CN111848130A - 一种高效除磷的改性陶粒及其制备方法 - Google Patents
一种高效除磷的改性陶粒及其制备方法 Download PDFInfo
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- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims description 6
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明提供一种高效除磷的改性陶粒及其制备方法，改性陶粒以造纸白泥和粉煤灰为主要原料，其中，造纸白泥40‑60wt%；粉煤灰40‑60wt%。制备方法包括如下步骤：（1）以造纸白泥和粉煤灰为主要原料，按配比混匀后，经离心式成球机制成生球，生球粒径在2‑20mm范围内可控；（2）将步骤（1）制得的生球自然养护20h‑24h后，经105℃烘干，最后煅烧获得陶粒；（3）将步骤（2）的陶粒投入总磷浓度为15‑20mg/L的KH2PO4溶液中，静态吸附至饱和后取出；（4）将吸附饱和的陶粒于105℃的干燥1‑2h，再经烧结炉煅烧，获得高效除磷的改性陶粒。本发明制备的陶粒在改性前后都具有供碱释钙能力，都能达到除磷的目的。本发明制备的改性陶粒，在吸附除磷时，速率快，吸附容量大，效果显著。
Description
技术领域
本发明属于材料制备和环境工程水处理的技术领域，具体涉及一种高效除磷的改性陶粒及其制备方法。
背景技术
近二十年来，我国磷化工得到了迅速发展，但同时磷带来的环境污染也日趋严重，已经威胁到水生生物的生存和人类的健康。例如，长期饮用磷超标的水可使人的骨质疏松，发生下颌骨坏死等病变。
目前，应用较广泛的除磷技术有化学沉淀法、生物法和吸附法等。吸附法由于具有占地面积小、工艺简单、操作方便、无二次污染等特点而倍受关注。吸附剂是吸附法的核心，其性能优劣决定了分离效果的好坏。常见的除磷吸附剂有氧化铝、沸石、硅藻土、膨润土等。但是硅藻土等天然吸附剂需要对大自然进行开采，为了保护环境，降低成本，本着“以废治污”的理念，利用废弃物制备的除磷吸附剂开始成为研究与应用热点。
可以制备除磷吸附剂的废弃物主要包括水厂污泥、生物质废物、工业废渣等。不同废弃物的理化性质不同，因此处理过程中不可避免的存在一些问题。水厂污泥常含有大量的颗粒和有机质，使得其有效除磷吸附位点较少，吸附能力较低。对水厂污泥的改性一般需要消耗大量的热能或化学试剂，增加吸附成本。生物质废物包括植物残渣、动物排泄物、城市污泥等，其通常制成生物炭，再经阳离子改性来增强除磷效果。而该过程中一般会产生有机尾气，造成环境污染。工业废渣包括钢渣、粉煤灰、赤泥等，原料选择范围广泛，除磷效果较为理想。生物质废物和工业废渣共同使用用于除磷，目前尚未见相关报道。
发明内容
本发明要解决的技术问题是提供一种高效除磷的改性陶粒及其制备方法，其原料为造纸厂和燃煤电厂的固体废弃物，制备过程简单、除磷快速且高效。
为解决上述技术问题，本发明的实施例提供一种高效除磷的改性陶粒，以造纸白泥和粉煤灰为主要原料，其中，造纸白泥40-60wt%；粉煤灰40-60wt%。
本发明还提供一种如权利要求1所述的高效除磷的改性陶粒的制备方法，包括如下步骤：
（1）以造纸白泥和粉煤灰为主要原料，按配比混匀后，经离心式成球机制成生球，生球粒径在2-20mm范围内可控；
（2）将步骤（1）制得的生球自然养护20h-24h后，经105℃烘干，最后煅烧获得陶粒；
（3）将步骤（2）的陶粒投入总磷浓度为15-20mg/L的KH2PO4溶液中，静态吸附至饱和后取出；
（4）将吸附饱和的陶粒于105℃的干燥1-2h，再经烧结炉煅烧，获得高效除磷的改性陶粒。
其中，步骤（1）中，造纸白泥的用量为40-60wt%。
其中，步骤（2）中的煅烧温度为1000-1150℃。
其中，步骤（2）获得的陶粒以钙长石和钙铝黄长石为主要矿物相。
其中，步骤（3）中，陶粒在20mg/L的KH2PO4溶液中，吸附16-28h达到平衡，吸附容量为0.25-0.85mg/g。
其中，步骤（3）中，陶粒吸附除磷后，表面形成一层羟基磷灰石的细小颗粒沉淀。
其中，步骤（4）中，吸附饱和后的陶粒改性煅烧温度为850℃。
本发明的上述技术方案的有益效果如下：
1、本发明制备的陶粒在改性前后都具有供碱释钙能力，都能达到除磷的目的。
2、本发明的改性过程简单，在改性时仍可以达到除磷的目的，一举两得。
3、本发明制备的改性陶粒，在吸附除磷时，速率快，吸附容量大，效果显著。
附图说明
图1为本发明中陶粒改性前后的XRD图谱；
图2为本发明中陶粒改性前后除磷效果；
图3为本发明中陶粒改性前后的SEM-EDS图谱。
具体实施方式
为使本发明要解决的技术问题、技术方案和优点更加清楚，下面将结合附图及具体实施例进行详细描述。
本发明提供一种高效除磷的改性陶粒，以造纸白泥和粉煤灰为主要原料，其中，造纸白泥40-60wt%；粉煤灰40-60wt%。
上述高效除磷的改性陶粒的制备方法包括如下步骤：
（1）以造纸白泥和粉煤灰为主要原料，按配比混匀后，经离心式成球机制成生球，生球粒径在2-20mm范围内可控；
（2）将步骤（1）制得的生球自然养护20h-24h后，经105℃烘干，最后煅烧获得陶粒；
（3）将步骤（2）的陶粒投入总磷浓度为15-20mg/L的KH2PO4溶液中，静态吸附至饱和后取出；
（4）将吸附饱和的陶粒于105℃的干燥1-2h，再经烧结炉煅烧，获得高效除磷的改性陶粒。
下面结合具体实施例进一步阐述本发明的技术方案。
实施例1
选择原料配比为50wt%造纸白泥和50wt%粉煤灰,经水泥砂浆搅拌机混匀，控制水固比为0.05，将混合料放入离心式成球机制成生球。将生球自然养护24h后放入干燥箱经105℃干燥12h，最后移入高温煅烧炉煅烧，升温速率为10℃/min至800℃，在800℃保温1h，然后以5℃/min升至1050℃并保温2 h，最后随炉冷却，制得以钙长石和钙铝黄长石为主要矿物相，具有供碱释钙特性的陶粒，其XRD图谱如图1所示。
实施例2 采用静态吸附法对陶粒进行除磷改性
以分析纯试剂KH2PO4配置总磷浓度为20mg/L的模拟含磷污水。以20g/L的投加量将实施例1中制备的陶粒投入模拟含磷污水中，放入水浴恒温振荡箱，在25℃、120r/min的条件下水平振荡，在不同时间间隔（0.5、1、3、6、9、12、16、20、24h）取样，经0.45μm的滤膜过滤提取水样，测定剩余磷浓度，计算除磷率，结果如图2所示。可以看出，陶粒在16h左右达到吸附平衡，去除率为82%，吸附容量为0.82mg/g。
实施例3
将实施例2中吸附饱和的陶粒在105℃干燥，然后在马弗炉中经850℃煅烧获得改性陶粒，其XRD图谱见图1。可见，改性前后陶粒的主要矿物相组成没有改变。将改性前后的陶粒进行SEM和EDS分析，结果如图3所示，其中图3（a）为陶粒SEM图，3（b）为陶粒EDS图，3（c）为改性陶粒SEM图，3（d）为改性陶粒EDS图。可见，在改性后陶粒表面检测出P元素，推测为羟基磷灰石。经静态浸出实验测试，改性陶粒在水溶液中无磷浸出。继续以静态吸附法对陶粒进行除磷实验，实验条件同实施例2，结果见图2。与改性前对比可以发现，改性陶粒在30min之内就可以达到吸附平衡，除磷率约98%，吸附容量提升至0.98mg/g，改性陶粒实现快速高效除磷的目的。
本发明的原理为：本发明制备的陶粒以钙长石CaO·Al2O3·2SiO2和钙铝黄长石2CaO·Al2O3·SiO2作为主要晶相，钙长石保证了陶粒的使用强度，钙铝黄长石使陶粒具有供碱释钙特性，即向水溶液中释放Ca2+和OH-的能力。释碱能力使陶粒能够自主调节溶液至碱性，有利于Ca2+与PO4 3-、HPO4 2-生成的磷酸钙Ca3(PO4) 2和磷酸氢钙CaHPO4沉淀，如式（1）和（2）所示。
3Ca2++2PO4 3-=Ca3(PO4) 2 （1）；
Ca2++HPO4 2-=CaHPO4 （2）。
在碱性氛围下，磷酸钙和磷酸氢钙沉淀会逐渐生成更稳定的羟基磷灰石（HAP，Ca5(PO4)3 OH），并被陶粒表面吸附。陶粒的供碱释钙属于缓释过程，因此该吸附除磷过程需要16-28h才能达到平衡，即吸附饱和。在本发明中，该步骤既可以作吸附除磷应用，也是为下一步改性做准备，将陶粒的除磷作用最大化。
将吸附饱和后的陶粒干燥后进行850℃煅烧，使羟基磷灰石沉淀稳定固化在陶粒表面，得到改性陶粒。当改性陶粒再次吸附除磷时，其仍保有供碱释钙能力，且陶粒表面的羟基磷灰石颗粒就可以作为籽晶，诱导磷酸盐沉淀的快速形成，使改性陶粒达到快速高效除磷的目的。
以上所述是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明所述原理的前提下，还可以作出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。
Claims (8)
1.一种高效除磷的改性陶粒，其特征在于，以造纸白泥和粉煤灰为主要原料，其中，造纸白泥40-60wt%；粉煤灰40-60wt%。
2.一种如权利要求1所述的高效除磷的改性陶粒的制备方法，其特征在于，包括如下步骤：
（1）以造纸白泥和粉煤灰为主要原料，按配比混匀后，经离心式成球机制成生球，生球粒径在2-20mm范围内可控；
（2）将步骤（1）制得的生球自然养护20h-24h后，经105℃烘干，最后煅烧获得陶粒；
（3）将步骤（2）的陶粒投入总磷浓度为15-20mg/L的KH2PO4溶液中，静态吸附至饱和后取出；
（4）将吸附饱和的陶粒于105℃的干燥1-2h，再经烧结炉煅烧，获得高效除磷的改性陶粒。
3.根据权利要求2所述的高效除磷的改性陶粒的制备方法，其特征在于，步骤（1）中，造纸白泥的用量为40-60wt%。
4.根据权利要求2所述的高效除磷的改性陶粒的制备方法，其特征在于，步骤（2）中的煅烧温度为1000-1150℃。
5.根据权利要求2或4所述的高效除磷的改性陶粒的制备方法，其特征在于，步骤（2）获得的陶粒以钙长石和钙铝黄长石为主要矿物相。
6.根据权利要求2所述的高效除磷的改性陶粒的制备方法，其特征在于，步骤（3）中，陶粒在20mg/L的KH2PO4溶液中，吸附16-28h达到平衡，吸附容量为0.25-0.85mg/g。
7.根据权利要求2或6所述的高效除磷的改性陶粒的制备方法，其特征在于，步骤（3）中，陶粒吸附除磷后，表面形成一层羟基磷灰石的细小颗粒沉淀。
8.根据权利要求2所述的高效除磷的改性陶粒的制备方法，其特征在于，步骤（4）中，吸附饱和后的陶粒改性煅烧温度为850℃。
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