CN113457622A - 一种铝锰复合改性生物炭的制备及其在磷去除方面的应用 - Google Patents
一种铝锰复合改性生物炭的制备及其在磷去除方面的应用 Download PDFInfo
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Abstract
本发明公开了一种铝锰复合改性生物炭的制备方法,包括(1)秸秆清洗后自然风干,粉碎后放置瓷坩埚内,放入马弗炉中炭化,自然冷却至室温后取出,用去离子水反复冲洗,洗净后在烘箱中干燥,干燥后的生物炭经研磨,过筛,得到秸秆生物炭,放于自封袋内密封保存;(2)称取秸秆生物炭于250ml锥形瓶中,然后加入AlCl3溶液和KMnO4溶液,搅拌,之后置于摇床中震荡,取出抽滤后用去离子水反复冲洗,置于烘箱中烘干,烘干后的生物炭称重后放入瓷坩埚,于生物炭制备温度下活化,自然冷却至室温后取出,即得铝锰复合改性生物炭;该制备方法简单易行,快捷方便,制备出的铝锰复合改性生物炭吸附能力强,对磷元素的吸附具有较宽的pH适应范围,具有较强的适应性。
Description
技术领域
本发明涉及一种铝锰复合改性生物炭的制备及其在磷去除方面的应用,属于活性炭制备领域。
背景技术
当前国内淡水湖泊富营养化日益严重,大量工业、农业、生活含磷废水排入自然水体对生态环境造成威胁,严重破坏水体生态多样性平衡,对水生生物的生存造成巨大威胁。为了缓解水环境压力,在控制源头排放的基础上,也要加大对现水体中磷元素的去除力度。从绿色环保的角度出发,多种除磷方法被开发利用,其中,吸附法由于其造价低廉、除磷效率高、二次污染小、易回收利用等优势得到了广泛的应用。生物炭是生物有机材料在缺氧环境中,经高温热裂解后产生的固态产物,具有巨大的比表面积,是一种极具潜力的吸附材料。然而由于生物炭原材料(多为植物秸秆)本身富含大量磷元素,经裂解制备的生物炭在水体中会产生磷释放作用,会抑制磷吸附作用。因此,研制一种对磷吸附能力强的生物炭具有重要意义。
酸碱改性是利用强酸强碱改性生物炭,使其表面的酸碱官能团发生变化,从而提高生物炭的吸附能力。如利用HNO3改性玉米秸秆生物炭,改性后生物炭表面含氧酸性官能团大量增加,比表面积增大,提高其对磷的吸附。利用镁改性生物炭,NH4 +与溶液中的Mg2+和PO4 3-发生沉淀反应,生成鸟粪石(MgNH4PO4•6H2O)促进磷的去除。利用FeCl3溶液改性小麦秸秆生物炭,改性后生物炭表面的羧基含量增加,碱性官能团含量显著降低,改性后生物炭的理论最大吸附量为10.1mg•g-1,是改性前的19.4倍。生物改性法是将微生物附着在生物炭表面以提高其吸附能力的一种改性方法,但该方法过程繁琐,稳定性差,难以广泛应用。除此之外,还有微波改性、超声改性等方法。微波加热相对于传统的加热方式具有快捷、便宜、高效等特点。经过微波强化改性活性炭能够进一步增强活性炭对磷的吸附能力。然而上述改性方法对提高生物炭对磷的吸附能力有限,因此,研发一种改性生物炭以显著提高生物炭对磷的吸附或去除能力成为本领域技术人员亟待解决的技术问题。
发明内容
本发明所要解决的技术问题是,克服现有技术的缺点,提供一种铝锰复合改性生物炭的制备及其在磷去除方面的应用,该制备方法简单易行,快捷方便,制备出的铝锰复合改性生物炭吸附能力强,对磷元素的吸附具有较宽的pH适应范围,具有较强的适应性。
为了解决以上技术问题,本发明提供一种铝锰复合改性生物炭的制备方法,具体包括以下步骤:
(1)生物炭的制备
将秸秆清洗后自然风干,经粉碎机粉碎后放置瓷坩埚内,然后放入马弗炉中于500~600℃下炭化3h,自然冷却至室温后取出,用去离子水反复冲洗5次,洗净后在80℃烘箱中干燥12h,干燥后的生物炭经研磨,过0.08mm筛,得到秸秆生物炭,放于自封袋内密封保存;
(2)AlCl3和KMnO4复合改性生物炭的制备
取步骤(1)中制备的秸秆生物炭于250ml锥形瓶中,然后加入AlCl3溶液和KMnO4溶液,用玻璃棒搅拌10min,之后置于200r·min-1摇床中震荡3h,取出抽滤后用去离子水反复冲洗,去除杂质和附着物后,置于烘箱中,80℃烘干,将烘干后的生物炭称重后放入瓷坩埚,于500~600℃温度下活化0.5h,自然冷却至室温后取出,即得铝锰复合改性生物炭。
本发明进一步限定的技术方案是:
进一步的,前述铝锰复合改性生物炭的制备方法中,步骤(1)中秸秆为玉米秸秆或芦苇秸秆。
前述铝锰复合改性生物炭的制备方法中,步骤(2)中按照质量比计AlCl3: KMnO4:秸秆生物炭=2:2:20的比例向锥形瓶中加入AlCl3溶液和KMnO4溶液。
一种铝锰复合改性生物炭的制备方法制备出的铝锰复合改性生物炭在磷去除方面的应用。
前述铝锰复合改性生物炭制备方法制备的铝锰复合改性生物炭在磷去除方面的应用中,磷去除方面的应用为应用于pH值在5-10含磷污水中磷的去除。
本发明的有益效果是:
本方法制备的铝锰复合改性生物炭对磷的吸附能力强,且对PH具有比较好的适应性,可广泛应用于污水的深度脱磷处理和黑臭水体磷的固定。
本发明铝锰复合改性秸秆生物炭具有良好的平均孔径、比表面积和孔容,提高了生物炭的吸附能力。
附图说明
图1为本发明实施例中铝锰复合改性芦苇秸秆生物炭对磷酸盐的吸附等温线图;
图2为本发明实施例中芦苇秸秆生物炭改性前后和吸附后的炭材料的FTIR图;
图3为本发明实施例中不同pH下铝锰复合改性芦苇秸秆生物炭(A2M2-RBC600)的吸附效果图;
图4为本发明实施例中阴离子SO4 2-对铝锰复合改性芦苇秸秆生物炭吸附磷的影响图;
图5为本发明实施例中阴离子NO3 -对铝锰复合改性芦苇秸秆生物炭吸附磷的影响图;
图6为本发明实施例中阴离子Cl-对铝锰复合改性芦苇秸秆生物炭吸附磷的影响图;
图7为本发明实施例中铝锰复合改性玉米秸秆生物炭对磷酸盐的吸附等温线图;
图8本发明实施例中玉米秸秆生物炭改性前后和吸附后的炭材料的FTIR图;
图9为本发明实施例中不同pH下铝锰复合改性芦苇秸秆生物炭(A2M2-RBC600)的吸附效果图;
图10为本发明实施例中阴离子SO4 2-对铝锰复合改性玉米秸秆生物炭吸附磷的影响图;
图11为本发明实施例中阴离子NO3 -对铝锰复合改性玉米秸秆生物炭吸附磷的影响图;
图12为本发明实施例中阴离子Cl-对铝锰复合改性玉米秸秆生物炭吸附磷的影响图。
具体实施方式
实施例1
本实施例提供的一种铝锰复合改性生物炭的制备方法,具体包括以下步骤:
(1)生物炭的制备
将芦苇秸秆清洗后自然风干,经粉碎机粉碎后放置瓷坩埚内,然后放入马弗炉中于500~600℃下炭化3h,自然冷却至室温后取出,用去离子水反复冲洗5次,洗净后在80℃烘箱中干燥12h,干燥后的生物炭经研磨,过0.08mm筛,得到芦苇秸秆生物炭(RBC600),放于自封袋内密封保存;
(2)AlCl3和KMnO4复合改性生物炭的制备
称取5g步骤(1)中制备的芦苇秸秆生物炭(RBC600)于250ml锥形瓶中,然后按照AlCl3: KMnO4: 芦苇秸秆生物炭质量比为2:2:20的比例加入AlCl3溶液和KMnO4溶液,用玻璃棒搅拌10min,之后置于200r·min-1摇床中震荡3h,取出抽滤后用去离子水反复冲洗,去除杂质和附着物后,置于烘箱中,80℃烘干,将烘干后的生物炭称重后放入瓷坩埚,于500~600℃温度下活化0.5h,自然冷却至室温后取出,即得铝锰复合改性芦苇生物炭(A2M2-RBC600)。
上述铝锰复合改性生物炭制备方法制备的铝锰复合改性芦苇生物炭(A2M2-RBC600)在pH值在5-10含磷污水中磷的去除方面的应用;
铝锰复合改性芦苇生物炭(A2M2-RBC600)对磷的吸附能力:
以铝锰复合改性芦苇秸秆生物炭为例,随环境温度的升高,改性生物炭A2M2-RBC600对磷酸盐的最大吸附量逐渐升高如图1所示,通过Langmuir吸附等温模型计算出,278K、293K和308K三种温度下的最大吸附容量qm分别为9.246、9.920和11.267mg·g-1。
铝锰复合改性芦苇生物炭(A2M2-RBC600)表面孔隙结构:
以600℃温度下制备的芦苇秸秆生物炭为例,RBC600的比表面积为83.22 m2•g-1,改性后A2M2-RCBC600的比表面积为357.13 m2•g-1,提高了4.2倍,具体数值见表1:
表1不同样品的平均孔径、比表面积、孔容
由表1可见,经改性后的生物炭总孔体积均大于未改性前,有利于提高生物炭的吸附能力,可以有效的提高对磷酸盐的吸附能力。
铝锰复合改性芦苇生物炭(A2M2-RBC600)红外光谱分析:
芦苇秸秆生物炭材料改性前后和吸附前后的炭材料的FTIR图如图2所示,图2中A2M2-RBC600-P为A2M2-RBC600吸附磷酸盐后的红外光谱图,从图中可以看出,661cm-1处出现较宽的吸收带对应Al-O的伸缩振动,3406 cm-1的-OH和661cm-1处Al-O的伸缩振动减弱,567cm-1处为PO4 3-弯曲振动,均表明A2M2-RBC600对溶液中的磷酸盐产生了吸附作用。
PH对铝锰复合改性芦苇生物炭(A2M2-RBC600)吸附磷的影响:
初始磷溶液初始pH对改性芦苇秸秆生物炭(A2M2-RBC600)吸附除磷效果的影响见图3,从图中可以看出随着pH的升高,A2M2-RBC600的最大吸附量先迅速上升后趋于平稳,后下降,强酸条件下,磷酸盐以稳定的H3PO4形态存在,很难发生化学吸附,在pH为5~10范围内,A2M2-RBC600对磷元素均保持很高的去除率,pH值较高时,OH-的存在会抑制吸附效果,与A2M2-CBC600在不同pH下的吸附规律相似,由此可见,A2M2-RBC600对磷元素的吸附具有较宽的pH适应范围,适用性较强,可广泛应用于污水的深度脱磷处理和黑臭水体磷的固定。
阴离子对铝锰复合改性芦苇生物炭(A2M2-RBC600)吸附磷的影响:
从图4-6中可以看出,阴离子和磷酸盐(以P计)浓度比为1:4和1:2时,三种阴离子对A2M2-CBC600吸附除磷效果的影响很小,随干扰阴离子和磷酸盐浓度比的增大,影响效果逐渐增大,pH为7时,阴离子和磷酸盐浓度比为1:1时如图4-6所示,SO4 2-、NO3 -和Cl-降低了A2M2-RBC600对磷的吸附量,降低率分别为6.64%、3.16%和2.14%,阴离子对铝锰复合改性芦苇生物炭吸附磷的影响程度为SO4 2- >NO3 ->Cl-,可见阴离子对吸附磷的影响小,其有较强的适应性。
实施例2
本实施例提供的一种铝锰复合改性生物炭的制备方法,具体包括以下步骤:
(1)生物炭的制备
将玉米秸秆清洗后自然风干,经粉碎机粉碎后放置瓷坩埚内,然后放入马弗炉中于500~600℃下炭化3h,自然冷却至室温后取出,用去离子水反复冲洗5次,洗净后在80℃烘箱中干燥12h,干燥后的生物炭经研磨,过0.08mm筛,得到玉米秸秆生物炭(CBC600),放于自封袋内密封保存;
(2)AlCl3和KMnO4复合改性生物炭的制备
称取5g步骤(1)中制备的玉米秸秆生物炭(CBC600)于250ml锥形瓶中,然后按照AlCl3: KMnO4: 玉米秸秆生物炭质量比为2:2:20的比例加入AlCl3溶液和KMnO4溶液,用玻璃棒搅拌10min,之后置于200r·min-1摇床中震荡3h,取出抽滤后用去离子水反复冲洗,去除杂质和附着物后,置于烘箱中,80℃烘干,将烘干后的生物炭称重后放入瓷坩埚,于500~600℃温度下活化0.5h,自然冷却至室温后取出,即得铝锰复合改性玉米秸秆生物炭(A2M2-CBC600)。
上述铝锰复合改性生物炭制备方法制备的铝锰复合改性玉米秸秆生物炭(A2M2-CBC600)在pH值在5-10含磷污水中磷的去除方面的应用。
铝锰复合改性玉米秸秆生物炭(A2M2-CBC600)对磷的吸附能力:
以铝锰复合改性玉米秸秆生物炭为例,A2M2-CBC600对磷的吸附量随温度变化如图7所示,从图中可以看出,随温度的升高,改性生物炭A2M2-CBC600对磷酸盐的吸附量逐渐升高,升高温度有利于改性生物炭对磷的吸附,通过Langmuir吸附等温模型计算出,278K、293K和308K三种温度下的最大吸附容量qm分别为12.220、13.586和15.303mg·g-1,可见本材料在使用过成中,温度越高除磷效果越好。
铝锰复合改性玉米秸秆生物炭(A2M2-CBC600)表面孔隙结构:
以600℃温度下制备的玉米秸秆生物炭为例,CBC600的比表面积为43.56 m2•g-1,改性后A2M2-CBC600的比表面积为268.133 m2•g-1,具体数值见表1,提高了6.2倍:
表1 AlCl3和KMnO4复合改性玉米秸秆生物炭的平均孔径、比表面积、孔容
生物炭 | 平均孔径nm | 比表面积m<sup>2</sup>·g<sup>-1</sup> | 孔容cc·g<sup>-1</sup> |
CBC600 | 19.06 | 43.56 | 0.076 |
A<sub>2</sub>M<sub>2</sub>-CBC600 | 20.18 | 268.13 | 0.112 |
铝锰复合改性玉米秸秆生物炭(A2M2-CBC600)红外光谱分析:
铝锰复合改性生物炭(A2M2-CBC600)在693cm-1处出现较宽的吸收带对应Al-O的伸缩振动如图8所示,图8中CBC、A2M2-CBC600和A2M2-CBC600-P分别表示为未改性生物炭、铝锰复合改性生物炭吸附磷前后的红外光谱图,说明铝成功负载在了生物炭表面,693cm-1处的Al-O吸收共振峰减弱,说明Al-O基也参与了P的吸附过程,磷通过单原子螯和配位和双齿颗粒内表面络合作用吸附在Al-O表面,吸附后A2M2-CBC600-P在573cm-1处出现PO4 3-弯曲振动,均表明A2M2-CBC600对溶液中的磷酸盐产生了吸附作用。
PH对铝锰复合改性玉米秸秆生物炭(A2M2-CBC600)吸附磷的影响:
磷溶液(含磷的污水)初始pH对玉米秸秆改性生物炭(A2M2-CBC600)吸附除磷效果的影响见图9,从图中可以看出,随着溶液初始pH的增大,改性生物炭对磷的吸附量呈先上升后下降的趋势,初始pH值为6时吸附量最大,为9.3 mg•g-1,随着pH值增大,溶液中OH-浓度增大,磷元素主以PO4 3-形式存在,与OH-存在竞争吸附,同时生物炭表面的Al3+与OH-易发生沉淀反应,生物炭表面的正电荷数降低,导致去除率会逐渐降低,可见pH对材料吸附磷的能力产生影响,过高的pH将降低材料对磷的吸附,因此本发明在使用时控制磷溶液的初始pH在5-10之间。
阴离子对铝锰复合改性玉米秸秆生物炭(A2M2-CBC600)吸附磷的影响:
从图10-12中可以看出,阴离子和磷酸盐(以P计)浓度比为1:4和1:2时,三种阴离子对A2M2-CBC600吸附除磷效果的影响很小,随干扰阴离子和磷酸盐浓度比的增大,影响效果逐渐增大,如图10-12所示,pH为7时,阴离子和磷酸盐浓度比为1:1时,SO4 2-、NO3 -和Cl-降低了A2M2-CBC600对磷的吸附量,其降低率分别为12.09%、6.57%和6.59%,可见阴离子对吸附磷的影响小,其有较强的适应性。
除上述实施例外,本发明还可以有其他实施方式。凡采用等同替换或等效变换形成的技术方案,均落在本发明要求的保护范围。
Claims (5)
1.一种铝锰复合改性生物炭的制备方法,其特征在于,具体包括以下步骤:
(1)生物炭的制备
将秸秆清洗后自然风干,经粉碎机粉碎后放置瓷坩埚内,然后放入马弗炉中于500~600℃下炭化3h,自然冷却至室温后取出,用去离子水反复冲洗5次,洗净后在80℃烘箱中干燥12h,干燥后的生物炭经研磨,过0.08mm筛,得到秸秆生物炭,放于自封袋内密封保存;
(2)AlCl3和KMnO4复合改性生物炭的制备
取步骤(1)中制备的秸秆生物炭于250ml锥形瓶中,然后加入AlCl3溶液和KMnO4溶液,用玻璃棒搅拌10min,之后置于200r·min-1摇床中震荡3h,取出抽滤后用去离子水反复冲洗,去除杂质和附着物后,置于烘箱中,80℃烘干,将烘干后的生物炭称重后放入瓷坩埚,于500~600℃下活化0.5h,自然冷却至室温后取出,即得铝锰复合改性生物炭。
2.根据权利要求1所述的铝锰复合改性生物炭的制备方法,其特征在于:步骤(1)中所述秸秆为玉米秸秆或芦苇秸秆。
3.根据权利要求1所述的铝锰复合改性生物炭的制备方法,其特征在于:步骤(2)中按照质量比计AlCl3: KMnO4: 秸秆生物炭=2:2:20的比例向锥形瓶中加入AlCl3溶液和KMnO4溶液。
4.一种权利要求1所述的铝锰复合改性生物炭制备方法制备的铝锰复合改性生物炭在磷去除方面的应用。
5.根据权利要求4所述的铝锰复合改性生物炭制备方法制备的铝锰复合改性生物炭在磷去除方面的应用,其特征在于:磷去除方面的应用为应用于pH值在5-10含磷污水中磷的去除。
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CN114034788A (zh) * | 2021-11-01 | 2022-02-11 | 广西壮族自治区海洋环境监测中心站 | 一种海洋沉积物中含硫有机化合物的检测方法 |
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