CN113416088A - 一种可吸附氨氮的改性钙长石陶粒及其制备方法 - Google Patents
一种可吸附氨氮的改性钙长石陶粒及其制备方法 Download PDFInfo
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- GWWPLLOVYSCJIO-UHFFFAOYSA-N dialuminum;calcium;disilicate Chemical class [Al+3].[Al+3].[Ca+2].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] GWWPLLOVYSCJIO-UHFFFAOYSA-N 0.000 title claims abstract description 34
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 39
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000001354 calcination Methods 0.000 claims abstract description 14
- 239000010881 fly ash Substances 0.000 claims abstract description 14
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- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 14
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 13
- 229910001629 magnesium chloride Inorganic materials 0.000 claims abstract description 13
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- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 8
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 8
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims abstract description 7
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
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- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
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- 235000019270 ammonium chloride Nutrition 0.000 description 1
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- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
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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
- 230000007613 environmental effect Effects 0.000 description 1
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Abstract
本发明提供了一种可吸附氨氮的改性钙长石陶粒及其制备方法,其中,改性钙长石陶粒为负载氧化镁的陶粒,改性钙长石陶粒由陶粒、氯化镁溶液及氢氧化钠溶液制得,陶粒由固体废弃物造纸白泥、粉煤灰制得;其制备方法,包括如下步骤:以固体废弃物造纸白泥和粉煤灰为主要原料,高岭土为添加剂,按配比混匀后,经离心式成球机制成生球;将制得的生球自然养护后,烘干,最后煅烧获得陶粒;将陶粒与氯化镁溶液混合并超声,再加入氢氧化钠溶液,经振荡、静置、过滤、清洗和干燥,获得负载氢氧化镁的陶粒;负载氢氧化镁的陶粒煅烧,获得负载氧化镁的陶粒。本发明制备的改性钙长石陶粒可以对氨氮实现快速的吸附去除,操作简单,经济环保。
Description
技术领域
本发明属于材料制备和环境工程水处理技术领域,具体涉及一种可吸附氨氮的改性钙长石陶粒及其制备方法。
背景技术
氮是水生生物生长的基本要素之一,然而过多的营养物质输入到湖泊、河流、水库和海岸线等地表水中会导致水体富营养化,水中溶解氧耗尽,水质开始下降。因此,在排放前去除水中的氮元素对防止地表水污染具有重要的意义。
目前,常用的脱氮工艺包括化学沉淀法、膜分离法、结晶法、生物法和吸附法。吸附法的应用范围很广,主要用来去除水中的微量污染物,如重金属、各种溶解性有机物、放射性元素等。利用吸附法进行水处理,具有运用范围广、处理效果好、操作过程简单、二次污染小、吸附剂可重复使用等优点。吸附剂是吸附法的关键,吸附剂决定吸附效果,常见的去除氨氮的吸附剂有氧化铝、沸石、硅藻土、膨润土等。
造纸白泥和粉煤灰是工业生产的废渣,利用造纸白泥和粉煤灰作为原料制备陶粒,能够减少过量固废物堆积对环境造成的危害,并将其应用于废水处理,从而达到以废治废的目的。制得的原始钙长石陶粒因其孔隙率小,比表面积较低,导致其吸附能力较弱,吸附效果不理想,几乎无吸附除氮的能力,应用范围受到很大的限制。因此,对钙长石陶粒进行改性,提高其除氮率,在开发一种多功能陶粒和对水资源回收利用方面具有重要意义。
发明内容
本发明要解决的技术问题是提供一种可吸附氨氮的改性钙长石陶粒及其制备方法,其原料为造纸厂和燃煤电厂的固体废弃物,可以对氮实现高效、快速的吸附去除,操作简单,经济环保。
为解决上述技术问题,本发明的实施例提供一种可吸附氨氮的改性钙长石陶粒,其特征在于,所述改性钙长石陶粒为负载氧化镁陶粒,所述改性钙长石陶粒由陶粒、氯化镁溶液及氢氧化钠溶液制得,所述陶粒的主要原料为固体废弃物造纸白泥和粉煤灰制得,可增加添加剂,所述添加剂为高岭土。
本发明的实施例还提供一种可吸附氨氮的改性钙长石陶粒的制备方法,其特征在于,包括如下步骤:
(1)将原料按配比混匀后,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20-24h后,经105℃烘干,最后煅烧获得陶粒;
(3)将步骤(2)中陶粒与氯化镁溶液混合并超声,再加入氢氧化钠溶液,经振荡、静置、过滤、清洗和干燥,获得负载氢氧化镁的陶粒;
(4)将步骤(3)中陶粒置于马弗炉中煅烧,获得负载氧化镁的陶粒,即改性陶粒。
进一步的,步骤(1)中,主要原料为固体废弃物造纸白泥和粉煤灰,添加剂为高岭土,其中,造纸白泥10-30wt%,粉煤灰70-80wt%,高岭土0-10wt%。
进一步的,步骤(2)中,煅烧温度为1000-1150℃,保温时间为0-2h。
进一步的,步骤(2)中,获得的陶粒以钙长石为主要矿物相。
进一步的,步骤(3)中,氯化镁溶液的浓度为1-2mol/L,氢氧化钠溶液的浓度为1-4mol/L,陶粒与溶液的固液比为1:10-20(固体单位为g,溶液单位为mL)。
进一步的,步骤(3)中,超声时间为20-40min;利用恒温水浴箱进行振荡,振荡时间为10-14h,水浴温度为20-30℃,振荡速率120r/min。
进一步的,步骤(3)中,静置时间为20-28h。
进一步的,步骤(3)中,过滤结束后用乙醇和纯水交替清洗3次,经鼓风干燥箱80℃干燥。
进一步的,步骤(4)中,马弗炉煅烧条件为升温速率10℃/min,温度450℃,保温时间2-4h。
本发明的上述技术方案的有效效果如下:
1、本发明的改性方法具有科技创新性高、操作过程简单、成本低廉等特点,不会造成二次污染,经济又环保。本发明所制备的改性陶粒为负载氧化镁层的陶粒,陶粒制备采用固体废弃物造纸白泥和粉煤灰制得陶粒,所制得的陶粒再与氯化镁溶液、氢氧化钠溶液制成改性陶粒,这种陶粒材料易得,改性过程简单,制备条件要求不高且制备效率高。
2、本发明制备的陶粒在改性后可以对氨氮实现高效、快速的去除,吸附效果显著;改性陶粒吸附氨氮时,2h左右达到吸附平衡,去除率为41%,吸附容量为1.23mg/g,本发明所制备的改性陶粒去除氨氮效果佳。
3、本发明制备的改性陶粒是一种绿色的水污染处理剂,解决了原始陶粒处理污水中氨氮效果差的问题,具有广阔的应用前景。
附图说明
图1为本发明实施例中陶粒改性前后的XRD图谱;
图2为本发明实施例中陶粒改性后除氮效果图。
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。
本发明提供一种可吸附氨氮的改性钙长石陶粒,所述改性钙长石陶粒为负载氧化镁的陶粒,所述改性钙长石陶粒由陶粒、氯化镁溶液及氢氧化钠溶液制得,所述陶粒的主要原料为固体废弃物造纸白泥和粉煤灰,所述陶粒的添加剂为高岭土。其中,造纸白泥10-30wt%,粉煤灰70-80wt%,高岭土0-10wt%。
上述可吸附氨氮的改性钙长石陶粒的制备方法包括如下步骤:
(1)将原料按配比混匀后,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20-24h后,经105℃烘干,最后煅烧获得陶粒;
(3)将步骤(2)中陶粒与氯化镁溶液混合并超声,再加入氢氧化钠溶液,经振荡、静置、过滤、清洗和干燥,获得负载氢氧化镁的陶粒;
(4)将步骤(3)中陶粒置于马弗炉中煅烧,获得负载氧化镁的陶粒,即改性陶粒。
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
选择原料质量比为造纸白泥:粉煤灰=20:80,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2h,最后随炉冷却,制得以钙长石为主要矿物相的陶粒,其XRD图谱如图1中“改性前”所示。
实施例2
将实施例1中制得的20g陶粒与200mL浓度为1.25mol/L的氯化镁溶液混合并超声30min,再加入200mL浓度为2.25mol/L的氢氧化钠溶液,利用恒温水浴箱进行振荡,振荡时间为12h,水浴温度为25℃,振荡速率120r/min。溶液静置24h,过滤,过滤结束后用乙醇和纯水交替清洗3次,经鼓风干燥箱80℃干燥,获得负载氢氧化镁的陶粒。再将负载氢氧化镁的陶粒煅烧,马弗炉煅烧条件为升温速率10℃/min,温度450℃,保温时间3h,获得负载氧化镁的陶粒,即改性陶粒,其XRD图谱如图1中“改性后”所示。
从实施例1和实施例2的结果对比可见,改性后陶粒仍以钙长石为主物相,但氯化镁和氢氧化钠溶液能浸透到陶粒内部并发生化学反应,使部分氧化镁生成。
实施例3
以分析纯试剂氯化铵配置氨氮溶液,氨氮初始浓度为60mg/L,实施例2中改性陶粒作为吸附剂,投加量为20g/L。放入恒温振荡箱,在25℃、120r/min的条件下水平振荡,在不同时间间隔(5min、10min、15min、20min、30min、40min、1h、2h、4h)取样,经过0.45μm的滤膜过滤提取水样,测定剩余氨氮浓度,计算氨氮的去除率,结果如图2所示。可以看出,改性陶粒吸附氨氮时,2h左右达到吸附平衡,去除率为41%,吸附容量为1.23mg/g。
本发明的原理为:本发明制备的陶粒以钙长石为主要晶相,以陶粒为载体负载氧化镁。改性前陶粒可能由于供碱能力不够,导致氨氮的去除效果不好。陶粒改性后,表面负载有氧化镁, Mg2+与NH4 +的离子交换是改性陶粒去除废水中氨氮的主要机理过程。此外,氨氮在废水中以NH4 +和 NH3·H2O 存在并保持平衡,这两种存在形式取决于废水 pH 和温度。陶粒负载氧化镁改性后,不仅增加了其比表面积,还提高了其供碱能力,使分子吸附也成为改性陶粒除氨氮的重要途径。
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 (10)
1.一种可吸附氨氮的改性钙长石陶粒,其特征在于,所述改性钙长石陶粒为负载氧化镁的陶粒,所述改性钙长石陶粒由陶粒、氯化镁溶液及氢氧化钠溶液制得,所述陶粒由固体废弃物造纸白泥、粉煤灰制得。
2.一种可吸附氨氮的改性钙长石陶粒的制备方法,其特征在于,包括如下步骤:
(1)将原料按配比混匀后,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20-24h后,经105℃烘干,最后煅烧获得陶粒;
(3)将步骤(2)中陶粒与氯化镁溶液混合并超声,再加入氢氧化钠溶液,经振荡、静置、过滤、清洗和干燥,获得负载氢氧化镁的陶粒;
(4)将步骤(3)中陶粒置于马弗炉中煅烧,获得负载氧化镁的陶粒,即改性陶粒。
3.根据权利要求2所述的一种可吸附氨氮的改性钙长石陶粒的制备方法,其特征在于,步骤(1)中,主要原料为固体废弃物造纸白泥和粉煤灰,添加剂为高岭土,其中,造纸白泥10-30wt%,粉煤灰70-80wt%,高岭土0-10wt%。
4.根据权利要求2所述的一种可吸附氨氮的改性钙长石陶粒的制备方法,其特征在于,步骤(2)中,煅烧温度为1000-1150℃,保温时间为0-2h。
5.根据权利要求2所述的一种可吸附氨氮的改性钙长石陶粒的制备方法,其特征在于,步骤(2)中,获得的陶粒以钙长石为主要矿物相。
6.根据权利要求2所述的一种可吸附氨氮的改性钙长石陶粒的制备方法,其特征在于,步骤(3)中,氯化镁溶液的浓度为1-2mol/L,氢氧化钠溶液的浓度为1-4mol/L,陶粒与溶液的固液比为1:10-20(固体单位为g,溶液单位为mL)。
7.根据权利要求2所述的一种可吸附氨氮的改性钙长石陶粒的制备方法,其特征在于,步骤(3)中,超声时间为20-40min;利用恒温水浴箱进行振荡,振荡时间为10-14h,水浴温度为20-30℃,振荡速率120r/min。
8.根据权利要求2所述的一种可吸附氨氮的改性钙长石陶粒的制备方法,其特征在于,步骤(3)中,静置时间为20-28h。
9.根据权利要求2所述的一种可吸附氨氮的改性钙长石陶粒的制备方法,其特征在于,步骤(3)中,过滤结束后用乙醇和纯水交替清洗3次,经鼓风干燥箱80℃干燥。
10.根据权利要求2所述的一种可吸附氨氮的改性钙长石陶粒的制备方法,其特征在于,步骤(4)中,马弗炉煅烧条件为升温速率10℃/min,温度450℃,保温时间2-4h。
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