CN113731363A - 一种吸附剂及其制备方法和应用 - Google Patents
一种吸附剂及其制备方法和应用 Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title abstract description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 49
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 48
- 239000011574 phosphorus Substances 0.000 claims abstract description 48
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 10
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
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- HZGFMPXURINDAW-UHFFFAOYSA-N iron zirconium Chemical compound [Fe].[Zr].[Zr] HZGFMPXURINDAW-UHFFFAOYSA-N 0.000 description 1
- VRHXRUMNXXJYQV-UHFFFAOYSA-N iron(2+) oxygen(2-) zirconium(4+) Chemical compound [O-2].[Fe+2].[O-2].[O-2].[Zr+4] VRHXRUMNXXJYQV-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了一种吸附剂及其制备方法和应用,属于环境吸附材料技术领域。所述吸附剂由铁、锆负载在生物炭上得到;所述生物炭为抗生素菌渣制得的生物炭。本发明制备吸附剂的主要原料采用抗生素菌渣,实现了废弃生物质的资源化。本发明制备的吸附剂除磷效率高,对不同含磷浓度的污水均有较好的去除效果,可以有效缓解水体富营养化。本发明方法简单可行,采用碳酸钾活化、盐酸酸洗,极大地提高了生物炭的比表面积,增强了其吸附能力,通过共沉淀法负载铁锆对由抗生素菌渣制得的生物质炭进行改性,极大地提高了吸附剂对磷的去除能力。
Description
技术领域
本发明涉及环境吸附材料技术领域,特别是涉及一种吸附剂及其制备方法和应用。
背景技术
磷的超标排放是导致水体富营养化的重要原因,如何有效地去除污水中的磷,是富营养化水体治理的关键。吸附法是一种环境友好、经济高效的技术,利用具有较高比表面积和孔隙结构的固体材料通过物理吸附或化学吸附对水体中的磷酸盐进行去除,而吸附法除磷的关键在于吸附材料的制备。
生物炭是一种富碳材料,在厌氧或缺氧条件下通过对不同类型的生物质进行热处理而产生。生物炭具有独特的性能,如高比表面积、高孔隙率、稳定的碳结构、丰富的含氧官能团等,常作为吸附剂用于污水处理。通常生物炭表面呈负电性,对阴离子吸附性能较差,这导致其对污水中磷的吸附能力较差。
抗生素菌渣是生产抗生素过程中所产生的废渣。在抗生素发酵过程中,微生物的繁殖代谢不仅产生了药用的抗生素,而且会形成大量的菌丝体和少量尚未用完的培养基。抗生素发酵液经过滤后,这二者共同构成了抗生素菌渣。目前并没有太好的对抗生素菌渣的处置方式。如果能够将抗生素菌渣用于去除污水中的磷,这一方面能够处理污水,另一方面还能够实现抗生素菌渣的废物再利用,对于抗生素菌渣的再利用以及环境吸附材料领域将具有重要意义。
发明内容
本发明的目的是提供一种吸附剂及其制备方法和应用,以解决上述现有技术存在的问题,提高生物炭对污水中磷的吸附能力,同时使青霉素菌渣,实现废弃生物质的资源化。
为实现上述目的,本发明提供了如下方案:
本发明技术方案之一,一种吸附剂,所述吸附剂由铁、锆负载在生物炭上得到;
所述吸附剂中铁、锆总负载量不低于15wt%;
所述生物炭为抗生素菌渣制得的生物炭。
本发明技术方案之二,上述吸附剂的制备方法,包括以下步骤:
步骤1,将干燥至恒重的抗生素菌渣粉碎,与活化剂以质量比1:1加入到水中混合均匀,离心分离,将分离得到的固体部分烘干得到预活化的抗生素菌渣;
活化剂能够增大生物炭的比表面积;
步骤2,将所述预活化的抗生素菌渣热解得到生物炭;
步骤3,将所述生物炭进行酸洗,之后离心分离、洗涤至中性,得到活性生物炭;
酸洗能够进一步增大生物炭的比表面积;
步骤4,将所述活性生物炭加入到氯氧化锆和氯化铁的混合水溶液中搅拌,之后调节pH值至10-12,搅拌、老化、过滤、洗涤至中性,烘干,得到所述吸附剂。
锆对污水中的磷具有很好的吸附作用,将锆负载到生物炭表面能够增加生物炭对磷的吸附效果。适量铁的介入使得锆氧化物形成更为细小的结构,增大了吸附剂的比表面积,使其表面拥有更多吸附位点,增强其对磷的吸附效果,同时铁本身对磷也有一定的亲和性,能够进一步提升吸附剂对磷的吸附效果。
进一步地,步骤1中,所述活化剂为碳酸钾。
进一步地,步骤1中,所述烘干的温度为100-110℃。
进一步地,步骤2中,所述热解具体为:氮气保护下,以5-10℃/min的速度升温至600-700℃保温1-2h。
进一步地,步骤3中所述酸为盐酸。
进一步地,步骤4中,所述氯氧化锆和氯化铁的混合水溶液中锆、铁离子摩尔比为7:3,锆、铁离子的浓度之和为0.1-0.3mol/L。
进一步地,步骤4中,所述调节pH值采用NaOH溶液进行调节。
进一步地,步骤4中,所述烘干的温度为100-110℃。
本发明技术方案之三,上述吸附剂在含磷污水处理方面的应用。
本发明公开了以下技术效果:
本发明制备吸附剂的主要原料采用抗生素菌渣,实现了废弃生物质的资源化。本发明制备的吸附剂除磷效率高,对不同含磷浓度的污水均有较好的去除效果,可以有效缓解水体富营养化。
本发明方法简单可行,采用碳酸钾活化、盐酸酸洗,极大地提高了生物炭的比表面积,增强了其吸附能力,通过共沉淀法负载铁锆对由抗生素菌渣制得的生物质炭进行改性,极大地提高了吸附剂对磷的去除能力。
本发明所制备的吸附剂在磷吸附饱和后可作为土壤改良剂,增加土壤中磷含量,同时生物质炭能够改善土壤板结情况,活化土壤,改善土壤质量。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案,下面将对实施例中所需要使用的附图作简单的介绍,显而易见地,下面描述中的附图仅仅是本发明的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其他的附图。
图1为本发明制备吸附剂的工艺流程图;
图2为实施例1制备的吸附剂的SEM图;
图3为实施例1制备的吸附剂的EDS图;
图4为实施例1步骤3制得的活性生物炭的脱附孔径分布图;
图5为实施例1制备的吸附剂的脱附孔径分布图。
具体实施方式
现详细说明本发明的多种示例性实施方式,该详细说明不应认为是对本发明的限制,而应理解为是对本发明的某些方面、特性和实施方案的更详细的描述。
应理解本发明中所述的术语仅仅是为描述特别的实施方式,并非用于限制本发明。另外,对于本发明中的数值范围,应理解为还具体公开了该范围的上限和下限之间的每个中间值。在任何陈述值或陈述范围内的中间值以及任何其他陈述值或在所述范围内的中间值之间的每个较小的范围也包括在本发明内。这些较小范围的上限和下限可独立地包括或排除在范围内。
除非另有说明,否则本文使用的所有技术和科学术语具有本发明所述领域的常规技术人员通常理解的相同含义。虽然本发明仅描述了优选的方法和材料,但是在本发明的实施或测试中也可以使用与本文所述相似或等同的任何方法和材料。本说明书中提到的所有文献通过引用并入,用以公开和描述与所述文献相关的方法和/或材料。在与任何并入的文献冲突时,以本说明书的内容为准。
在不背离本发明的范围或精神的情况下,可对本发明说明书的具体实施方式做多种改进和变化,这对本领域技术人员而言是显而易见的。由本发明的说明书得到的其他实施方式对技术人员而言是显而易见的。本发明说明书和实施例仅是示例性的。
关于本文中所使用的“包含”、“包括”、“具有”、“含有”等等,均为开放性的用语,即意指包含但不限于。
本发明实施例所用抗生素菌渣具体为青霉素菌渣。
本发明实施例所采用的工艺流程如图1所示。
实施例1
步骤1,将青霉素菌渣烘干至恒重,粉碎研磨通过60目筛,收集备用;将烘干后的青霉素菌渣和碳酸钾以质量比1:1加入到去离子水中得到混合物,去离子水的用量是青霉素菌渣质量的5倍,将混合物置于磁力搅拌器上转速1000rpm搅拌2h,搅拌结束后置于离心管中离心得到固体部分,将固体部分放于110℃烘箱中烘干,得到预活化的青霉素菌渣;
步骤2,将预活化的青霉素菌渣放置于管式炉中,在氮气保护下,以10℃/min的速度从室温升温至600℃保温2h进行绝氧热解,得到生物炭;
步骤3,将步骤2制得的生物炭用3mol/L盐酸浸泡10min,离心分离,再用去离子水清洗至中性并110℃烘干保存,得到活性生物炭;
步骤4,将氯氧化锆和氯化铁以锆、铁离子摩尔比7:3,总摩尔浓度为0.1mol/L,加入到200mL去离子水中,充分混合后,再加入2g活性生物炭,在磁力搅拌器上转速1000rpm搅拌1h,然后逐渐滴加1mol/L NaOH溶液调整pH至10,继续搅拌1h,停止搅拌后静置30min,过滤,用去离子水反复洗涤至上清液为中性,之后放于110℃烘箱中烘干,得到铁锆负载生物炭,即吸附剂。
对本实施例制得的吸附剂的磷吸附量进行测定,方法如下:称取0.1g吸附剂,与40mL 100mg/L的KH2PO4溶液,于离心管中在25℃、200rpm条件下震荡吸附24h,测定吸附材料的磷吸附量。
经检测,在上述条件下本实施例制得的吸附剂的磷吸附量为16.77mg/g。
本实施例制得的吸附剂的平均孔径为1.9286nm,比表面积为695.8994m2/g,吸附剂中铁的负载量为8.3wt%,锆的负载量为9.1wt%。
本实施例制得的吸附剂的SEM图如图2所示,由图2能够看出该吸附剂具有丰富的孔隙结构,其表面粗糙,附着有小颗粒物质,说明铁锆氧化物已成功负载于生物炭表面,同时为该吸附剂提供大量的吸附位点。
本实施例制得的吸附剂的EDS图如图3所示,由图3能够看出铁锆成功负载于生物炭表面,其中锆的负载量为9.1wt%,铁的负载量为8.3wt%。
本实施例步骤3制得的活性生物炭通过BJH方法得到的脱附孔径分布图如图4所示,由图4能够看出该活性生物炭孔径分布以微孔为主,集中于1-2nm之间,属于微孔生物炭,且其介孔部分,平均孔径约为4nm。表明该活性生物炭可作为优秀的载体。
本实施例制得的吸附剂通过BJH方法得到的脱附孔径分布图如图5所示,由图5能够看出该吸附剂经铁锆负载,较之步骤3制得的活性生物炭平均孔径略微增加,但仍主要集中于1-2nm之间,属于微孔生物炭。其介孔部分平均孔径约为3nm。该吸附剂的孔径分布使得该吸附剂具有大量吸附位点且具有较强的磷吸附能力。
实施例2
与实施例1相同,区别仅在于,步骤2中热解的时间为1h。
对本实施例制得的吸附剂的磷吸附量进行测定,方法同实施例1。经检测,本实施例制得的吸附剂的磷吸附量为13.37mg/g。吸附剂平均孔径为1.6432nm,比表面积为612.3566m2/g,吸附剂中铁的负载量为7.9wt%,锆的负载量为8.4wt%。
实施例3
与实施例1相同,区别仅在于,步骤2中热解的温度为700℃,时间为1h。
对本实施例制得的吸附剂的磷吸附量进行测定,方法同实施例1。经检测,本实施例制得的吸附剂的磷吸附量为9.81mg/g。吸附剂平均孔径为1.5782nm,比表面积为565.4753m2/g,吸附剂中铁的负载量为7.5wt%,锆的负载量为7.7wt%。
实施例4
与实施例1相同,区别仅在于,步骤2中热解的温度为700℃。
对本实施例制得的吸附剂的磷吸附量进行测定,方法同实施例1。经检测,本实施例制得的吸附剂的磷吸附量为12.53mg/g。吸附剂平均孔径为1.6138nm,比表面积为642.6349m2/g,吸附剂中铁的负载量为7.3wt%,锆的负载量为7.9wt%。
实施例5
与实施例1相同,区别仅在于,步骤1中烘干的温度为100℃,步骤2中升温的速率为5℃/min,步骤4中锆、铁离子总摩尔浓度为0.2mol/L,pH值为11,烘干的温度为100℃。
对本实施例制得的吸附剂的磷吸附量进行测定,方法如下:称取0.1g吸附剂,与40mL 80mg/L的KH2PO4溶液,于离心管中在25℃、170rpm条件下震荡吸附24h,测定吸附材料的磷吸附量。
经检测,本实施例制得的吸附剂的磷吸附量为12.53mg/g。吸附剂平均孔径为1.4528nm,比表面积为593.5482m2/g,吸附剂中铁的负载量为8.9wt%,锆的负载量为9.4wt%。
实施例6
与实施例1相同,区别仅在于,步骤1中烘干的温度为105℃,步骤2中升温的速率为8℃/min,步骤4中锆、铁离子总摩尔浓度为0.3mol/L,pH值为12,烘干的温度为105℃。
对本实施例制得的吸附剂的磷吸附量进行测定,方法同实施例1。经检测,本实施例制得的吸附剂的磷吸附量为9.41mg/g。吸附剂平均孔径为1.4387nm,比表面积为503.5315m2/g,吸附剂中铁的负载量为9.1wt%,锆的负载量为9.3wt%。
对比例1
与实施例1相同,区别仅在于,步骤4中不添加氯化铁。
对本对比例制得的吸附剂的磷吸附量进行测定,方法同实施例1。经检测,本对比例制得的吸附剂的磷吸附量为8.28mg/g。吸附剂平均孔径为1.7693nm,比表面积为732.1855m2/g,锆的负载量为10.4wt%。
对比例2
与实施例1相同,区别仅在于,将青霉素菌渣替换为卤虫卵壳。
对本对比例制得的吸附剂的磷吸附量进行测定,方法如下:称取0.1g吸附剂,与100mL磷浓度为500mg/L的KH2PO4溶液,于离心管中在25℃、170rpm条件下震荡吸附24h,测定吸附材料的磷吸附量。
经检测,本对比例吸附剂的磷吸附量为427mg/g。
本对比例制得的吸附剂的磷吸附量显著优于实施例1-4,这可能是由于卤虫卵壳本身的物质组成以及结构特性所导致的。
对比例3
吸附剂为市售的活性炭,活性炭的孔密度为150孔/平方英寸、空塔风速为0.8米/秒、比表面积约为700平方/克。
对本对比例吸附剂的磷吸附量进行测定,方法同实施例1。经检测,本对比例吸附剂的磷吸附量为7.64mg/g。
本发明制得的吸附剂的磷吸附量显著优于市售的活性炭对磷的吸附量,说明本发明制备的吸附剂可以用于污水处理,为抗生素菌渣的应用提供了一个新的方向。
对比例4
与实施例1相同,区别仅在于,步骤4中锆、铁离子总摩尔浓度为0.05mol/L。
对本对比例制得的吸附剂的磷吸附量进行测定,方法同实施例1。经检测,本对比例制得的吸附剂的磷吸附量为7.12mg/g。吸附剂平均孔径为1.8446nm,比表面积为768.1291m2/g,吸附剂中铁的负载量为6.3wt%,锆的负载量为5.4wt%。
对比例5
与实施例1相同,区别仅在于,步骤4中锆、铁离子总摩尔浓度为0.4mol/L。
对本对比例制得的吸附剂的磷吸附量进行测定,方法同实施例1。经检测,本对比例制得的吸附剂的磷吸附量为9.19mg/g。吸附剂平均孔径为1.6411nm,比表面积为539.9371m2/g,吸附剂中铁的负载量为10.1wt%,锆的负载量为9.8wt%。
以上所述的实施例仅是对本发明的优选方式进行描述,并非对本发明的范围进行限定,在不脱离本发明设计精神的前提下,本领域普通技术人员对本发明的技术方案做出的各种变形和改进,均应落入本发明权利要求书确定的保护范围内。
Claims (10)
1.一种吸附剂,其特征在于,所述吸附剂由铁、锆负载在生物炭上得到;
所述吸附剂中铁、锆总负载量不低于15wt%;
所述生物炭为抗生素菌渣制得的生物炭。
2.根据权利要求1所述的一种吸附剂的制备方法,其特征在于,包括以下步骤:
步骤1,将干燥至恒重的抗生素菌渣粉碎,与活化剂以质量比1:1加入到水中混合均匀,离心分离,将分离得到的固体部分烘干得到预活化的抗生素菌渣;
步骤2,将所述预活化的抗生素菌渣热解得到生物炭;
步骤3,将所述生物炭进行酸洗,之后离心分离、洗涤至中性,得到活性生物炭;
步骤4,将所述活性生物炭加入到氯氧化锆和氯化铁的混合水溶液中搅拌,之后调节pH值至10-12,搅拌、老化、过滤、洗涤至中性,烘干,得到所述吸附剂。
3.根据权利要求2所述的一种吸附剂的制备方法,其特征在于,步骤1中,所述活化剂为碳酸钾。
4.根据权利要求2所述的一种吸附剂的制备方法,其特征在于,步骤1中,所述烘干的温度为100-110℃。
5.根据权利要求2所述的一种吸附剂的制备方法,其特征在于,步骤2中,所述热解具体为:氮气保护下,以5-10℃/min的速度升温至600-700℃保温1-2h。
6.根据权利要求2所述的一种吸附剂的制备方法,其特征在于,步骤3中所述酸为盐酸。
7.根据权利要求2所述的一种吸附剂的制备方法,其特征在于,步骤4中,所述氯氧化锆和氯化铁的混合水溶液中锆、铁离子摩尔比为7:3,锆、铁离子的浓度之和为0.1-0.3mol/L。
8.根据权利要求2所述的一种吸附剂的制备方法,其特征在于,步骤4中,采用NaOH溶液进行pH值调节。
9.根据权利要求2所述的一种吸附剂的制备方法,其特征在于,步骤4中,所述烘干的温度为100-110℃。
10.如权利要求1所述的吸附剂在含磷污水处理方面的应用。
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CN115138333B (zh) * | 2022-07-21 | 2024-04-05 | 闽江学院 | 一种富钙/铁抗生素菌渣无害化及资源化利用方法 |
CN116062830A (zh) * | 2022-12-12 | 2023-05-05 | 东北林业大学 | 一种利用改性大豆秸秆生物炭去除废水中化学需氧量的方法 |
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