CN111715194A - 一种改性银杏叶生物炭的制备方法及应用 - Google Patents
一种改性银杏叶生物炭的制备方法及应用 Download PDFInfo
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Abstract
本发明公开了一种改性银杏叶生物炭的制备方法及应用,其制备方法包括以下步骤:(1)以银杏叶为原料,在惰性气氛下进行热解及碳化,制得未活化生物炭;(2)将未活化生物炭经KOH浸渍,过滤、干燥,于惰性气氛下活化,冷却,将所得固体经二氧化碳活化,得到活化生物炭;(3)将活化生物炭加至酒石酸溶液中,微波下酯化反应,然后将体系中和至中性,然后加入β‑环糊精、蒸馏水、醋酸钾,再在微波下反应,经冷却、洗涤、烘干后,得改性银杏叶生物炭。本发明制备方法制备方法可靠易行、成本低廉、原料来源广泛,适用于实际大规模生产,所得产品可对水体中的双酚A进行高效去除,同时具有适用水体pH范围广及耐离子干扰等优点。
Description
技术领域
本发明涉及水体中双酚A污染修复技术领域,特别是涉及一种改性银杏叶生物炭的制备方法及其应用。
背景技术
双酚A是世界上大量生产的化学品之一,其广泛用于生产聚碳酸酯塑料、环氧树脂、食品容器、纸张、水管、玩具、医疗设备以及电子产品等等。近年来,双酚A的污染变得日益严重。有研究报道称,人体的血清、尿、胎盘组织、脐带血和母乳中已经检测出双酚A。双酚A对人类及动物的生殖发育、神经网络和心血管、代谢和免疫系统等会产生严重影响。美国对双酚A的生产和使用已进行明确限制;2010年,加拿大政府出台了禁止进口和销售含有双酚A的聚碳酸酯奶瓶等相关规定;2011年以来,欧盟也开始禁止使用含有双酚A的婴儿奶瓶。水体中双酚A的污染是威胁人类健康的主要途径,因此这一问题亟待解决。
通常用于除去水体中有害污染物的方法有生物降解、膜过滤、吸附、催化降解等等技术手段,其中吸附过程是最基础并且应用最为广泛的水处理技术之一,其简单的操作,低廉的成本是大多数技术无可比拟的,开发性能优异、原料广泛、成本低廉的水处理剂成为发展吸附技术的核心内容。生物炭水处理剂近年来发展迅速,这是一类利用天然生物质原料经过热解之后形成的产物,其主要成分是碳,将其用于水质净化具有优异的效果。制备生物炭的原料通常有动植物废料、垃圾、污泥、煤等等。银杏叶作为一种植物废料,具有来源广泛、成本极低等诸多优点,将其变废为宝开发成一种新型双酚A修复水处理剂具有重要意义。
发明内容
本发明的目的在于克服上述现有技术的不足,提供一种改性银杏叶生物炭的制备方法及应用,制备方法可靠易行、成本低廉、原料来源广泛,适用于实际大规模生产,所得产品可对水体中的双酚A进行高效去除,同时具有适用水体pH范围广及耐离子干扰等优点。
为了实现上述目的,本发明采用如下技术方案:
一种改性银杏叶生物炭的制备方法,包括以下步骤:
(1)以银杏叶为原料,将其洗净、烘干、破碎后在惰性气氛下进行热解及碳化,制得未活化生物炭;
(2)将未活化生物炭置于KOH溶液中浸渍12h,过滤、干燥,将所得产物于500℃惰性气氛下活化1.5h,冷却至室温,将所得固体转移至管式炉中,通入二氧化碳气体后升温700℃并在该温度下活化1h,冷却至室温,得到活化生物炭;
本步骤中,以KOH溶液为活化剂对生物炭进行初步活化,KOH会伸入生物炭孔隙结构中继续深度开孔,增大生物炭的比表面积,以二氧化碳为活化剂对生物炭进行进一步活化,使生物炭内的孔隙结构变得更加发达和复杂,进一步增大生物炭的比表面积,进而提升吸附性能。另在生物炭经KOH初步活化过程中,残留的KOH转变成K2CO3后留在生物炭中,而K2CO3的残留对后续酒石酸与生物炭的酯化反应具有一定的催化作用,能够促进反应的正常进行。
(3)将活化生物炭加入至1mol/L的酒石酸溶液中,搅拌均匀,升温至100℃并在微波下酯化反应3h,冷却后采用氢氧化钾中和至中性,过滤,反复洗涤,然后将产物与、β-环糊精、蒸馏水、醋酸钾加入反应釜中,充分搅拌后于110℃微波下反应2h,冷却至室温,将所得产物用超纯水多次洗涤,烘干,得到β-环糊精修饰生物炭,即为改性银杏叶生物炭,其中生物炭、酒石酸、β-环糊精、蒸馏水、醋酸钾的质量比为1:15:20:28:0.3。
经步骤(1)、(2)后所得活化生物炭表面具有羧基、羟基、酯基等多种官能团,活化生物炭与酒石酸酯化反应时,酒石酸分子中的羧基与活化生物炭表面的羟基发生酯化反应,加入β-环糊精及醋酸钾后,在醋酸钾催化作用下,活化生物炭与酒石酸的酯化产物与β-环糊精发生酯交换反应,实现β-环糊精修饰生物炭材料的制备,通过上述改性方法赋予了生物炭物理吸附与化学吸附的共同功效,大大提高了吸附性能及吸附效率。
步骤(1)中,热解反应温度为250℃,反应时间为1h。
步骤(1)中,碳化反应温度为460℃~650℃,反应时间为3~6h。
步骤(1)中,未活化生物炭与KOH溶液的浸渍比为1:2。
一种改性银杏叶生物炭的应用,以所述改性银杏叶生物炭为吸附剂,置于有机污染水源中,用于吸附污染水源中的有机污染物双酚A。
本发明的有益效果是:
(1)采用原料来源广泛且成本低廉的植物废料银杏叶为碳源,通过惰性气氛下热解及碳化反应制备了内部互相连通的多孔状银杏叶生物炭,所获得的生物炭在治理双酚A有机污染水体中具有良好的去除效用;
(2)以KOH为活化剂对生物炭进行初步活化,达到扩孔的作用,增大生物炭的比表面积,以二氧化碳为活化剂对生物炭进行进一步活化使生物炭内的孔隙结构变得更加发达和复杂,进一步增大生物炭的比表面积,进而提升吸附性能,另以KOH活化时生成的K2CO3可催化后续酒石酸与生物炭的酯化反应,促进反应进行;
(3)以β-环糊精改性生物炭,赋予了生物炭物理吸附与化学吸附的共同功效,增强了生物炭的吸附性能,提升了双酚A的去除效率(25℃时的饱和吸附容量在323mg/g以上,在30min内即能达到44.9%以上的去除率),且改性银杏叶生物炭作为水处理吸附剂的适用水体pH范围广且基本不受离子强度的干扰(吸附性能在离子强度0.001-0.1mol/L内基本不变,在水质条件pH=2-9范围内吸附性能优异);
(4)本发明制备方法成本低廉、原料来源广泛、反应条件温和、操作简单、对设备无特殊性要求,产品稳定性好、性能优异,适用于实际大规模生产,是将银杏叶生物炭水处理吸附剂推向有机污染水体修复领域的成功实例。
附图说明
图1为实施例1所得未活化叶生物炭的扫描电镜图;
图2为实施例1所得未活化叶生物炭的元素分布图;
图3为实施例1所得改性银杏叶生物炭的X射线衍射图;
图4为实施例1所得改性银杏叶生物炭的氮气吸附-脱附等温线;
图5为实施例1所得改性银杏叶生物炭的孔径分布曲线图;
图6为实施例1所得改性银杏叶生物炭吸附双酚A的吸附动力学曲线;
图7为水体pH和离子强度对实施例1所得改性银杏叶生物炭去除双酚A性能的影响。
具体实施方式
下面结合附图和具体实施方式对本发明作进一步描述:
实施例1
一种改性银杏叶生物炭的制备方法,包括以下步骤:
(1)以银杏叶为原料,用大量自来水洗净后于60℃鼓风干燥箱中烘干,烘干后的银杏叶置于粉碎机中充分破碎,破碎后的材料过50目筛后干燥;将干燥后的材料于惰性气氛下以10℃/min升温至250℃并在此温度下保持1h对材料进行热解,然后继续以10℃/min升温至650℃并在650℃下保持3h对材料进行碳化,制得未活化生物炭;
(2)将未活化生物炭按浸渍比为1:2置于KOH溶液中浸渍12h,过滤、干燥,将所得产物于500℃惰性气氛下活化1.5h,冷却至室温,将所得固体转移至管式炉中,通入二氧化碳气体后升温700℃并在该温度下活化1h,冷却至室温,得到活化生物炭;
(3)将活化生物炭加入至1mol/L的酒石酸溶液中,搅拌均匀,升温至100℃并在微波下酯化反应3h,冷却后采用氢氧化钾中和至中性,过滤,反复洗涤,然后将产物与、β-环糊精、蒸馏水、醋酸钾加入反应釜中,充分搅拌后于110℃微波下反应2h,冷却至室温,将所得产物用超纯水多次洗涤,烘干,得到β-环糊精修饰生物炭,即为改性银杏叶生物炭,其中生物炭、酒石酸、β-环糊精、蒸馏水、醋酸钾的质量比为1:15:20:28:0.3。
一种改性银杏叶生物炭的应用,以本实施例制备的改性银杏叶生物炭为吸附剂,置于有机污染水源中,用于吸附污染水源中的有机污染物双酚A。
实施例2
按照实施例1的制备方法制备改性银杏叶生物炭并将其用于吸附污染水源中的有机污染物双酚A,不同之处在于,步骤(1)中的碳化温度为550℃。
实施例3
按照实施例1的制备方法制备改性银杏叶生物炭并将其用于吸附污染水源中的有机污染物双酚A,不同之处在于,步骤(1)中的碳化温度为650℃。
实施例4
按照实施例1的制备方法制备改性银杏叶生物炭并将其用于吸附污染水源中的有机污染物双酚A,不同之处在于,步骤(1)中的碳化时间为4h。
实施例5
按照实施例1的制备方法制备改性银杏叶生物炭并将其用于吸附污染水源中的有机污染物双酚A,不同之处在于,步骤(1)中的碳化时间为5h。
实施例6
按照实施例1的制备方法制备改性银杏叶生物炭并将其用于吸附污染水源中的有机污染物双酚A,不同之处在于,步骤(1)中的碳化时间为6h。
结论分析:
对实施例1所得未活化叶生物炭进行扫描电镜图及元素分布测试,如图1-2所示,由图1可以看出样品表面呈现致密的褶皱状,样品侧面内部出现丰富的孔隙结构,由图2可知未活化叶生物炭元素成分主要由碳、氧组成,另外其中还含有氯、钾、镁、铝等多种元素。
对实施例1所得改性银杏叶生物炭进行晶体结构测试,如图3所示,由图3可知,银杏叶生物炭在25°、30°左右出现了特征衍射峰,其分别对应于非晶态无定形碳以及样品表面的盐类结晶,说明该方法能够得到生物炭。
分别对实施例1-6所得改性银杏叶生物炭进行氮气吸附-脱附测试。图4为实施例1所得改性银杏叶生物炭的氮气吸附-脱附等温线图,从图中可以看出,改性银杏叶生物炭的相对比表面积达到了6.11m2/g;图5为实施例1所得改性银杏叶生物炭的孔径分布曲线图,由图5可知,改性银杏叶生物炭内部的孔径分布于18nm左右,属于介孔材料范畴。经测试,实施例2-6所得改性银杏叶生物炭的相对比表面积分别为6.19m2/g、6.27m2/g、6.14m2/g、6.19m2/g、6.21m2/g。
分别对实施例1-6所得改性银杏叶生物炭进行吸附双酚A的动力学测试。测试方法为:于玻璃容器中加入银杏叶生物炭、人工配置模拟双酚A污染液(浓度为20mg/L),使得吸附剂的固液比达到0.2g/L。加入背景电解质NaNO3溶液使得体系中背景电解质浓度为0.01mol/L。用HNO3和KOH调节pH至5±0.05。然后在25℃下,开始进行振荡吸附平衡反应并计时。达到特定反应时间后取2mL反应悬浮液,将其用孔径为0.45μm的聚醚砜滤膜进行过滤,通过高效液相色谱法对滤液中双酚A的浓度进行测定。
图6为实施例1所得改性银杏叶生物炭的吸附双酚A的动力学曲线,由图中可知,改性银杏叶生物炭对双酚A的去除率在30min就能达到44.9%。另经测试,实施例2-6所得改性银杏叶生物炭对双酚A的去除率在30min分别达到45.6%、47.5%、45.3%、46.1%、48.2%。
分别对实施例1-6所得改性银杏叶生物炭在25℃时进行吸附双酚A的饱和吸附容量测试。结果表明,实施例1-6所得改性银杏叶生物炭的饱和吸附量分别为323mg/g、335.7mg/g、345.2mg/g、328.6mg/g、339.4mg/g、348.1mg/g。
按动力学测试方法研究体系pH对实施例1-6所得改性银杏叶生物炭去除双酚A的性能影响,不同之处在于:利用HNO3和KOH调节体系pH在2-11;按动力学测试方法研究体系离子强度对实施例1-6所得改性银杏叶生物炭去除双酚A的性能影响,不同之处在于:背景电解质NaNO3浓度分别控制在0.001-0.1mol/L。
图7为不同pH和不同离子强度下对实施例1所得改性银杏叶生物炭去除双酚A性能影响的结果,由图7可知,改性银杏叶生物炭吸附剂适用水体pH范围广泛,其吸附双酚A的适用水体pH范围为2-9,且在背景电解质NaNO3浓度0.001-0.1mol/L范围内,银杏叶生物炭吸附剂的吸附性能基本不变,即银杏叶生物炭吸附性能不受离子强度干扰。对于实施例2-6所得改性银杏叶生物炭而言,同样能够得出上述结论。
对比例1~6
对应按照实施例1~6的方法及原料配比制备活化生物炭,按照对应实施例中步骤(3)中加入量将活化生物炭、β-环糊精加入双酚A有机污染物中,以与实施例中相同的方法、试验条件进行生物炭吸附双酚A的动力学测试。结果表明,活化生物炭、β-环糊精复配混合物对双酚A的去除率在30min分别达到36.7%、37.4%、39.1%、37.8%、38.1%、39.9%,低于实施例1~6所得改性生物炭在30min对双酚A的去除率,即β-环糊精修饰的生物炭对双酚A的去除效率更高,这是因为在吸附体系中,β-环糊精与生物炭发生了更好的协同吸附作用。
对比例7~12
对应按照实施例1~6的方法及原料配比制备活化生物炭,按照对应实施例中步骤(3)中加入量将活化生物炭、β-环糊精加入双酚A有机污染物中,以与实施例中相同的方法、试验条件进行不同pH下的生物炭去除双酚A的测试。结果表明,活化生物炭、β-环糊精复配混合物作为吸附剂,其吸附双酚A的适用水体pH范围为3-8,其适用水体pH范围较改性银杏叶生物炭要小。
对比例13~18
对应按照实施例1~6的方法及原料配比制备活化生物炭,按照对应实施例中步骤(3)中加入量将活化生物炭、β-环糊精加入双酚A有机污染物中,以与实施例中相同的方法、试验条件进行不同离子强度下的生物炭去除双酚A的测试。结果表明,活化生物炭、β-环糊精复配混合物作为吸附剂,在背景电解质NaNO3浓度超过0.07mol/L时,其吸附性能有所下降,即活化生物炭、β-环糊精复配混合物吸附性能易受离子强度干扰。
以上所述仅为本发明的较佳实施例,并不用以限制本发明,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (5)
1.一种改性银杏叶生物炭的制备方法,其特征在于:包括以下步骤:
(1)以银杏叶为原料,将其洗净、烘干、破碎后在惰性气氛下进行热解及碳化,制得未活化生物炭;
(2)将未活化生物炭置于KOH溶液中浸渍12h,过滤、干燥,将所得产物于500℃惰性气氛下活化1.5h,冷却至室温,将所得固体转移至管式炉中,通入二氧化碳气体后升温700℃并在该温度下活化1h,冷却至室温,得到活化生物炭;
(3)将活化生物炭加入至1mol/L的酒石酸溶液中,搅拌均匀,升温至100℃并在微波下酯化反应3h,冷却后采用氢氧化钾中和至中性,过滤,反复洗涤,然后将产物与、β-环糊精、蒸馏水、醋酸钾加入反应釜中,充分搅拌后于110℃微波下反应2h,冷却至室温,将所得产物用超纯水多次洗涤,烘干,得到β-环糊精修饰生物炭,即为改性银杏叶生物炭,其中生物炭、酒石酸、β-环糊精、蒸馏水、醋酸钾的质量比为1:15:20:28:0.3。
2.如权利要求1所述一种改性银杏叶生物炭的制备方法,其特征在于:步骤(1)中,热解反应温度为250℃,反应时间为1h。
3.如权利要求1所述一种改性银杏叶生物炭的制备方法,其特征在于:步骤(1)中,碳化反应温度为460℃~650℃,反应时间为3~6h。
4.如权利要求1所述一种改性银杏叶生物炭的制备方法,其特征在于:步骤(1)中,未活化生物炭与KOH溶液的浸渍比为1:2。
5.一种如权利要求1~4中任意一项所述方法制得的改性银杏叶生物炭的应用,其特征在于:以所述改性银杏叶生物炭为吸附剂,置于有机污染水源中,用于吸附污染水源中的有机污染物双酚A。
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Cited By (2)
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CN112908721A (zh) * | 2021-02-03 | 2021-06-04 | 桂林理工大学 | 一种多孔炭/Ni(OH)2复合电极材料及其制备方法 |
CN114678538A (zh) * | 2022-01-07 | 2022-06-28 | 齐鲁工业大学 | 一种生物质衍生多孔碳作为锌碘电池正极材料 |
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