气分离得到炭化裂解油和炭化裂解气,炭化裂解气通过炭化燃烧得到燃烧尾气和热量,产生的热量直接为炭化裂解提供热源;
(2)炭化裂解得到的炭化裂解渣进行破碎风选得到破碎料和粉尘,破碎风选过程中,破碎粒度小于100目;破碎料进行磁选得到铁磁性物质和非铁磁性物质,非铁磁性物质进行电选得到金属和非金属,铁磁性物质和非金属分别进行综合利用;
(3)破碎风选得到的粉尘进行气化裂解得到气化裂解渣和气化裂解尾气,气化裂解温度为950℃,水蒸气/物料质量流量比为1,气化裂解时间为2小时;气化裂解尾气通过水气分离得到水和气化裂解气;
(4)炭化裂解油、炭化裂解气和气化裂解气进入蒸汽锅炉燃烧得到燃烧尾气和水蒸气,燃烧尾气进行二次燃烧和急冷的尾气净化,达标后排空,产生的水蒸气为气化裂解和多金属回收提供热源,气化裂解得到的裂解渣和电选得到的金属进行多金属回收得到有价金属及其化合物。
金属回收率为99.5%,烟气二噁英浓度为0.11ngTEQ/m3。
实施例3
按照如下步骤进行回收:
(1)将废集成线路板通过炭化裂解得到炭化裂解渣和炭化裂解尾气,炭化裂解过程中,控制氧分压为3%,采用氮气保护,炭化裂解温度为450℃,炭化裂解时间为2小时;炭化裂解尾气通过油气分离得到炭化裂解油和炭化裂解气,炭化裂解气通过炭化燃烧得到燃烧尾气和热量,产生的热量直接为炭化裂解提供热源;
(2)炭化裂解得到的炭化裂解渣进行破碎风选得到破碎料和粉尘,破碎风选过程中,破碎粒度小于100目;破碎料进行磁选得到铁磁性物质和非铁磁性物质,非铁磁性物质进行电选得到金属和非金属,铁磁性物质和非金属分别进行综合利用;
(3)破碎风选得到的粉尘进行气化裂解得到气化裂解渣和气化裂解尾气,气化裂解温度为850℃,水蒸气/物料质量流量比为0.6,气化裂解时间为1小时;气化裂解尾气通过水气分离得到水和气化裂解气;
(4)炭化裂解油、炭化裂解气和气化裂解气进入蒸汽锅炉燃烧得到燃烧尾气和水蒸气,燃烧尾气进行二次燃烧和急冷的尾气净化,达标后排空,产生的水蒸气为气化裂解和多金属回收提供热源,气化裂解得到的裂解渣和电选得到的金属进行多金属回收得到有价金属及其化合物。
金属回收率为98.8%,烟气二噁英浓度为0.09ngTEQ/m3。
实施例4
按照如下步骤进行回收:
(1)将废集成线路板通过炭化裂解得到炭化裂解渣和炭化裂解尾气,炭化裂解过程中,控制氧分压为3%,采用氮气保护,炭化裂解温度为600℃,炭化裂解时间为1.5小时;炭化裂解尾气通过油气分离得到炭化裂解油和炭化裂解气,炭化裂解气通过炭化燃烧得到燃烧尾气和热量,产生的热量直接为炭化裂解提供热源;
(2)炭化裂解得到的炭化裂解渣进行破碎风选得到破碎料和粉尘,破碎风选过程中,破碎粒度小于100目;破碎料进行磁选得到铁磁性物质和非铁磁性物质,非铁磁性物质进行电选得到金属和非金属,铁磁性物质和非金属分别进行综合利用;
(3)破碎风选得到的粉尘进行气化裂解得到气化裂解渣和气化裂解尾气,气化裂解温度为750℃,水蒸气/物料质量流量比为0.8,气化裂解时间为1.5小时;气化裂解尾气通过水气分离得到水和气化裂解气;
(4)炭化裂解油、炭化裂解气和气化裂解气进入蒸汽锅炉燃烧得到燃烧尾气和水蒸气,燃烧尾气进行二次燃烧和急冷的尾气净化,达标后排空,产生的水蒸气为气化裂解和多金属回收提供热源,气化裂解得到的裂解渣和电选得到的金属进行多金属回收得到有价金属及其化合物。
金属回收率为99.1%,烟气二噁英浓度为0.06ngTEQ/m3。
实施例5
按照如下步骤进行回收:
(1)将废集成线路板通过炭化裂解得到炭化裂解渣和炭化裂解尾气,炭化裂解过程中,控制氧分压为2%,采用氮气保护,炭化裂解温度为650℃,炭化裂解时间为2小时;炭化裂解尾气通过油气分离得到炭化裂解油和炭化裂解气,炭化裂解气通过炭化燃烧得到燃烧尾气和热量,产生的热量直接为炭化裂解提供热源;
(2)炭化裂解得到的炭化裂解渣进行破碎风选得到破碎料和粉尘,破碎风选过程中,破碎粒度小于100目;破碎料进行磁选得到铁磁性物质和非铁磁性物质,非铁磁性物质进行电选得到金属和非金属,铁磁性物质和非金属分别进行综合利用;
(3)破碎风选得到的粉尘进行气化裂解得到气化裂解渣和气化裂解尾气,气化裂解温度为800℃,水蒸气/物料质量流量比为0.75,气化裂解时间为2小时;气化裂解尾气通过水气分离得到水和气化裂解气;
(4)炭化裂解油、炭化裂解气和气化裂解气进入蒸汽锅炉燃烧得到燃烧尾气和水蒸气,燃烧尾气进行二次燃烧和急冷的尾气净化,达标后排空,产生的水蒸气为气化裂解和多金属回收提供热源,气化裂解得到的裂解渣和电选得到的金属进行多金属回收得到有价金属及其化合物。
金属回收率为99.6%,烟气二噁英浓度为0.15ngTEQ/m3。
实施例6
按照如下步骤进行回收:
(1)将废集成线路板通过炭化裂解得到炭化裂解渣和炭化裂解尾气,炭化裂解过程中,控制氧分压为5.5%,采用氮气保护,炭化裂解温度为550℃,炭化裂解时间为1小时;炭化裂解尾气通过油气分离得到炭化裂解油和炭化裂解气,炭化裂解气通过炭化燃烧得到燃烧尾气和热量,产生的热量直接为炭化裂解提供热源;
(2)炭化裂解得到的炭化裂解渣进行破碎风选得到破碎料和粉尘,破碎风选过程中,破碎粒度小于100目;破碎料进行磁选得到铁磁性物质和非铁磁性物质,非铁磁性物质进行电选得到金属和非金属,铁磁性物质和非金属分别进行综合利用;
(3)破碎风选得到的粉尘进行气化裂解得到气化裂解渣和气化裂解尾气,气化裂解温度为950℃,水蒸气/物料质量流量比为0.5,气化裂解时间为2小时;气化裂解尾气通过水气分离得到水和气化裂解气;
(4)炭化裂解油、炭化裂解气和气化裂解气进入蒸汽锅炉燃烧得到燃烧尾气和水蒸气,燃烧尾气进行二次燃烧和急冷的尾气净化,达标后排空,产生的水蒸气为气化裂解和多金属回收提供热源,气化裂解得到的裂解渣和电选得到的金属进行多金属回收得到有价金属及其化合物。
金属回收率为99.3%,烟气二噁英浓度为0.07ngTEQ/m3。
Claims (5)
1.废集成线路板热质协同绿色资源化方法,其特征在于包括如下部分:
(1)炭化裂解系统:包括炭化裂解、油气分离和炭化燃烧;废集成线路板通过炭化裂解得到炭化裂解渣和炭化裂解尾气,炭化裂解尾气通过油气分离得到炭化裂解油和炭化裂解气,炭化裂解气通过炭化燃烧得到燃烧尾气和热量,产生的热量直接为炭化裂解提供热源;
(2)破碎分选系统:包括破碎风选、磁选和电选;炭化裂解得到的炭化裂解渣进行破碎风选得到破碎料和粉尘,破碎料进行磁选得到铁磁性物质和非铁磁性物质,非铁磁性物质进行电选得到金属和非金属,铁磁性物质和非金属分别进行综合利用;
(3)气化裂解系统:包括气化裂解和水气分离;破碎风选得到的粉尘进行气化裂解得到气化裂解渣和气化裂解尾气,气化裂解尾气通过水气分离得到水和气化裂解气;
(4)热值利用及综合回收系统:包括蒸汽发生、尾气净化和多金属回收;炭化裂解油、炭化裂解气和气化裂解气进入蒸汽锅炉燃烧得到燃烧尾气和水蒸气,燃烧尾气进行尾气净化达标后排空,水蒸气为气化裂解和多金属回收提供所需的热源,气化裂解得到的裂解渣和电选得到的金属进行多金属回收得到有价金属及其化合物。
2.如权利要求1所述的废集成线路板热质协同绿色资源化方法,其特征在于,在炭化裂解系统的炭化裂解过程中,控制氧分压≤6%,采用氮气保护,炭化裂解温度为400~700℃,炭化裂解时间为1~3小时。
3.如权利要求1所述的废集成线路板热质协同绿色资源化方法,其特征在于,在破碎分选系统的破碎风选过程中,破碎粒度小于100目。
4.如权利要求1所述的废集成线路板热质协同绿色资源化方法,其特征在于,在气化裂解系统的气化裂解过程中,气化裂解温度为700~950℃,水蒸气/物料质量流量比为0.5~1,气化裂解时间为0.5~2小时。
5.如权利要求1所述的废集成线路板热质协同绿色资源化方法,其特征在于,在热值利用及综合回收系统中,产生的燃烧尾气进行二次燃烧和急冷。
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