CN115178233B - 一种以大宗固废为原料的除氨氮硬质材料及其制备方法 - Google Patents

一种以大宗固废为原料的除氨氮硬质材料及其制备方法 Download PDF

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CN115178233B
CN115178233B CN202210591364.6A CN202210591364A CN115178233B CN 115178233 B CN115178233 B CN 115178233B CN 202210591364 A CN202210591364 A CN 202210591364A CN 115178233 B CN115178233 B CN 115178233B
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王昊
王超
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CNOOC Tianjin Chemical Research and Design Institute Co Ltd
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Abstract

本发明公开了一种利用大宗固废制备的除氨氮硬质材料及其制备方法。该制备方法包括：将低铝煤矸石、赤泥和粉煤灰按比例混合后的物料研磨至300～450目，将研磨经干燥的物料在950℃～1050℃恒温煅烧3～6h，然后自然冷却；将煅烧后的物料进行酸化活性处理，然后浸入0.1mol/L～0.15mol/L的高锰酸钾溶液，恒温搅拌，然后缓慢添加2％～4％氢氧化钠溶液，搅拌均匀后，过滤后得到固体产物，水洗干燥后得到除氨氮硬质材料。本发明除氨氮硬质材料能配合曝氧装置，＝实现在水体中持续的吸附和催化氧化过程，从而实现氨氮的长时间持续降解，且产品强度高，可根据现场需求制作不同形状的载体材料，使用方便。

Description

一种以大宗固废为原料的除氨氮硬质材料及其制备方法
技术领域
本发明涉及一种用于自然水体环境治理的以大宗固废为原料的除氨氮硬质 材料，具体涉及一种应用于自然水体环境，用以降低水体中氨氮含量，提高水质 质量的除氨氮硬质材料。
背景技术
我国在经济飞速发展的几十年间，随着经济和社会的不断发展，环境污染也 与日俱增。氨氮作为污染最为广泛的一种污染物，在我国土壤、地下水、地表水 等均普遍存在。氨氮作为营养物质，当进入水体后会造成富营养化，能在短时间 内急速加剧水体的水质恶化，使水体发黑发臭。蓝藻、赤潮等由于富营养化造成 的自然现象曾一度侵袭我国大部分淡水流域和沿海地区。
传统去除氨氮的方法主要包括生化工艺、吹脱工艺、折点加氯工艺，在工业 污水的氨氮处理中得到了广泛应用，但由于工艺技术特点，难以应用在自然水体 环境的治理上。
吸附材料产品是目前用以解决自然大面积水体氨氮污染的主要方向：沸石、 火山岩、蛭石、硅藻土等天然矿物及改性产品是目前主要的市场技术产品。但由 于大宗产品的价格上涨、吸附材料的一次性使用和再生方式不适用与大面积水 域，材料的使用成本是亟待解决的问题。
发明内容
为了克服现有除氨氮材料使用成本高、难以再生处理等问题和不足，本发明 提供了一种在大面积自然水体中，配合简单曝气操作，即可实现降低氨氮，提升 水质的以大宗固废为原料的除氨氮硬质材料。该材料通过使用大宗固废作为原材 料，构建高通量骨架，并负载催化剂，使材料在水体中配合曝气装置，可以长时间使用，不用再生处理，降低了使用成本。
本发明解决其技术问题所采用的技术方案是：
本发明提供一种用于自然水体环境治理的以大宗固废为原料的除氨氮硬质 材料的制备方法，包括如下步骤：
1)原料配料：将低铝煤矸石、赤泥和粉煤灰等物料，按照以下质量百分比 充分混合：低铝煤矸石20％～30％、赤泥5％～15％、余量为粉煤灰；
2)混合物料处理：将混合后的物料研磨至300～450目，在150℃～200℃温 度范围内干燥1～2h；
3)煅烧处理：将研磨干燥好的物料在950℃～1050℃恒温煅烧3～6h，然后自 然冷却至室温后取出；
4)负载处理：将煅烧后的物料用5％～10％的无机酸溶液进行酸化活性处理， 然后将处理后的物料浸渍入0.1mol/L～0.15mol/L的高锰酸钾溶液，随后将混合物 从室温加热至60～70℃并保持恒温搅拌30～60min，然后缓慢添加质量浓度为 2％～4％的氢氧化钠溶液；搅拌均匀后，过滤后得到固体产物，水洗干燥后得到材 料产品。
本发明上述制备方法中，所述的无机酸优选为硫酸和盐酸。
本发明还进一步提供了上述制备方法制备得到除氨氮硬质材料，更进一步提 供了该除氨氮硬质材料在自然水体环境治理中的应用。
本发明的有益效果是：本发明制备方法以大宗固废作为原料，降低了产品成 本，利用原料中的硅、铝、铁等元素构建中等强度高通量载体架构，利用煤矸石 中的有机成分在煅烧时挥发从而形成通道，并对混合其中的铁进行活性化处理， 并进一步负载锰元素，通过水热反应实现铁锰复合氧化物的有效负载，避免了通 常浸渍法容易脱落的缺点。本发明制备得到除氨氮硬质材料可以克服现有材料在使用成本和连续使用不便的缺点，配合曝氧装置，即可实现在水体中持续的吸附 和催化氧化过程，从而实现氨氮的长时间持续降解，且产品强度高，可根据现场 需求，后期制作不同形状的载体材料，以便于应用。
具体实施方式：
实施例一：本发明的以大宗固废为原料的除氨氮硬质材料将低铝煤矸石、赤 泥和粉煤灰等物料，按照以下质量百分比充分混合：低铝煤矸石30％、赤泥5％、 余量为粉煤灰；将混合后的物料研磨至400目，在150℃恒温干燥1h；将研磨干 燥好的物料在950℃恒温煅烧4h，然后自然冷却至室温后取出；将煅烧后的物料用10％的硫酸溶液进行酸化活性处理，然后将处理后的物料浸渍入0.1mol/L的 高锰酸钾溶液，加热升温至65℃恒温搅拌30min，然后缓慢添加4％氢氧化钠溶 液。搅拌均匀后，过滤后得到固体产物，水洗干燥后得到材料产品。
取用一处劣五类河道水体水样作为测试水样，使用市售沸石类氨氮吸附材料 和活性炭氨氮吸附材料作为对比样品，同质量比填充柱进行过滤测试，实施例产 品与对比样品性能测试数据如下：
表1实施例一除氨氮测试对比数据
由表1数据可以看出，实施例一的产品的氨氮去除量明显高于市售对比产 品，使用成本低。
实施例二：本发明的以大宗固废为原料的除氨氮硬质材料将低铝煤矸石、赤 泥和粉煤灰等物料，按照以下质量百分比充分混合：低铝煤矸石20％、赤泥10％、 余量为粉煤灰；将混合后的物料研磨至350目，在200℃恒温干燥1.5h；将研磨 干燥好的物料在1050℃恒温煅烧3h，然后自然冷却至室温后取出；将煅烧后的物料用7％的盐酸溶液进行酸化活性处理，然后将处理后的物料浸渍入0.15mol/L 的高锰酸钾溶液，加热至60℃保持恒温搅拌60min，然后缓慢添加3％氢氧化钠 溶液。搅拌均匀后，过滤后得到固体产物，水洗干燥后得到材料产品。
取用一段黑臭湖泊水体水样作为测试水样，使用市售沸石类氨氮吸附材料和 活性炭氨氮吸附材料作为对比样品，同质量比填充柱进行过滤测试，实施例产品 与对比样品性能测试数据如下：
表1实施例二除氨氮测试对比数据
由表1数据可以看出，实施例二的产品的氨氮去除量明显高于市售对比产 品，使用成本低。

Claims (4)

1.一种以大宗固废为原料的除氨氮硬质材料的制备方法，其特征在于，包括如下步骤：
原料配料：将低铝煤矸石、赤泥和粉煤灰按照以下质量百分比充分混合：低铝煤矸石20%~30%、赤泥5%~15%、余量为粉煤灰；
混合物料处理：将混合后的物料研磨至300~450目，在150℃~200℃温度范围内干燥1~2h；
煅烧处理：将研磨干燥好的物料在950℃~1050℃恒温煅烧3~6h，然后自然冷却至室温后取出；
负载处理：将煅烧后的物料用5%~10%的无机酸溶液进行酸化活性处理，然后将处理后的物料浸渍入0.1mol/L~0.15mol/L的高锰酸钾溶液，随后将混合物从室温加热至60~70℃并保持恒温搅拌30~60min，然后缓慢添加质量浓度为2%~4%的氢氧化钠溶液；搅拌均匀后，过滤后得到固体产物，水洗干燥后得到材料产品。
2.根据权利要求1所述的制备方法，其特征在于，所述的无机酸为硫酸、盐酸。
3.一种权利要求1所述的制备方法制备得到除氨氮硬质材料。
4.一种权利要求3所述的除氨氮硬质材料在自然水体环境治理中的应用。
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CN102188953A (zh) * 2011-03-30 2011-09-21 山西大学 一种用于处理氨氮废水的改性粉煤灰及其制备方法
CN107051413B (zh) * 2017-01-10 2019-11-19 中国科学院过程工程研究所 一种由赤泥与煤/炭制备铁-活性炭复合材料的方法
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