CN113600122B - 一种天然硫化矿物改性材料、制备方法及其应用 - Google Patents

一种天然硫化矿物改性材料、制备方法及其应用 Download PDF

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CN113600122B
CN113600122B CN202110979784.7A CN202110979784A CN113600122B CN 113600122 B CN113600122 B CN 113600122B CN 202110979784 A CN202110979784 A CN 202110979784A CN 113600122 B CN113600122 B CN 113600122B
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CN113600122A (zh
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李海龙
孟凡悦
杨建平
屈文麒
杨泽群
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Central South University
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Abstract

本发明公开了一种天然硫化矿物改性材料、制备方法及其应用。本发明以天然硫化矿物和铜盐为原料，经过机械研磨活化、干燥等步骤改性合成了硫化矿复合材料，作为汞吸附剂用于汞的固化脱除。铜盐在硫化矿物的表面发生反应，提供更多的金属位点，在机械力的作用下形成细小的微晶颗粒，晶体结构发生变化，使活性位点更充分的暴露，研磨和干燥过程强化了物料之间的传质，促进了反应的发生。本发明的天然硫化矿改性材料与气相或/和液相中的汞接触，将汞转化为稳定的化合物，实现汞的固化脱除，具有汞吸附容量大和吸附速率快、应用温度范围广的优点，成本低、原料储备丰富、操作简单、脱汞产物环境友好无二次污染，具有良好的工业应用前景。

Description

一种天然硫化矿物改性材料、制备方法及其应用
技术领域
本发明属于环境污染防治净化技术领域，具体涉及一种天然硫化矿物改性材料、制备方法及其应用。
背景技术
汞，又被称为水银，是自然界中唯一一种在常温下以液态形式存在的金属。汞及其化合物具有剧毒性、持久性、高腐蚀性、易挥发性、全球迁移扩散性和生物富集性，会对人体健康和周围环境造成严重危害。汞的排放来源可分为自然来源和人为来源，其中人为来源的汞主要来自于金属冶炼、燃煤电厂、石油化工、垃圾处理、水泥生产等行业废气、废水、废渣的排放。2013年联合国环境规划署制定了关于汞的《水俣公约》，旨在对全球范围内的汞排放进行控制，2017年《水俣公约》在全球100多个国家正式生效，标志着减少汞污染物排放已成为国际社会的共识。
目前常用的脱除汞的方法包括吸附、催化氧化、吸收、离子交换、低温分离等，其中吸附法是一种最广泛应用的方法。活性炭是一类较为成熟的商业脱汞剂，已在煤烟气脱汞领域使用，但其受工况条件的影响较大，不适用于高温、高酸、高湿、高SO2浓度的环境，且其用量大，无法再生，运行成本较高，不适宜规模化应用。近年来，飞灰、沸石材料、钙基材料、贵金属、金属硫化物等都被尝试用于汞的固定脱除，其中金属硫化物由于其表面富集了较多低温条件下可以与汞自发反应的化学基团（如表面单体硫、多硫链、金属活性位点等），可以将Hg固定为稳定的化合物(HgS)，具有优越的脱汞效率，被认为是传统活性炭类吸附剂的最有利替代品。但是具有高效脱汞效率的金属硫化物吸附剂合成过程复杂，需由复杂的前驱体并通过添加表面活性剂严格控制精准合成，这显著增加难度，大大提高了成本，阻碍了金属硫化物吸附剂规模化生产与应用。
天然金属硫化矿中含有丰富的硫位点和金属位点，在矿物形成过程中还存在可类质同像代替现象导致晶胞结构发生变化，产生电子心或空穴心等，这些结构特点可能会对脱汞有积极作用。但是大多数的天然金属硫化矿由于结构致密、表面积较小、粒径较大，活性位点不能暴露，并没有脱汞能力。因此，对天然的金属硫化矿进行改性处理，降低微晶颗粒尺寸，改变晶体结构，提供更多的活性位点或使活性位点更充分暴露，可提高脱汞效果，使金属硫化物吸附剂在脱汞领域的大规模化应用成为可能。
发明内容
为了克服现有脱汞材料的缺陷与不足，本发明提供了一种天然硫化矿物改性材料、制备方法及其应用；本发明利用铜盐在硫化矿物的表面发生反应，提供更多的金属位点，在机械力的作用下形成细小的微晶颗粒，晶体结构发生变化，使活性位点更充分的暴露，研磨和干燥过程强化了物料之间的传质，促进了反应的发生。本发明的改性合成的天然硫化矿复合材料作为汞吸附剂与气相或/和液相中的汞接触，将汞转化为稳定的化合物，实现汞的固化脱除，具有汞吸附容量大和吸附速率快、应用温度范围广的优点，成本低、原料储备丰富、操作简单、脱汞产物环境友好无二次污染，具有良好的工业应用前景。本发明的技术方案具体介绍如下。
本发明提供一种天然硫化矿物改性材料，其用于汞的固化脱除，将汞转化为稳定的化合物；其通过将天然硫化矿物与铜盐混合后机械球磨活化、干燥制得。
优选的，天然硫化矿物选自黄铜矿、辉铜矿、斑铜矿、黝铜矿、方铅矿、闪锌矿、铁闪锌矿、辉钼矿或辉锑矿中的一种或组合；铜盐选自氯化亚铜、氯化铜或其水合物中的一种或组合。
优选的，铜盐与天然硫化矿物的质量比为1:20-2:1。
优选的，天然硫化矿物经过球磨处理。
优选的，天然硫化矿物球磨处理前，用稀酸进行清洗除杂处理。
本发明中，天然硫化矿物改性材料通过以下方法制备获得：
（1）用稀酸清洗天然硫化矿的表面氧化膜与杂质，后用清水清洗，干燥后破碎处理备用，将破碎后的天然硫化矿物添加到球磨机内进行充分球磨粉碎；
（2）将一定比例的铜盐添加到球磨机内继续机械研磨活化，活化后将矿物置于真空干燥箱内干燥或冷冻干燥，
（3）干燥后再次机械研磨，研磨后筛分。
本发明还提供一种天然硫化矿物改性材料的制备方法，其通过将天然硫化矿物与铜盐混合后机械球磨活化、干燥制得天然硫化矿物改性材料；具体包括如下步骤：
（1）用稀酸清洗天然硫化矿的表面氧化膜与杂质，后用清水清洗，干燥后破碎处理备用，将破碎后的天然硫化矿物添加到球磨机内进行充分球磨粉碎；
（2）将一定比例的铜盐添加到球磨机内继续机械研磨活化，活化后将矿物置于真空干燥箱内干燥或冷冻干燥，
（3）干燥后再次机械研磨，研磨后筛分。
优选的，步骤（1）中，稀酸的浓度为1-5wt%，酸选自硫酸、盐酸、硝酸、乙酸中的一种，浸泡清洗时间为5-20min干燥温度为100-200℃，球磨时间为5-30min；步骤（2）中，铜盐与天然硫化矿的质量比为1:20-2:1，机械研磨时间为5-60min，研磨温度为25-75℃，真空干燥温度为60-150℃，冷冻干燥温度为-20℃--40℃；步骤（3）中，再次强化研磨时间为5-20min，筛分至74μm以下。
本发明进一步提供一种根据上述的天然硫化矿物改性材料作为脱汞剂在脱汞领域的应用，天然硫化矿物改性材料直接喷射于烟道、脱汞塔、流化床或湿法烟气净化系统，或以成型材料的形式在固定床系统使用。
金属硫化物表面的活性基团可与汞在常温下自发发生反应，将汞转化为稳定的化合物固定在吸附剂上，被认为是一类最有商业应用潜力的脱汞材料。现阶段研究较多的金属硫化物脱汞剂一般由化学合成获得，制备过程复杂，需由复杂的前驱体通过添加表面活性剂严格控制精准合成，导致成本较高，制约了金属硫化物材料在脱汞领域的应用。天然金属硫化矿物如黄铜矿、辉铜、方铅矿等储量丰富，但天然金属硫化矿物一般呈块状聚集，表面被氧化膜包裹，粒径较大、结构致密、比表面积较小，且被脉石包裹、互相伴生、成分复杂，导致化学活性基团不能暴露，并没有脱汞能力。天然金属硫化矿中含有丰富的硫位点、金属位点、晶格氧位点，且在矿物形成过程中存在可类质同像代替现象导致晶胞结构发生变化，产生电子心或空穴心等。本发明中，利用天然金属硫化矿的化学组成和结构特点，用稀酸破坏硫化矿物的表面氧化膜并溶解部分脉石杂质，使矿物更多的暴露出来，添加铜盐对其进行研磨改性处理，铜盐在硫化矿物的表面发生反应，提供更多的金属位点，在机械力的作用下形成细小的微晶颗粒，晶体结构发生变化，使活性位点更充分的暴露，研磨和干燥过程强化了物料之间的传质，促进了反应的发生。
与现有技术相比，本发明技术方案的优势如下：
（1）改性方法简单，大幅度的提高了天然硫化矿物的脱汞性能，改性后饱和脱汞容量超过80mg/g，饱和脱汞容量和脱汞速率比改性前提高几十倍甚至上百倍。
（2）天然硫化矿物储量巨大、易获取，与化学合成硫化物脱汞剂相比，成本显著降低，且避免了化学合成过程中的环境污染问题。
（3）通过控制改性过程，可制备适应不同工况条件的硫化矿物脱汞材料，应用温度区间范围广。
（4）汞以稳定化合物的形式固定在改性硫化矿物上，可有效避免二次释放，具有巨大的环境效益。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。此外，下面所描述的本发明各个实施方式中所涉及到的技术特征只要彼此之间未构成冲突就可以相互组合。
实施例1
用4wt%的稀盐酸浸泡清洗黄铜矿，浸泡时间为10min，150℃下干燥3h，用破碎机破碎后将黄铜矿置于球磨机内球磨5min；将氯化亚铜与黄铜矿按照质量3:2的比例添加到球磨机内机械研磨活化，机械研磨时间为20min，研磨温度为50℃，随后100℃下真空干燥8h；干燥后的矿物再次强化研磨10min，过筛至74μm以下得到改性矿物材料。
称取300mg改性矿物材料到模拟烟气洗涤装置中，模拟洗涤液的温度为25℃，模拟洗涤液的pH=4，模拟洗涤液的体积为200mL。通过汞渗透管产生单质汞，使用VM-3000测汞仪进行汞浓度的实时测量，质量流量计精准控制各成分气体流量来模拟烟气的成分，气体总流量为0.5L/min，初始Hg0浓度为200±2μg/m3，在纯N2气氛下，1h内改性天然硫化矿物材料对Hg0脱除效率为94.8%。
实施例2
用2wt%的稀硫酸浸泡清洗辉钼矿，浸泡时间为20min，120℃下干燥6h，用破碎机破碎后将辉钼矿置于球磨机内球磨20min；将氯化铜与辉钼矿按照质量比1:2的比例添加到球磨机内机械研磨活化，机械研磨时间为30min，研磨温度为75℃，随后120℃下真空干燥12h；干燥后的矿物再次强化研磨20min，过筛至74μm以下得到改性矿物材料。
称取75mg改性矿物材料喷入体积为1 m3的中试喷射塔中，通过汞发生装置产生单质汞，使用VM-3000测汞仪进行汞浓度的实时测量，烟气流量阀控制气体流量，Hg0的初始浓度为100μg/m3，烟气流量为1m3/min，温度为125℃，纯N2气氛下，1h内Hg0脱除率为97.2%。
实施例3
用3wt%的稀硫酸浸泡清洗辉铜矿，浸泡时间为10min，100℃下干燥8h，用破碎机破碎后将辉铜矿置于球磨机内球磨10min；将氯化铜与辉铜矿按照质量比3:4的比例添加到球磨机内机械研磨活化，机械研磨时间为25min，研磨温度为40℃，随后-35℃下冷冻干燥6h；干燥后的矿物再次强化研磨15min，过筛至74μm以下得到改性矿物材料，黏土添加到矿物材料中，挤压成型为2-3mm的小球。
称取80mg小球置于模拟固定床反应器中，通过汞渗透管产生单质汞，使用VM-3000测汞仪进行汞浓度的实时测量，质量流量计精准控制各成分气体流量来模拟烟气的成分，气体总流量为1L/min，初始Hg0浓度为65±1μg/m3，反应温度为100℃。纯N2气氛下，Hg0脱除率为98.2%；N2+500 ppm SO2气氛下，Hg0脱除率为96.5%；N2+8%H2O+500 ppm SO2气氛下，2h内Hg0脱除率为94.1%。
实施例4
用2wt%的稀硫酸浸泡清洗黄铜矿，浸泡时间为15min，100℃下干燥8h，用破碎机破碎后将黄铜矿置于球磨机内球磨15min；将氯化铜与黄铜矿按照质量比2:3的比例添加到球磨机内机械研磨活化，机械研磨时间为30min，研磨温度为50℃，随后120℃下真空干燥6h；干燥后的矿物再次强化研磨15min，过筛至74μm以下得到改性矿物材料。
称取25mg改性矿物材料置于模拟固定床反应器中，通过汞渗透管产生单质汞，使用VM-3000测汞仪进行汞浓度的实时测量，质量流量计精准控制各成分气体流量来模拟烟气的成分，气体总流量为1L/min，初始Hg0浓度为500±2μg/m3，反应温度为100℃。纯N2气氛下，Hg0脱除率为95.2%；N2+200 ppm SO2气氛下，4h内Hg0脱除率为92.5%；纯N2气氛下，饱和脱汞容量为83.5mg/g。
实施例5
在某电厂进行了中试实验，烟气量为6000m3/min，汞的浓度为0.31-0.36mg/m3，在湿法脱硫装置的上游（温度约100℃）喷射实施案例4获得的改性天然矿物材料，喷射量为120mg/m3时，烟气中汞的脱除率到达95%以上。
对比例1
称取300mg实施例1中未改性黄铜矿到模拟烟气洗涤装置中，模拟洗涤液的温度为25℃，模拟洗涤液的pH=4，模拟洗涤液的体积为200mL。通过汞渗透管产生单质汞，使用VM-3000测汞仪进行汞浓度的实时测量，质量流量计精准控制各成分气体流量来模拟烟气的成分，气体总流量为0.5L/min，初始Hg0浓度为200±2μg/m3，在纯N2气氛下，1h内改性天然硫化矿物材料对Hg0脱除效率为3.2%。
对比例2
将实施例2中的辉钼矿用2wt%的稀硫酸浸泡清洗，浸泡时间为20min，120℃下干燥6h，用破碎机破碎后将辉钼矿置于球磨机内球磨20min。
称取75mg球磨后辉钼矿喷入体积为1 m3的中试喷射塔中，通过汞发生装置产生单质汞，使用VM-3000测汞仪进行汞浓度的实时测量，烟气流量阀控制气体流量，Hg0的初始浓度为100μg/m3，烟气流量为1m3/min，温度为125℃，纯N2气氛下，1h内Hg0脱除率为5.6%。
对比例3
将实施例2中的辉钼矿用2wt%的稀硫酸浸泡清洗，浸泡时间为20min，120℃下干燥6h，用破碎机破碎后将辉钼矿置于球磨机内球磨20min；将氯化铜与辉钼矿按照质量比1:2的比例简单混合，得到混合物。
称取75mg混合物喷入体积为1 m3的中试喷射塔中，通过汞发生装置产生单质汞，使用VM-3000测汞仪进行汞浓度的实时测量，烟气流量阀控制气体流量，Hg0的初始浓度为100μg/m3，烟气流量为1m3/min，温度为125℃，纯N2气氛下，1h内Hg0脱除率为7.4%。

Claims (3)

1.一种天然硫化矿物改性材料的制备方法，其特征在于，所述天然硫化矿物改性材料用于汞的固化脱除，将汞转化为稳定的化合物；所述天然硫化矿物改性材料通过将天然硫化矿物与铜盐混合后机械球磨活化、干燥制得；与铜盐混合前，天然硫化矿物经过球磨处理；其中：天然硫化矿物选自黄铜矿、辉铜矿、斑铜矿、黝铜矿、方铅矿、闪锌矿、铁闪锌矿、辉钼矿或辉锑矿中的一种或组合；铜盐选自氯化亚铜、氯化铜或其水合物中的一种或组合；铜盐与天然硫化矿物的质量比为1：20-2：1；
具体步骤如下：
（1）用稀酸清洗天然硫化矿物的表面氧化膜与杂质，后用清水清洗，干燥后破碎处理备用，将破碎后的天然硫化矿物添加到球磨机内进行充分球磨粉碎；
（2）将一定比例的铜盐添加到球磨机内继续机械研磨活化，活化后将矿物置于真空干燥箱内干燥或冷冻干燥；
（3）干燥后再次强化研磨，研磨后筛分。
2.根据权利要求1所述的制备方法，其特征在于，步骤（1）中，稀酸的浓度为1-5wt%，酸选自硫酸、盐酸、硝酸或乙酸中的一种，浸泡清洗时间为5-20min，干燥温度为100-200℃，球磨时间为5-30min；步骤（2）中，研磨时间为5-60min，研磨温度为25-75℃，真空干燥温度为60-150℃，冷冻干燥温度为-20℃~-40℃；步骤（3）中，再次强化研磨时间为5-20min，筛分至74μm以下。
3.一种根据权利要求1所述的制备方法制得的天然硫化矿物改性材料作为脱汞剂在脱汞领域的应用，其特征在于，天然硫化矿物改性材料直接喷射于烟道、脱汞塔、流化床或湿法烟气净化系统，或以成型材料的形式在固定床系统使用。
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