CN105749952A - B、N、Ti共掺杂漂浮型环境修复材料的制备方法及其应用 - Google Patents
B、N、Ti共掺杂漂浮型环境修复材料的制备方法及其应用 Download PDFInfo
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Abstract
B、N、Ti共掺杂漂浮型环境修复材料的制备方法及其应用，属于环境修复领域，本发明选择使用低成本、易分离回收的膨胀珍珠岩为载体，制成负载B、TiO2的膨胀珍珠岩经烘干后，再在氨气气氛中于400℃焙烧，取得B、N、Ti共掺杂漂浮型环境修复材料。达到高效降解环境中有机污染物的目的，经研究其使用条件和回收方法，以获得新型廉价高效易回收可重复使用的有机废水环境修复材料。
Description
技术领域
本发明属于环境修复领域，具体涉及去除水体、土壤环境中有机污染物的环境修复材料的制备和使用方法。
背景技术
化学工业和化学农业所带来的水体、土壤的有机污染问题日益严重，部分化工厂、农药厂搬迁遗留场地以及石油矿井周边水体和土壤也存在较严重的有机污染，因此如何将污染物从污染环境中去除已成为急待解决的科学问题。目前通过吸附去除水中有机物被认为是最有效的手段。粒状活性炭、吸附树脂、粘土矿物等都被应用于水体有机污染物的去除。
目前，水处理有机污染物技术基本上都属于分离处理过程如沉降、絮凝、过滤、吸附、气提等，但分离处理只是将污染物分离或浓缩，或者只是将污染物从一相转移到另一相，不能使污染物得到彻底分解而实现无害化有的方法还不可避免地带来二次污染的问题；稀释处理只是通过稀释废水来减轻水体的污染，既未把污染物分离，也不会改变污染物的化学性质，转化处理则是通过化学的或生化的作用改变污染物的化学本性，使其转化为无害的或可分离的物质。同时，土壤有机污染的治理方法主要有淋洗、氧化还原和电动力学修复的化学方法、微生物方法、植物方法和菌根修复方法为代表的生物方法以及热处理、固化/稳定化的物理方法。
其中，光催化氧化技术处理有机污染物是近年来才发展起来的新型处理水、土壤的技术，其工艺设备简单、处理成本相对较低、操作条件易控制、氧化能力极强、可在常温常压下，在足够的反应时间里，将水中结构稳定的有机污染物彻底非选择性地氧化为CO2和H2O等简单无机物质，避免了二次污染，显示了良好的应用前景。
膨胀珍珠岩是由酸性火山玻璃质熔岩，经高温膨化而成的一种轻质多孔材料，可漂浮于水面且对有机物具有很强的吸附性，且膨胀珍珠岩的SiO2易与TiO2形成牢固的Ti-O-Si键的特点，在能量大于其禁带宽度（Eg）的紫外光照射下可产生由价带跃迁至导带的电子，生成电子(e-)-空穴(h+)对，电子和空穴在水溶液中产生有强氧化作用的羟基自由基和超氧自由基氧化降解水中有机污染物。将膨胀珍珠岩轻质多孔的特性与TiO2高效光催化性能相结合，硼、氮共掺杂二氧化钛表现出较强的光催化活性，在紫外和可见光照射下，硼、氮协同作用，从而制备出可用于修复有机污染环境的新型环境修复材料。
以上几种处理方法中，物理方法费用昂贵、难用于大规模污染改良，易破坏环境结构；化学方法引入的清洗剂易引发二次污染；生物方法对环境要求高、受影响因素多，且不利于修复高浓度、高毒性有机物。
发明内容
本发明的目的是提供一种基于膨胀珍珠岩的B、N共掺杂负载纳米TiO2的环境修复材料的制备方法。
本发明包括以下步骤：
1）将膨胀珍珠岩用硝酸洗净、烘干，制成粒径为8～20目的膨胀珍珠岩载体；
2）将膨胀珍珠岩置于容器中，加入由无水乙醇和异丙醇钛混合组成的溶液，经磁力搅拌后，再滴加由硼酸水溶液和醋酸组成的混合液，待形成凝胶后，再进行老化处理，取得负载B、TiO2的膨胀珍珠岩；
3）将负载B、TiO2的膨胀珍珠岩烘干后，再在氨气气氛中于400℃焙烧，取得B、N、Ti共掺杂漂浮型环境修复材料。
为了获得新型廉价高效易回收的环境修复材料，本发明选择使用低成本、易分离回收的膨胀珍珠岩为载体，并在该载体上负载光催化剂以达到高效降解环境中有机污染物的目的，研究其使用条件和回收方法，以获得新型廉价高效易回收可重复使用的有机废水环境修复材料。
制成的产品结构特征是：共掺杂漂浮型光催化剂的载体为具有轻质多孔、可漂浮的、粒径为8～20目的膨胀珍珠岩；载体上负载纳米TiO2和B的掺杂体；经氨气气氛下高温改性后制得B、N共掺杂TiO2漂浮型环境修复材料，最终TiO2的负载量为50～63%，B的负载量为1.5～12.6%，N的负载量为0.6～5.0%。
本发明利用廉价的膨胀珍珠岩和B-N/TiO2共掺杂制备新型环境修复材料处理环境中有机污染物。本发明优点在于膨胀珍珠岩材料来源丰富，方便易得，成本低廉，并充分利用B-N/TiO2共掺杂技术提高其光催化能力，制备流程简单，其处理废水中难降解有机污染物的效果显著优于常规活性炭和常见的TiO2修复材料；同时利用了其轻质多孔可漂浮于水的特点，可方便的将其从水体、土壤中分离取出，易于回收再生利用，也避免对水体、土壤后续利用的影响。
进一步地，本发明所述老化时间为24h。
老化时间对锐钛矿型TiO2的结晶度有一定的影响，由于溶胶有粘度，不利于短时间内结晶，因此需要24h老化。该老化时间目的主要是提高结晶度，也有助于形成晶形沉淀、同晶取代等的进行。
本发明的另一目的是提出以上B、N、Ti共掺杂漂浮型环境修复材料用于对有机废水进行净化处理。
即：以1∶50～500的质量比将所述环境修复材料与有机废水混合，置于暗处吸附后，再以光照催化处理，然后捞起漂浮的环境修复材料，取得净化水体。
另外，B、N、Ti共掺杂漂浮型环境修复材料还可以用于对有机污染土壤进行净化处理。
即：以1∶15～30的质量比将所述环境修复材料与有机污染土壤和水混合制成泥浆，置于暗处吸附，然后以光照催化处理，最后捞起漂浮的环境修复材料，获得净化后的泥浆，完成对土壤的净化。
以上两种方法捞起的环境修复材料可采用超声清洗2min，于200～300℃环境中活化1～3小时，得到活化后的环境修复材料，可重复用于有机污染土壤处理。
净化原理：当光照射在TiO2晶粒表面时，能量大于或等于3.2eV的光子可激发带电子向导带跃迁，形成电子（e-）空穴（h+）对，吸附于表面的h+、e-与O2、H2O等发生反应生成-OH、O2 -等高活性基团，这些活性物质再与表面吸附的有机物结合，从而使该物质氧化，最终分解为CO2和H2O。
本发明先采用暗处吸附再光照的目的：使催化剂与污染物达到吸附平衡。特殊效果：在搅拌下暗反应放氢放氧，且当TiO2在黑暗处放置一段时间后，经光照，其亲水性就可在短时间内完全恢复。
本发明作为环境修复材料用于环境中有机染料的降解，可高效去除水体和土壤中有机污染物，且催化剂稳定性强，因而具有广泛的应用前景。
所述的有机废水中的有机污染物为甲基橙、罗丹明B、苯酚和多环芳烃、双酚A等。所述的有机污染土壤中的有机污染物为苯酚、多环芳烃和石油等。环境修复材料的回收活化后重复使用的次数为5至7次。
具体实施方式
根据膨胀珍珠岩具有轻质多孔，可漂浮于水和超强的表面吸附作用，对持久性有机污染物具有很强的吸附能力的原理，将其与TiO2的光催化能力结合，并利用B-N/TiO2共掺杂进一步增加其光催化能力，制备出易于打捞、可重复利用的新型环境修复材料，用于环境中有机污染物的去除。有机废水中的有机污染物为甲基橙、罗丹明B、苯酚和多环芳烃、双酚A等；有机污染土壤中的有机污染物为苯酚、多环芳烃和石油等。
三、制备工艺：
取10mL无水乙醇、5～7mL异丙醇钛倒入烧杯搅拌得到溶液A。
取0.14～1.09g以硼酸和水混后形成硼酸水溶液，然后再加5～7mL的乙酸常温下磁力搅拌器混匀，得到溶液B。
将以硝酸洗净、风干、过筛后得到8～20目膨胀珍珠岩颗粒放入溶液A中，混匀后，再将溶液B逐滴加入至溶液A及膨胀珍珠岩的混合物中，制得稳定均一的透明凝胶后，在室温下老化24h。
将老化后的半制品烘干后于管式炉，氨气气氛（300～400ml/min）下，400℃焙烧2h，制得B-N/TiO2负载的环境修复材料。
另外，按照以上工艺，以下表混合量分别制备含有不同B-N-Ti比例的溶胶，经处理，可分别取得负载率不同的B-N/TiO2负载的环境修复材料。
（下表中未注的所有单位为：mL）
经试验，如将以上工艺中原料异丙醇钛置换为钛酸四丁酯也可用于本发明，由钛酸四丁酯制得的TiO2粘度大、稳定性高，但水解效果略差。而异丙醇钛自然水解之后便具有一定的锐钛矿晶型，结晶程度很高，且具有较强的催化性能。
二、应用：
1、对污染水体进行处理：
例1：取制备的B-N/TiO2负载的环境修复材料0.1g与50mL甲基橙溶液（质量比1∶500）混合后加入50mL石英管中，置于暗处吸附2h，500w氙灯光照2小时后捞起漂浮在水面上的环境修复材料，取得净化水，实验测得甲基橙的去除率35～72%。
例2：取制备的B-N/TiO2负载的环境修复材料0.1g与50mL甲基橙溶液（质量比1∶500）混合后加入50mL石英管中，置于暗处吸附2h，500w氙灯光照4小时后捞起漂浮在水面上的环境修复材料，取得净化水，实验测得甲基橙的去除率为70～100%。
以上两例中甲基橙溶液浓度范围：5～15mg/L。
2、对污染土壤进行处理：
取10g苯酚污染土壤（40mg苯酚/kg土）于玻璃培养皿(直径为90mm，下同)中，加入制备的B-N/TiO2负载的环境修复材料，加水混匀，使之成泥浆状。置于暗处吸附2h，然后加50ml纯水使材料漂浮，500w氙灯光照6小时，然后捞起漂浮在水面上的环境修复材料，完成对土壤的净化。实验测得苯酚的去除率50～60%。
三、活化处理：
捞起处理甲基橙有机废水后的环境修复材料，经滤干、超声清洗2分钟后，于250℃活化2小时，得到活化再生的环境修复材料；活化后环境修复材料重新用于有机废水的处理，效果可达原效果的80%以上。
Claims (4)
1.B、N、Ti共掺杂漂浮型环境修复材料的制备方法，其特征在于包括以下步骤：
1）将膨胀珍珠岩用硝酸洗净、烘干，制成粒径为8～20目的膨胀珍珠岩载体；
2）将膨胀珍珠岩置于容器中，加入由无水乙醇和异丙醇钛混合组成的溶液，经磁力搅拌后，再滴加由硼酸水溶液和醋酸组成的混合液，待形成凝胶后，再进行老化处理，取得负载B、TiO2的膨胀珍珠岩；
3）将负载B、TiO2的膨胀珍珠岩烘干后，再在氨气气氛中于400℃焙烧，取得B、N、Ti共掺杂漂浮型环境修复材料。
2.根据权利要求1所述的制备方法，其特征在于所述老化时间为24h。
3.如权利要求1所述方法制备的B、N、Ti共掺杂漂浮型环境修复材料用于对有机废水进行净化处理，其特征在于以1∶50～500的质量比将所述环境修复材料与有机废水混合，置于暗处吸附后，再以光照催化处理，然后捞起漂浮的环境修复材料，取得净化水体。
4.如权利要求1所述方法制备的B、N、Ti共掺杂漂浮型环境修复材料用于对有机污染土壤进行净化处理，其特征在于以1∶15～30的质量比将所述环境修复材料与有机污染土壤和水混合制成泥浆，置于暗处吸附，然后以光照催化处理，最后捞起漂浮的环境修复材料，获得净化后的泥浆。
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