CN107649098B - 一种吸附重金属离子的富巯基吸附材料的制备方法 - Google Patents

一种吸附重金属离子的富巯基吸附材料的制备方法 Download PDF

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CN107649098B
CN107649098B CN201711109852.4A CN201711109852A CN107649098B CN 107649098 B CN107649098 B CN 107649098B CN 201711109852 A CN201711109852 A CN 201711109852A CN 107649098 B CN107649098 B CN 107649098B
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王龙
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Tenon and mortise Technology Service (Wenzhou) Co.,Ltd.
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Abstract

本发明提供一种富巯基吸附材料组合物的制备方法，其特征在于：(a)、占组合物总质量的60‑75%的介孔分子筛原粉，占组合物总质量的10‑20%的碱金属氧化物，余下组分包括粘结剂、扩孔剂，按配比混合形成均一体系的混合粉末；（b）、高温下烧结后粉碎研磨至平均粒径0.1‑10um。（c）、上述组分以悬浮液形式在溶液中加入3‑巯基丙基三甲氧基硅烷，调节pH至8‑10，200℃高压水热，过滤干燥。本发明制备的方法制备了针对水中重金属离子，吸附容量大的吸附材料，该吸附材料价格比较廉价，制备简单。

Description

一种吸附重金属离子的富巯基吸附材料的制备方法
技术领域
本发明涉及吸附材料的制备方法，具体地说，是一种吸附重金属离子的富巯基吸附材料的制备方法。
背景技术
有害金属离子对水的污染已经成为日益严重的环境问题，研究从 受污染的水中除去有害的金属离子的材料引起了人们越来越多的重 视。汞作为重金属之一，会对人们的身体健康乃至社会经济带来严重危害。从废水中分离去除汞离子，对保护环境有重要意义。近年来巯基官能化的吸附剂激起了人们浓厚的兴趣，这类吸附剂对汞离子具有较大的负载容量和较强的亲和力。巯基现已被固定到多种基底物上， 如硅胶、黏土及多孔材料等。然而由于这些基底物如比表面积低等自身的缺点，使孔道不利于离子的传输而影响其吸附效率。
CN1136960C公开了一种制备巯基官能化MCM－48介孔分子筛的方法。其利用MCM－48介孔分子筛与巯丙基三甲氧基硅烷甲苯溶液回流12～24小时制备。该方法制备时间长，成本高，同时是使用甲苯作为反应介质，不绿色环保。CN102009983A公开了一种巯基改性SBA-15分子筛及其制备和使用方法，其利用将SBA-15分子筛加入所配制的巯基改性剂乙醇水溶液中，常温搅拌36～48h，获得巯基改性SBA-15分子筛产物。其使用乙醇作为介质，并且反应时间过长，最后的产品效率也不令人满意。
发明内容
针对上述问题，本发明的目的在于提供一种针对水中重金属离子，吸附容量大的吸附材料的合成制备，该吸附材料价格比较廉价，制备简单。
一种富巯基吸附材料组合物的制备方法，其特征在于：
(a)、占组合物总质量的60-75%的介孔分子筛原粉，占组合物总质量的10-20%的碱金属氧化物，余下组分包括粘结剂、扩孔剂，按配比混合形成均一体系的混合粉末；
（b）、高温下烧结后粉碎研磨至平均粒径0.1-10um。
（c）、上述组分以悬浮液形式在溶液中加入3-巯基丙基三甲氧基硅烷，调节pH至8-10，200℃高压水热，过滤干燥。
优选地，介孔分子筛原粉为SAB-15分子筛原粉。
优选地，烧结温度为700℃以上。高温的目的是使金属氧化物，与分子筛粉进一步结合，从而增大负载量，增强吸附能力。同时可以分解扩孔剂，分子筛粉中其它残余物质，增大孔道直径，增大比表面积。扩孔剂为易热分解物质，在加热过程中会分解成气体，从而扩充孔容。优选田菁粉作为扩孔剂，其中田菁粉焙烧后转变为二氧化碳离开载体。
优选地，碱金属可优选包含氧化钙80重量％，氧化铝10重量％，氧化镁10重量％。碱金属组成不做限定的，但为了更好实现本发明的效果，优选按以上比例配比。
所述氧化物粘结剂选自二氧化硅溶胶。
优选地，研磨至平均粒径1um。越细的粉末在作为水体吸附剂时，能更好的分散，和提高与与水的接触面积，但是过于微细的粉末将阻碍水体流动或者难以沉降，增加处理成本，因此0.1-10um比较合适的范围，优选为1-10um，更优选为1um。
优选地，3-巯基丙基三甲氧基硅烷溶液是水溶液。通常的3-巯基丙基三甲氧基硅烷作为修饰剂的溶液为甲苯或乙醇溶液，但是使用甲苯和乙醇将导致二次污染，并且增加成本，因此本发明中使用水热方法，使用水溶液即可达到发明的目的。
优选地，水热时间2小时。其中水热温度为200-300℃，时间为2-4小时。优选为200℃，反应2h。水热的目的是在于使各物质以悬浮液的形式进一步充分混合，互相渗透负载，同时使3-巯基丙基三甲氧基硅烷与制备的分子筛表面的羟基充分反应，将巯基充分修饰到其表面上。水热溶液的pH优选为8-10。在该pH范围内，可以使制备的分子筛表面的羟基充分活化，促进与3-巯基丙基三甲氧基硅烷的反应。过碱导致3-巯基丙基三甲氧基硅烷与水中的碱发生反应，导致其用量大大提高，过酸导致分子筛表面羟基失活。
本发明还提供了一种吸附水中重金属离子的方法，使用根据上述制备的富巯基改性吸附材料组合物
与现有技术相比，本发明的有益效果在于：
1. 制备的负载碱金属的分子筛，表面具有富羟基结构，可与3-巯基丙基三甲氧基硅烷充分反应，提高负载量。
2.水热法制备，绿色环保，不使用有毒溶剂，同时大大缩短了制备周期。
3. 制备得到的产品，具有良好重金属吸附量。
具体实施方式
下面是本发明的实施例，所述的实施例只是用来说明本发明，而不应当被视为是对本发明的限制。
实施例1
1， 充分混合65质量份X分子筛的原粉，8质量份氧化钙，1质量份氧化铝，1质量份氧化镁，3质量份硅溶胶作为粘结剂，2质量份田菁粉作为扩孔剂。
2，将1中得到的混合粉末充分混合后，在700℃高温下煅烧后，用粉碎机充分粉碎至粒径为1um。
3，上述组分以悬浮液形式在水溶液中加入过量的3-巯基丙基三甲氧基硅烷，调节pH至8，在200℃水热条件下加热2小时，过滤干燥。
实施例2
与实施例1相同，除了粒径为10um。
实施例3
与实施例1相同，除了pH调节至10。
对比例1
与实施例1相同，除了粒径为0.1um。
对比例2
与实施例1相同，除了粒径为20um。
对比例3
与实施例1相同，除了pH为5。
对比例4
与实施例1相同，除了水热溶液换成甲苯。
对比例5
与实施例1相同，除了不添加碱金属氧化物。
对比例6
使用商购的SAB-15分子筛研磨至1um粒径，悬浮在水溶液中加入过量的3-巯基丙基三甲氧基硅烷，调节pH至8，在200℃水热条件下加热2小时，过滤干燥。
测试使用标准汞溶液，加入等量的实施例与对比例产品，超声震荡5分钟，静置，估算完成自然沉降至澄清透明所需的时间，静置2h后，离心分离后，用原子吸收光谱仪计算被吸附的汞金属量，计算饱和吸附量。最终产品使用全自动比表面积分析仪测试比表面积，孔容，孔径。
实施例1 实施例2 实施例3 对比例1 对比例2 对比例3 对比例4 对比例5 对比例6
Hg饱和吸附量（mmol/g） 3.45 2.62 3.12 4.10 1.37 1.05 3.71 1.28 1.42
比表面积m<sup>2</sup>/g 650 456 631 969 307 672 614 578 653
完成澄清所需时间h 1.0 0.5 1.2 24 0.2 0.9 1.0 0.9 1.0
对比实施例1-3和对比例1，2，可知粒径在1-10um之间使其沉降时间在合适的范围内，方便本发明的产品用于水处理净化剂。对比实施例1,3和对比例3，可知溶液酸度过大将影响分子筛的表面羟值，从而导致巯基无法修饰在分子筛表面，从而影响Hg饱和吸附量。对比例4中将水溶液换成甲苯溶液，可知本发明的制备方法，使用水溶液对最终的产品的性能没有太大的影响，但是水比甲苯更经济环保。对比例5和6中，没有添加碱金属氧化物，与实施例1对比可知，未添加碱金属氧化物将大大降低表面的巯基密度，导致Hg饱和吸附量也大大降低。
以上实施例的说明只是用于帮助理解本发明的方法及其核心思想；同时，对于本领域的一般技术人员，依据本发明的思想，在具体实施方式及应用范围上均会有改变之处，综上所述，本说明书内容不应理解为对本发明的限制。

Claims (7)

1.一种富巯基吸附材料组合物的制备方法，其特征在于：
（a）、65质量份X分子筛的原粉，8质量份氧化钙，1质量份氧化铝，1质量份氧化镁，3质量份粘结剂，2质量份扩孔剂，按配比混合形成均一体系的混合粉末；
（b）、高温下烧结后粉碎研磨至平均粒径1-10um；
（c）、上述组分以悬浮液形式在溶液中加入3-巯基丙基三甲氧基硅烷，调节pH至8-10，200℃高压水热，过滤干燥。
2.根据权利要求1所述的富巯基吸附材料组合物的制备方法，其中烧结温度为700℃以上。
3.根据权利要求1所述的富巯基吸附材料组合物的制备方法，其中所述氧化物粘结剂为二氧化硅溶胶。
4.根据权利要求1所述的富巯基吸附材料组合物的制备方法，其中3-巯基丙基三甲氧基硅烷溶液是水溶液。
5.根据权利要求1所述的富巯基吸附材料组合物的制备方法，其中水热时间2小时。
6.根据权利要求1所述的富巯基吸附材料组合物的制备方法，其中研磨至平均粒径1um。
7.一种吸附水中重金属离子的方法，所述方法使用根据权利要求1-6任一项所述富巯基吸附材料组合物的制备方法制备的富巯基改性吸附材料组合物。
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