CN106512936B - 一种水热法制备除氟吸附剂及其应用 - Google Patents
一种水热法制备除氟吸附剂及其应用 Download PDFInfo
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 66
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 59
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- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 6
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- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
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- 208000004042 dental fluorosis Diseases 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
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- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 1
- CFYGEIAZMVFFDE-UHFFFAOYSA-N neodymium(3+);trinitrate Chemical compound [Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CFYGEIAZMVFFDE-UHFFFAOYSA-N 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
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- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
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- B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
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- C—CHEMISTRY; METALLURGY
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Abstract
本发明属于复合材料合成技术领域,涉及除氟吸附剂的制备,尤其涉及水热法制备除氟吸附剂及其应用。先以废纸为原材料经铝盐浸渍、氮气保护下500~800℃焙烧3~6h制备氧化铝/生物质碳材料,然后采用水热法在生物质碳材料表面原位生长一层纳米片,制得复合氧化物/生物质碳,再通过稀土硝酸盐对其表面改性,氮气保护下200~400℃焙烧3~6h后制成。本发明所制备的高比表面积和高吸附性能除氟材料,由生物质碳、复合氧化物纳米片和稀土氧化物构成,充分结合了生物质碳材料、复合氧化物和稀土材料在吸附水体中氟离子的优势。除氟吸附剂的应用主要针对水中污染物的净化处理,制备的吸附材料具有吸附性能高、成本低廉且工艺简单,符合绿色化学的主旨。
Description
技术领域
本发明属于复合材料合成技术领域,涉及除氟吸附剂的制备,尤其涉及水热法制备除氟吸附剂及其应用。
背景技术
氟元素是人和动物所必需的微量元素,在人体内主要分布于牙齿和骨骼中。饮水中含有适量氟(0.5~1.5mg/L)对人体健康是有益的,但是长期饮用高浓度含氟饮水时,易患氟斑牙病;严重氟中毒时,氟元素可以使骨骼变形,导致氟骨病。天然地质条件和使用含氟原材料的工业都可能导致地表水和地下水的氟污染,从而引起氟中毒。人体摄氟途径主要通过饮水实现,饮用水中约80%左右的氟可以被人体吸收,因此,控制饮用水中氟的含量具有重要意义。
目前,常用的除氟法有吸附法、离子交换法、电渗析法和膜处理法,其中,应用最广泛的是吸附法。常用的除氟吸附剂有稀土氧化物、氧化铝、层状双氢氧化物(LDHs)、沸石和海泡石等。稀土吸附材料有着优良的除氟性能,但稀土材料不但价格高,而且在制备和实际水处理中,还可能造成重金属污染。氧化铝是除氟应用最广泛的吸附剂,有着较高的表面积,但吸附性能要低于稀土材料。层状双氢氧化物(LDHs)由带正电荷的纳米片构成,有着潜在吸附水体中氟离子的性能,但是LDHs表面积较小,氟离子很难扩散到吸附剂内部。因此,制备高比表面积和高吸附性能除氟吸附剂具有重要的意义。
我国是世界上纸张消费大国,但废纸回收利用率却比较低。纸张的回收和开发利用,对于资源利用和环境保护有着重要意义。
本发明以废纸为原料,制备高比表面积和高吸附性能的环保材料,不仅提供了一种水污染控制材料的制备方法,还提供了一种废纸资源利用的方法。
发明内容
针对上述现有技术中存在的除氟材料比表面积低、除氟效果不理想的缺点,本发明公开了水热法制备除氟吸附剂及其应用。
本发明一个目的在于公开了一种水热法制备除氟吸附剂,以克服现有吸附材料吸附能效低,制备过程复杂,成本高等缺点。
技术方案:本发明先利用废纸为原材料经铝盐浸渍、氮气保护下500~800℃焙烧3~6h制备氧化铝/生物质碳材料,然后采用水热法在生物质碳材料表面原位生长一层纳米片,制得复合氧化物/生物质碳,再通过稀土硝酸盐对其表面改性,氮气保护下200~400℃焙烧3~6h,最终制得复合除氟吸附剂。
一种水热法制备除氟吸附剂的方法,具体包括如下步骤:
S1.制备氧化铝/生物质碳:
将废纸依次在蒸馏水中和无水乙醇中清洗3~5次,50~80℃下干燥6~12h,得预处理纸张;
按每100mL溶液加入1~5g预处理纸张计,将预处理纸张浸渍在0.05~0.5mol/L的铝盐溶液中,浸渍1~2h,取出,蒸馏水洗涤1~3次,50~80℃下干燥6~12h,氮气保护下500~800℃焙烧3~6h后,浸渍-氮气保护下焙烧重复3~5次,得氧化铝/生物质碳;
S2.制备复合氧化物/生物质碳:
按氧化铝/生物质碳与六亚甲基四胺质量比为1:1~2:1计,优选1:1,二价金属M盐与六亚甲基四胺比摩尔比为1:1~2:1计,优选2:1,将氧化铝/生物质碳和六亚甲基四胺加入到0.05~0.5mol/L二价金属M盐溶液中,混合均匀后,转移到内衬聚四氟乙烯的高压反应釜中,75~160℃优选120℃,水热反应12~24h优选15h,冷却、过滤,蒸馏水洗涤3~5次,50~80℃下干燥12~24h,氮气保护下400~600℃焙烧2~6h优选4h,得复合氧化物/生物质碳;
S3.除氟吸附剂的制备:
按每100mL稀土硝酸盐溶液中加入1~5g,优选3g复合氧化物/生物质碳计,将复合氧化物/生物质碳浸渍在浓度为0.5~0.15mol/L的稀土硝酸盐溶液中,优选0.1mol/L,浸渍1~2h,取出,50~80℃下干燥6~12h,氮气保护下200~400℃焙烧3~6h,优选4h,得除氟吸附剂。
本发明的较优实施例中,S1所述铝盐为硝酸铝、氯化铝和硫酸铝中的一种或者多种组合。
本发明的较优实施例中,S2所述的二价金属M为镁、镍、锌或铜中的一种或者多种组合,M盐为硝酸盐、氯化盐、硫酸盐或醋酸盐中的一种或者多种组合。
本发明的较优实施例中,S3所述的稀土硝酸盐为镧、铈、镨或钕中的一种或者多种硝酸盐组合。
根据上述方法制得的除氟吸附剂,由生物质碳、复合氧化物纳米片和稀土氧化物构成,具有分级多孔结构,该分级多孔结构由废纸为原料制备的生物质碳为基体,复合氧化物纳米片原位生长在基体表面,稀土氧化物附着于生物质碳和复合氧化物纳米片表面。
所述的除氟吸附剂,所述生物质碳具有纤维结构,由废纸为原料和前驱体制备而成;所述复合氧化物纳米片由氧化镁、氧化镍、氧化锌或氧化铜中一种或者多种与氧化铝复合而成,其尺寸为500nm~1μm;所述稀土氧化物由氧化镧、氧化铈、氧化镨或氧化钕一种或者多种组合。
本发明的另外一个目的,是公开了所述除氟吸附剂在去除水中氟离子的应用。
有益效果
本发明利用廉价的纸张为原材料,制备高比表面积和高吸附性能除氟材料。该材料由生物质碳、复合氧化物纳米片和稀土氧化物构成,充分结合了生物质碳材料、复合氧化物和稀土材料在吸附水体中氟离子的优势。本发明的应用主要针对水中污染物的净化处理,制备的吸附材料具有吸附性能高、成本低廉且工艺简单,符合绿色化学的主旨。
本发明的特点为:
(1)、本发明的原材料为纸张,原材料来源具有广泛性和可再生性,不仅提供了一种廉价的污染控制材料,还提供一种废纸资源利用的方法。
(2)、本发明所制备的除氟材料具有高效的吸附性能,结合了生物质碳、复合氧化物和稀土材料在吸附水体中氟离子的优点,能够有效控制水体中氟离子的含量,并且本发明制备的吸附材料能够应用在水体中其他污染物治理。
(3)、本发明所公开的水热法制备除氟吸附剂,吸附材料的制备过程可控,吸附材料的组分可调,不会对环境造成污染。
附图说明
图1为除氟吸附剂纤维结构的扫描电镜图;
图2为除氟吸附剂表面纳米片的扫描电镜图。
具体实施方式
下面结合实施例对本发明进行详细说明,以使本领域技术人员更好地理解本发明,但本发明并不局限于以下实施例。
实施例1
以废弃报纸为碳源和前驱体,将废弃报纸分别在蒸馏水和和无水乙醇中清洗3次,80℃下干燥12h,得预处理纸张。取5g预处理纸张浸渍在100mL硝酸铝溶液中,浸渍时间2h,取出,蒸馏水洗涤3次,50~80℃下干燥12h,氮气保护下600℃焙烧4h后,浸渍-氮气保护下焙烧重复3次,得氧化铝/生物质碳;
取氧化铝/生物质碳0.28g和六亚甲基四胺0.28g加入到20mL浓度为0.1mol/L的硝酸镁溶液中,混合均匀后,转移将到内衬聚四氟乙烯的高压反应釜中,120℃下反应12h,冷却、过滤,蒸馏水洗涤3次,80℃下干燥12h,氮气保护下500℃焙烧4h,得复合氧化物/生物质碳;
取3g复合氧化物/生物质碳加入到100mL浓度为0.1mol/L的硝酸镧溶液中,浸渍时间2h,取出,80℃下干燥12h,氮气保护下300℃焙烧4h,得除氟吸附剂。
取50mg实施例1中的除氟吸附材料,加入20mL浓度为20mg/L氟化钠溶液中,静态吸附24h,测量吸附前后氟离子浓度,对水体中氟离子的去除率可达98.5%。
实施例2
以废弃卷纸为碳源和前驱体,将卷纸分别在蒸馏水和和无水乙醇中清洗3次,80℃下干燥12h,得预处理纸张。取5g预处理纸张浸渍在100mL硝酸铝溶液中,浸渍时间2h,取出,蒸馏水洗涤3次,50~80℃下干燥12h,氮气保护下600℃焙烧4h后,浸渍-氮气保护下焙烧重复3次,得氧化铝/生物质碳;
取氧化铝/生物质碳0.28g和六亚甲基四胺0.28g加入到20mL浓度为0.1mol/L的硝酸镁溶液中,混合均匀后,转移将到内衬聚四氟乙烯的高压反应釜中,120℃下反应12h,冷却、过滤,蒸馏水洗涤3次,80℃下干燥12h,氮气保护下500℃焙烧4h,得复合氧化物/生物质碳;
取3g复合氧化物/生物质碳加入到100mL浓度为0.1mol/L的硝酸镧溶液中,浸渍时间2h,取出,80℃下干燥12h,氮气保护下300℃焙烧4h,得除氟吸附剂。
取50mg实施例2中的除氟吸附材料,加入20mL浓度为20mg/L氟化钠溶液中,静态吸附24h,测量吸附前后氟离子浓度,对水体中氟离子的去除率可达99.2%。
实施例3
以废弃卷纸为碳源和前驱体,将卷纸分别在蒸馏水和和无水乙醇中清洗3次,80℃下干燥12h,得预处理纸张。取4g预处理纸张浸渍在100mL硫酸铝溶液中,浸渍时间2h,取出,蒸馏水洗涤3次,50~80℃下干燥12h,氮气保护下600℃焙烧4h后,浸渍-氮气保护下焙烧重复3次,得氧化铝/生物质碳;
取氧化铝/生物质碳0.28g和六亚甲基四胺0.28g加入到20mL浓度为0.1mol/L的硝酸锌溶液中,混合均匀后,转移将到内衬聚四氟乙烯的高压反应釜中,120℃下反应12h,冷却、过滤,蒸馏水洗涤3次,80℃下干燥12h,氮气保护下500℃焙烧4h,得复合氧化物/生物质碳;
取3g复合氧化物/生物质碳加入到100mL浓度为0.1mol/L的硝酸镧溶液中,浸渍时间2h,取出,80℃下干燥12h,氮气保护下300℃焙烧4h,得除氟吸附剂。
取50mg实施例3中的除氟吸附材料,加入20mL浓度为20mg/L氟化钠溶液中,静态吸附24h,测量吸附前后氟离子浓度,对水体中氟离子的去除率可达96.9%。
实施例4
以废弃报纸为碳源和前驱体,将报纸分别在蒸馏水和和无水乙醇中清洗3次,80℃下干燥12h,得预处理纸张。取5g预处理纸张浸渍在100mL氯化铝溶液中,浸渍时间2h,取出,蒸馏水洗涤3次,50~80℃下干燥12h,氮气保护下600℃焙烧4h后,浸渍-氮气保护下焙烧重复3次,得氧化铝/生物质碳;
取氧化铝/生物质碳0.28g和六亚甲基四胺0.28g加入到20mL浓度为0.1mol/L的硝酸镍溶液中,混合均匀后,转移将到内衬聚四氟乙烯的高压反应釜中,120℃下反应12h,冷却、过滤,蒸馏水洗涤3次,80℃下干燥12h,氮气保护下500℃焙烧4h,得复合氧化物/生物质碳;
取3g复合氧化物/生物质碳加入到100mL浓度为0.1mol/L的硝酸镧溶液中,浸渍时间2h,取出,80℃下干燥12h,氮气保护下300℃焙烧4h,得除氟吸附剂。
取50mg实施例4中的除氟吸附材料,加入20mL浓度为20mg/L氟化钠溶液中,静态吸附24h,测量吸附前后氟离子浓度,对水体中氟离子的去除率可达95.8%。
实施例5
以废弃卷纸为碳源和前驱体,将卷纸分别在蒸馏水和和无水乙醇中清洗3次,80℃下干燥12h,得预处理纸张。取5g预处理纸张浸渍在100mL硝酸铝溶液中,浸渍时间2h,取出,蒸馏水洗涤3次,50~80℃下干燥12h,氮气保护下600℃焙烧4h后,浸渍-氮气保护下焙烧重复3次,得氧化铝/生物质碳;
取氧化铝/生物质碳0.28g和六亚甲基四胺0.28g加入到20mL浓度为0.1mol/L的醋酸锌溶液中,混合均匀后,转移将到内衬聚四氟乙烯的高压反应釜中,75℃下反应12h,冷却、过滤,蒸馏水洗涤3次,80℃下干燥12h,氮气保护下500℃焙烧4h,得复合氧化物/生物质碳;
取3g复合氧化物/生物质碳加入到100mL浓度为0.1mol/L的硝酸镧溶液中,浸渍时间2h,取出,80℃下干燥12h,氮气保护下300℃焙烧4h,得除氟吸附剂。
取50mg实施例5中的除氟吸附材料,加入20mL浓度为20mg/L氟化钠溶液中,静态吸附24h,测量吸附前后氟离子浓度,对水体中氟离子的去除率可达97.8%。
实施例6
以废弃报纸为碳源和前驱体,将报纸分别在蒸馏水和和无水乙醇中清洗3次,80℃下干燥12h,得预处理纸张。取5g预处理纸张浸渍在100mL硝酸铝溶液中,浸渍时间2h,取出,蒸馏水洗涤3次,50~80℃下干燥12h,氮气保护下600℃焙烧4h后,浸渍-氮气保护下焙烧重复3次,得氧化铝/生物质碳;
取氧化铝/生物质碳0.28g和六亚甲基四胺0.28g加入到20mL浓度为0.1mol/L的氯化镁溶液中,混合均匀后,转移将到内衬聚四氟乙烯的高压反应釜中,120℃下反应12h,冷却、过滤,蒸馏水洗涤3次,80℃下干燥12h,氮气保护下500℃焙烧4h,得复合氧化物/生物质碳;
取3g复合氧化物/生物质碳加入到100mL浓度为0.1mol/L的硝酸镧溶液中,浸渍时间2h,取出,80℃下干燥12h,氮气保护下300℃焙烧4h,得除氟吸附剂。
取50mg实施例6中的除氟吸附材料,加入20mL浓度为20mg/L氟化钠溶液中,静态吸附24h,测量吸附前后氟离子浓度,对水体中氟离子的去除率可达99.3%。
以上所述仅为本发明的实施例,并非因此限制本发明的专利范围,凡是利用本发明说明书所作的等效结构或等效流程变换,或直接或间接运用在其他相关的技术领域,均同理包括在本发明的专利保护范围内。
Claims (9)
1.一种水热法制备除氟吸附剂的方法,其特征在于,包括如下步骤:
S1.制备氧化铝/生物质碳:
将废纸依次在蒸馏水中和无水乙醇中清洗3~5次,50~80℃下干燥6~12h,得预处理纸张;
按每100mL溶液加入1~5g预处理纸张计,将预处理纸张浸渍在0.05~0.5mol/L的铝盐溶液中,浸渍1~2h,取出,蒸馏水洗涤1~3次,50~80℃下干燥6~12h,氮气保护下500~800℃焙烧3~6h后,浸渍-氮气保护下焙烧重复3~5次,得氧化铝/生物质碳;
S2.制备复合氧化物/生物质碳:
按氧化铝/生物质碳与六亚甲基四胺质量比为1:1~2:1计,二价金属M盐与六亚甲基四胺比摩尔比为1:1~2:1计,将氧化铝/生物质碳和六亚甲基四胺加入到0.05~0.5mol/L二价金属M盐溶液中,混合均匀后,转移到内衬聚四氟乙烯的高压反应釜中,75~160℃,水热反应12~24h,冷却、过滤,蒸馏水洗涤3~5次,50~80℃下干燥12~24h,氮气保护下400~600℃焙烧2~6h,得复合氧化物/生物质碳;
S3.除氟吸附剂的制备:
按每100mL稀土硝酸盐溶液中加入1~5g复合氧化物/生物质碳计,将复合氧化物/生物质碳浸渍在浓度为0.5~0.15mol/L的稀土硝酸盐溶液中,浸渍1~2h取出,50~80℃下干燥6~12h,氮气保护下200~400℃焙烧3~6h,得除氟吸附剂。
2.根据权利要求1所述的水热法制备除氟吸附剂的方法,其特征在于:S1所述铝盐为硝酸铝、氯化铝和硫酸铝中的一种或者多种组合。
3.根据权利要求1所述的水热法制备除氟吸附剂的方法,其特征在于:S2所述的二价金属M为镁、镍、锌或铜中的一种或者多种组合,M盐为硝酸盐、氯化盐、硫酸盐或醋酸盐中的一种或者多种组合。
4.根据权利要求1所述的水热法制备除氟吸附剂的方法,其特征在于:S3所述的稀土硝酸盐为镧、铈、镨或钕中的一种或者多种硝酸盐组合。
5.根据权利要求1所述的水热法制备除氟吸附剂的方法,其特征在于:S2所述按氧化铝/生物质碳与六亚甲基四胺质量比为1:1,二价金属M盐与六亚甲基四胺比摩尔比为2:1。
6.根据权利要求1所述的水热法制备除氟吸附剂的方法,其特征在于:S2所述转移到内衬聚四氟乙烯的高压反应釜中,120℃水热反应15h。
7.根据权利要求1所述的水热法制备除氟吸附剂的方法,其特征在于:S2所述氮气保护下400~600℃焙烧4h。
8.根据权利要求1-7任一所述方法制备的除氟吸附剂,其特征在于:所述除氟吸附剂由生物质碳、复合氧化物纳米片和稀土氧化物构成,具有分级多孔结构,该分级多孔结构由废纸为原料制备的生物质碳为基体,复合氧化物纳米片原位生长在基体表面,稀土氧化物附着于生物质碳和复合氧化物纳米片表面。
9.一种权利要求8所述除氟吸附剂的应用,其特征在于:将其应用于去除水中氟离子。
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