CN106807726B - 含钛高炉渣与废旧印刷线路板协同全组分资源化方法 - Google Patents
含钛高炉渣与废旧印刷线路板协同全组分资源化方法 Download PDFInfo
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Classifications
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- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
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- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/20—Agglomeration, binding or encapsulation of solid waste
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- B09B3/29—Agglomeration, binding or encapsulation of solid waste using mineral binders or matrix involving a melting or softening step
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B5/00—Operations not covered by a single other subclass or by a single other group in this subclass
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- C—CHEMISTRY; METALLURGY
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- C—CHEMISTRY; METALLURGY
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- C01F7/00—Compounds of aluminium
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- C—CHEMISTRY; METALLURGY
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- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
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- C—CHEMISTRY; METALLURGY
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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- Y02W30/82—Recycling of waste of electrical or electronic equipment [WEEE]
Abstract
本发明公开一种含钛高炉渣与废旧印刷线路板协同全组分资源化方，属于无机材料制备技术领域。该方法首先将含钛高炉渣与适量的废旧印刷线路板WPCBs混合均匀加热至熔融确保混合均匀，再与一定的Na2CO3混合均匀进行热态改性处理，经过稀盐酸酸浸过滤后获得的CaTiO3含量达到75％以上；滤液用氨水调节pH，过滤后再用酸洗除去Fe3+即得到水合二氧化硅，滤液再用氨水调pH以获得镁铝尖晶石的前驱物，高温灼烧得到多元掺杂镁铝尖晶石与钙铝石复合材料。本发明方法能够分别制备烟气选择性还原(SCR)脱硝催化剂、水合二氧化硅和镁铝尖晶石与钙铝石复合材料，本发明方法对高炉渣与WPCBs进行了协同资源化利用，具有显著的经济和社会效益。
Description
技术领域：
本发明属于无机材料制备技术领域，具体涉及一种含钛高炉渣与废旧印刷线路板协同全组分高值资源化方法。本发明方法以含钛高炉渣与废旧印刷线路板(WPCBs)协同资源化利用，分别制备烟气SCR脱硝催化剂、水合二氧化硅和镁铝尖晶石与钙铝石复合材料。
背景技术：
含钛高炉渣是中国特有的二次资源，其含有大量的Ca、Mg、Al、Si、Ti等有价元素，资源化利用潜力巨大。自从上个世纪60年代起，含钛高炉渣综合利用一直备受关注，国内一批专家学者对含钛高炉渣的综合利用做了大量的研究工作，也取得了一定成果，但目前含钛高炉渣的综合利用率仍然低，且绝大多数利用方式仍处于较为低端阶段，即使对其进行资源化利用(如：提取钛及含钛组分，生产水玻璃以及制矿渣棉等)，也只是提取单一组分，附加值较低，且生产流程长且复杂，难以实现大宗量高附加值利用。
现有高炉渣利用的技术方案主要有：用作建筑材料、酸浸提取TiO2、碱处理高炉渣相分离技术、熔融电解法制取硅钛复合合金工艺、高温碳化—低温氯化制取TiCl4残渣制水泥、硫酸铵熔融反应法提钛技术以及熔融法制备微晶玻璃等七种；目前从技术、经济、环保、市场等多方面，专家对上述七种典型高炉渣利用技术进行综合评价后认为，所列七种高炉渣利用技术均只以一种或多种元素为目标组分，其虽具有一定经济效益，但是非目标组分白白浪费并可能产生一定的环境影响。
而废旧印刷线路板(Waste Printed Circuit Boards，WPCBs)是电子电器产品的核心组件，随着电子产品更新换代和淘汰速度的加快，WPCBs的废弃量逐年增加。中国国家统计局数据显示，2013年中国的电子废弃物总量为5.5百万吨，2014年超过6百万吨，预计2020年中国的电子废弃物将达到一千万吨，占全球总量的一半。并且全球产生的电子废弃物有80％转移到亚洲，其中90％进入到中国，数量庞大的电子废弃物将对中国的生态环境安全造成严重的威胁。印刷电路板(PCBs)中成分复杂，其中含有的重金属(铅、汞、铬、镉)以及非金属(溴代助燃剂、液态光致阻焊剂)，随意丢弃暴露在环境中，极易造成土壤、水体的严重污染。同时，这些废旧印刷线路板含有大量的有价金属，具有可观的经济价值。特别是线路板中的Cu含量在10-20％，而目前我国铜矿中Cu的平均品位是0.6％，这表明WPCBs中的Cu是铜矿的数十倍，如果将WPCBs中的Cu进行合理的资源化利用，将会产生巨大的环境效益和经济价值。现有WPCBs资源化方法主要有：火法冶金技术、湿法冶金技术、机械处理技术、生物冶金技术以及热解技术；目前，上述处理WPCBs的技术方法还存在一定的缺点和问题，现有技术水平很难满足社会、市场的需求。
发明内容：
本发明为了克服现有高炉渣单一组分资源化与WPCBs利用的缺陷，提供一种含钛高炉渣与废旧印刷线路板协同全组分高值资源化方法。本发明方法包括WPCBs掺杂固溶、热改性工序和分段回收有价组分工序。
本发明提供一种含钛高炉渣与废旧印刷线路板协同全组分高值资源化方法，该方法具体步骤如下：
(1)废旧印刷线路板WPCBs的掺杂固溶：
(1A)将含钛高炉渣烘干，置于粉磨罐粉磨，得到含钛高炉渣粉末；
(1B)将废旧印刷线路板WPCBs用颚式破碎机破碎，将除去铁片后的废旧印刷线路板WPCBs碎块置于箱式炉中700-900℃保温2h热分解有机高分子材料，然后将热处理后的废旧印刷线路板WPCBs碎块用研钵研磨,得到废旧印刷线路板WPCBs粉末；
(1C)将步骤(1A)和(1B)中所得的所述含钛高炉渣粉末与所述废旧印刷线路板WPCBs粉末按质量比10:1研磨混合均匀后置于坩埚中，加热至1350-1550℃熔融状态保温1h后自然冷却得到废旧印刷线路板WPCBs掺杂固溶的含钛高炉渣。
(2)热改性：
(2A)将步骤(1C)得到的所述废旧印刷线路板WPCBs掺杂固溶的含钛高炉渣进行破碎，然后用粉磨罐粉磨得到废旧印刷线路板WPCBs掺杂固溶的含钛高炉渣粉末，烘干备用；
(2B)将步骤(2A)所得的所述废旧印刷线路板WPCBs掺杂固溶的含钛高炉渣粉末与Na2CO3按质量比10：3混合研磨均匀后置于坩埚中，于1350-1550℃条件下热改性，保温1h后自然冷却得到改性含钛高炉渣。
(3)分段回收有价组分：
(3A)制备烟气SCR脱硝催化剂：将步骤(2B)中得到的所述改性含钛高炉渣破碎研磨得到改性含钛高炉渣粉末，将所述改性含钛高炉渣粉末置于5wt％-10wt％盐酸溶液中，在温度25-60℃下，搅拌反应1h，过滤并用水洗涤至中性，烘干得到烟气SCR脱硝催化剂：CaTiO3复合催化剂，滤液保留；
(3B)制备水合二氧化硅：将步骤(3A)中保留的滤液调节pH值至2.8-3.5，过滤得到粗制水合二氧化硅，滤液保留备用；将所得粗制水合二氧化硅与酸混合搅拌、过滤、水洗、烘干后，得到水合二氧化硅；
(3C)制备镁铝尖晶石与钙铝石复合材料：
将步骤(3B)所得滤液用氨水调节pH至7.5-8.5，置于25-65℃水浴陈化1h，过滤得到前驱物；将所述前驱物置于箱式炉中，于1300-1550℃下焙烧2h，得到镁铝尖晶石与钙铝石复合材料。
本发明方法的主要化学反应及原理如下：
1、制备的主要化学反应
高温反应：
SiO2+Na2CO3→Na2SiO3+CO2↑+O2↑
酸解反应：
Al2O3+6HCl→2AlCl3+3H2O
Fe2O3+6HCl→2FeCl3+3H2O
MgO+2HCl→MgCl2+H2O
CaO+2HCl→CaCl2+H2O
2、本发明的主要原理：
(1)将WPCBs与含钛高炉渣高温共熔，使WPCBs中的Cu等元素固溶于含钛高炉渣中，实现含钛高炉渣中催化活性物质的原位优化掺杂。
(2)通过将WPCBs掺杂固溶后的含钛高炉渣进行碱热处理，使Ti组分富集到不易与酸反应的CaTiO3物相中并且促进硅酸盐矿物相重构形成能被酸完全溶解的硅酸盐，同时，实现WPCBs中诸如Cu、Ag、Au等多种高价值元素掺杂至SCR催化活性物质中。
(3)使用盐酸酸浸(2)经过热改性的渣样，使渣样中的Al2O3、Fe2O3、MgO和SiO2等组分进入滤液，再通过过滤和水洗涤除去，获得SCR催化剂。
(4)将(3)中的滤液收集保留，调节pH使Si、Mg、Al、Ca等元素分段提取出来。
本发明的优点是通过WPCBs与含钛高炉共熔，再经热改性将含钛高炉渣中Ti组分富集到不易与酸反应的多元掺杂CaTiO3(主要SCR活性物质)物相中并使其相富集长大，以及促进硅酸盐矿物相重构形成能被酸完全溶解的硅酸盐，同时，将WPCBs中的Cu等元素掺杂固溶于钙钛矿相。然后通过稀盐酸酸浸将Al2O3、Fe2O3、MgO和SiO2等组分除去，获得高效SCR催化剂，其在350-400℃下的脱硝效率均达到85-99％。再通过后续分段调节pH制备水合二氧化硅(SiO2含量达96-98％)和镁铝尖晶石与钙铝石复合材料。该方法工艺简单、成本低、实现了高炉渣与WPCBs的协同资源化高附加值利用，实现含钛高炉渣与WPCBs的的大宗量绿色高效利用，具有巨大的经济及社会效益。
附图说明：
图1为本发明方法所制备的SCR催化剂酸浸后的XRD图；
图2为本发明方法所制备的水合二氧化硅的红外图谱；
图3为本发明方法所制备的镁铝尖晶石和钙铝石复合材料的XRD图。
具体实施方式：
实施例1：将WPCBs用颚式破碎机破碎后置于箱式炉中，加热至700℃保温2h，除去塑料等有机成分，自然冷却后用研钵研磨至较小粒径；含钛高炉渣烘干，取100g置于粉磨罐中粉磨60s；取上述含钛高炉渣100g与WPCBs粉末10g混合均匀置于坩埚中，箱式炉中加热至1350℃保温1h随炉冷却；将上述WPCBs掺杂含钛高炉渣用粉磨罐粉磨(100g研磨30s)；取100g上述WPCBs掺杂含钛高炉渣和30g Na2CO3粉体混合研磨均匀，置于坩埚中在1350℃下保温1h，自然冷却备用；将经过热改性高炉渣粉磨罐粉磨后，取粉末15.0108g，置于100-300ml5-10wt％的盐酸溶液中，在25-60℃下搅拌反应1h，过滤获得固相样品Ⅰ和液相样品Ⅰ，水洗固相样品Ⅰ、烘干获得高效SCR催化剂。液相样品Ⅰ收集保留备用；调节液相样品ⅠpH至3.68，过滤获得固相样品Ⅱ和液相样品Ⅱ，将固相样品Ⅱ烘干得到粗制水合二氧化硅，粗制水合二氧化硅经酸浸、水洗、烘干后得到高纯水合二氧化硅；将液相样品Ⅱ调节pH＝8.05，置于65℃水浴锅中陈化1h，过滤、烘干后得到镁铝尖晶石前驱物；将镁铝尖晶石前驱物置于箱式炉中1300℃保温2h，即得到镁铝尖晶石与钙铝石复合材料。
实施例2：将WPCBs用颚式破碎机破碎后置于箱式炉中，加热至800℃保温2h，除去塑料等有机成分，自然冷却后用研钵研磨至较小粒径；含钛高炉渣烘干，取100g置于粉磨罐中粉磨60s；取上述含钛高炉渣100g与WPCBs粉末10g混合均匀置于坩埚中，箱式炉中加热至1450℃保温1h随炉冷却；将上述WPCBs掺杂固溶含钛高炉渣用粉磨罐粉磨，(100g研磨30s)；取100g上述WPCBs掺杂含钛高炉渣和30g Na2CO3粉体混合研磨均匀，置于坩埚中在1450℃下保温1h，自然冷却备用；将经过热改性高炉渣粉磨罐粉磨后，取粉末15.0209g，置于100-300ml5-10wt％的盐酸溶液中，在25-60℃下搅拌反应1h，过滤获得固相样品Ⅰ和液相样品Ⅰ，水洗固相样品Ⅰ、烘干获得高效SCR催化剂。液相样品Ⅰ收集保留备用；调节液相样品ⅠpH至3.06，过滤获得固相样品Ⅱ和液相样品Ⅱ，将固相样品Ⅱ烘干得到粗制水合二氧化硅，粗制水合二氧化硅经酸浸、水洗、烘干后得到水合二氧化硅；将液相样品Ⅱ调节pH＝8.06，置于65℃水浴锅中陈化1h，过滤、烘干后得到镁铝尖晶石前驱物；将镁铝尖晶石前驱物置于箱式炉中1450℃保温2h，即得到镁铝尖晶石与钙铝石复合材料。
实施例3：将WPCBs用颚式破碎机破碎后置于箱式炉中，加热至900℃保温2h，除去塑料等有机成分，自然冷却后用研钵研磨至较小粒径；含钛高炉渣烘干，取100g置于粉磨罐中粉磨60s；取上述含钛高炉渣100g与WPCBs粉末10g混合均匀置于坩埚中，箱式炉中加热至1550℃保温1h随炉冷却；将上述WPCBs掺杂的含钛高炉渣用粉磨罐粉磨，(100g研磨30s)；取100g上述WPCBs掺杂含钛高炉渣和30g Na2CO3粉体混合研磨均匀，置于坩埚中在1550℃下保温1h，自然冷却备用；将经过热改性高炉渣粉磨罐粉磨后，取粉末15.0120g，置于100-300ml5-10wt％的盐酸溶液中，在50℃下搅拌反应1h，过滤获得固相样品Ⅰ和液相样品Ⅰ，水洗固相样品Ⅰ、烘干获得高效SCR催化剂。液相样品Ⅰ收集保留备用；调节液相样品ⅠpH至3.46，过滤获得固相样品Ⅱ和液相样品Ⅱ，将固相样品Ⅱ烘干得到粗制水合二氧化硅，粗制水合二氧化硅经酸浸、水洗、烘干后得到水合二氧化硅；将液相样品Ⅱ调节pH＝7.56，置于65℃水浴锅中陈化1h，过滤、烘干后得到镁铝尖晶石前驱物；将镁铝尖晶石前驱物置于箱式炉中1550℃保温2h，即得到镁铝尖晶石与钙铝石复合材料。
表1为本发明方法所制备的SCR催化剂酸浸后的化学组成。由图1可知，SCR催化剂酸浸后的固相XRD图与标准卡片峰位相对应，再结合XRF数据，可知该催化剂的主要晶型为钙钛矿、Fe2O3及镁铝尖晶石等，具有SCR脱硝活性物质。3421.81cm-1的振动峰为H2O分子伸缩振动峰；1636.43cm-1出现的振动峰是H-O-H键的弯曲振动峰；1075cm-1，794.83cm-1，467.58cm-1出现的吸收峰，分别为Si-O-Si键的反对称伸缩振动峰，对称伸缩振动峰和弯曲振动峰，为二氧化硅的特征峰。测试结果表明，所制得样品的图谱与标准水合二氧化硅图谱一致，说明制得样品为无定形水合二氧化硅。
见图3，XRD图比对镁铝尖晶石标准卡片99-0098和钙铝石标准卡片45-0946，峰位基本对应，可知焙烧后样品为镁铝尖晶石和钙铝石复合材料。
表1本发明方法制备的SCR催化剂酸浸后的化学组成
Claims (1)
1.含钛高炉渣与废旧印刷线路板协同全组分资源化方法，其特征在于该方法具体步骤如下：
(1)废旧印刷线路板的掺杂固溶：
(1A)将含钛高炉渣烘干，置于粉磨罐粉磨，得到含钛高炉渣粉末；
(1B)将废旧印刷线路板用颚式破碎机破碎，将除去铁片后的废旧印刷线路板碎块置于箱式炉中700-900℃保温2h热分解有机高分子材料，然后将热处理后的废旧印刷线路板碎块用研钵研磨,得到废旧印刷线路板粉末；
(1C)将步骤(1A)和(1B)中所得的所述含钛高炉渣粉末与所述废旧印刷线路板粉末按质量比10:1研磨混合均匀后置于坩埚中，加热至1350-1550℃熔融状态保温1h后自然冷却得到废旧印刷线路板掺杂固溶的含钛高炉渣；
(2)热改性：
(2A)将步骤(1C)得到的所述废旧印刷线路板掺杂固溶的含钛高炉渣进行破碎，然后用粉磨罐粉磨得到废旧印刷线路板掺杂固溶的含钛高炉渣粉末，烘干备用；
(2B)将步骤(2A)所得的所述废旧印刷线路板掺杂固溶的含钛高炉渣粉末与Na2CO3按质量比10：3混合研磨均匀后置于坩埚中，于1350-1550℃条件下热改性，保温1h后自然冷却得到改性含钛高炉渣；
(3)分段回收有价组分：
(3A)制备烟气SCR脱硝催化剂：将步骤(2B)中得到的所述改性含钛高炉渣破碎研磨得到改性含钛高炉渣粉末，将所述改性含钛高炉渣粉末置于5wt％-10wt％盐酸溶液中，在温度25-60℃下，搅拌反应1h，过滤并用水洗涤至中性，烘干得到烟气SCR脱硝催化剂：CaTiO3复合催化剂，滤液保留；
(3B)制备水合二氧化硅：将步骤(3A)中保留的滤液调节pH值至2.8-3.5，过滤得到粗制水合二氧化硅，滤液保留备用；将所得粗制水合二氧化硅与酸混合搅拌、过滤、水洗、烘干后，得到水合二氧化硅；
(3C)制备镁铝尖晶石与钙铝石复合材料：
将步骤(3B)所得滤液用氨水调节pH至7.5-8.5，置于25-65℃水浴陈化1h，过滤得到前驱物；将所述前驱物置于箱式炉中，于1300-1550℃下焙烧2h，得到镁铝尖晶石与钙铝石复合材料。
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2007203154A (ja) * | 2006-01-31 | 2007-08-16 | Nikko Kinzoku Kk | 産業廃棄物の溶融処理法 |
| CN101428233A (zh) * | 2007-11-07 | 2009-05-13 | 中国石油化工股份有限公司 | 用于催化裂解的催化剂 |
| JP2009233531A (ja) * | 2008-03-26 | 2009-10-15 | Kobelco Eco-Solutions Co Ltd | Ｐｃｂ汚染物処理方法 |
| CN102583515A (zh) * | 2012-01-09 | 2012-07-18 | 安徽工业大学 | 一种用缓冷含钛高炉渣制备CaTiO3复合材料的方法 |
| CN105782986A (zh) * | 2016-03-15 | 2016-07-20 | 江苏理工学院 | 一种含铜电子废弃物的协同处理工艺 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| JP2007203154A (ja) * | 2006-01-31 | 2007-08-16 | Nikko Kinzoku Kk | 産業廃棄物の溶融処理法 |
| CN101428233A (zh) * | 2007-11-07 | 2009-05-13 | 中国石油化工股份有限公司 | 用于催化裂解的催化剂 |
| JP2009233531A (ja) * | 2008-03-26 | 2009-10-15 | Kobelco Eco-Solutions Co Ltd | Ｐｃｂ汚染物処理方法 |
| CN102583515A (zh) * | 2012-01-09 | 2012-07-18 | 安徽工业大学 | 一种用缓冷含钛高炉渣制备CaTiO3复合材料的方法 |
| CN105782986A (zh) * | 2016-03-15 | 2016-07-20 | 江苏理工学院 | 一种含铜电子废弃物的协同处理工艺 |
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