CN111151225A - 一种钛氧簇凝胶吸附剂及其应用 - Google Patents
一种钛氧簇凝胶吸附剂及其应用 Download PDFInfo
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- CN111151225A CN111151225A CN202010022918.1A CN202010022918A CN111151225A CN 111151225 A CN111151225 A CN 111151225A CN 202010022918 A CN202010022918 A CN 202010022918A CN 111151225 A CN111151225 A CN 111151225A
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- titanium
- adsorbent
- solution
- gel adsorbent
- cluster gel
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 69
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- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 25
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 18
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- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 14
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- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 12
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims description 11
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- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
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- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 3
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Images
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J20/28014—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 form
- B01J20/28047—Gels
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- C—CHEMISTRY; METALLURGY
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/06—Contaminated groundwater or leachate
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Dispersion Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
本发明提供一种钛氧簇凝胶吸附剂及其应用,该吸附剂通过如下方法获得:将有机配体加入有机钛源与醇类溶剂的混合溶液中,获得A液,然后将水醇溶液缓慢滴入A液中,搅拌至形成凝胶,最后老化至恒重或冻干,即获得钛氧簇凝胶吸附剂;该吸附剂可应用于地下水及饮用水的处理,吸附各类重金属污染物,吸附效果好、稳定性高,为重金属污染地区的社区或家庭提供了一种简便、易行的方案。
Description
技术领域
本发明涉及水处理技术领域,是一种高效去除水中重金属污染物的吸附剂。
背景技术
地下水中天然存在的重金属,特别是砷(As),严重威胁着公众健康,是世界性的环境问题之一。长期饮用含砷地下水可能会引起严重的健康问题,如神经系统症状和皮肤病变,甚至癌症等。各种技术已被用于处理水中的As,包括常规的吸附、砂滤、混凝、离子交换以及膜过滤等工艺。其中,吸附被认为是当前最适用的处理方式。然而,由于三价砷(As(III))在天然水中不带电,难以通过吸附去除。因此通常需要将其氧化成在环境条件下带电的五价砷(As(V)),再通过吸附去除。例如,Xu等(J.Xu,W.Ding,F.Wu,G.Mailhot,D.Zhou,K.Hanna,Applied Catalysis B:Environmental 2016,186,56.)研究了在Fe(III)/亚硫酸盐体系中可见光诱导As(III)催化氧化为As(V)的情况,结果表明,在接近中性的pH值下,辐照30分钟后,通过离心处理从溶液中去除了93%的As(III);Lan等(S.Lan,H.Ying,X.Wang,F.Liu,W.Tan,Q.Huang,J.Zhang,X.Feng,Water Research 2018,128,92.)发现Mn(II)能够促进亚铁酸盐表面上溶解的O2有效氧化As(III),开发了Mn(II)/ferrihydrite催化氧化去除As(III)技术。专利CN104876374A报道了一种同时还原铬和氧化砷的电化学水处理方法,是将球形金钯合金负载的碳纳米管复合物电极应用于电催化反应中原位高效催化O2还原生成H2O2,进而氧化去除废水中的砷、铬等重金属;预氧化系统增加了工艺成本,同时会产生一些不利的氧化副产物,例如消毒副产物,因此不宜饮用水处理。目前,直接从水中除去As(III)且能满足当代饮用水处理要求的新型高效吸附剂的开发成为近年来重金属去除领域的研究热点。
而地下水中除砷外,通常都含有大量的还原铁和锰,即亚铁离子和锰离子,这些离子被人们忽视其危害。在一些集中供水设施中,这些离子通常通过氧化处理后过滤去除,但同样会有引入不利的氧化副产物风险,不宜于饮水系统。
溶胶-凝胶法是一种以无机钛盐或钛醇酯为原料,经水解形成溶胶,再进一步缩聚得到凝胶的方法。在溶胶-凝胶制备过程中,通常通过加入水解抑制剂来调节水解-缩聚的速率以控制凝胶的合成。例如,专利ZL 201210509803.3公开了一种TiO2干凝胶材料及其制备方法与应用。该专利利用钛酸四丁酯为钛源,乙酰丙酮为水解抑制剂,通过调节原料配比,合成了一种TiO2干凝胶;该干凝胶对带有负电荷的偶氮染料具有良好的吸附性能,吸附容量可与常规的活性炭相媲美。但如前所述,地下水中的三价砷为电中性,无法通过静电吸附作用去除。专利CN200610049186.5公开一种制备不开裂二氧化钛膜的方法,其利用钛酸异丙酯为钛源水解后水热合成获得中间产物二氧化钛凝胶,然后烧结获得二氧化钛膜,由于该方案钛基凝胶结构中不含有乙酰丙酮等有机配体络合在钛表面,且该制备过程需要通过水热煅烧成型,能耗高,限制了其在水污染治理方面的应用。目前尚未见有利用钛基材料吸附去除水中As(III)的公开报道。
发明内容
针对上述问题,本发明提供一种钛氧簇凝胶吸附剂,对电中性和阳离子重金属的吸附效果好,可广泛应用于地下水和废水处理领域。
本发明首先提供了一种钛氧簇凝胶吸附剂,该吸附剂是通过如下方法获得的:
(a)将有机配体加入有机钛源与醇类溶剂的混合溶液中,以100~300rpm的速率搅拌10min,获得A液,备用;
上述有机配体优选乙酰丙酮、乙酸、乙二胺四乙酸、丙二酸、丁二酸中的一种或多种;
上述有机钛源可以选择钛酸四丁酯、钛酸异丙酯中的一种或两种;
本步骤中,醇类溶剂的目的是分散有机钛源和水,防止二者反应过于剧烈,其作为溶剂本身并不参与反应,故该醇类溶剂选择范围宽泛,可以使用目前常见的各种醇,如甲醇、乙醇、丙醇、丁醇、辛醇、戊醇、己醇、庚醇、葵醇、乙二醇、丙三醇、丙二醇、季戊四醇、丙烯醇、乙烯醇中的任意一种或多种;有机钛源与醇类溶剂的比值可以为任意比,一般以有机钛源完全溶解于醇类溶剂中为宜;
(b)将去离子水与醇溶液混合后获得水醇溶液,备用;
本步骤利用通过醇溶液稀释反应物水的浓度,以确保向A液中滴加时不会出现局部水浓度过高而产生水解沉淀,因此醇溶液可以使用目前常见的各种醇,如甲醇、乙醇、丙醇、丁醇、辛醇、戊醇、己醇、庚醇、葵醇、乙二醇、丙三醇、丙二醇、季戊四醇、丙烯醇、乙烯醇中的任意一种或多种,且去离子水与醇溶液的比例可以为任意比(实践中,一般以去离子水与醇的体积比3:3-10为宜);在具体实施中,本步骤的醇溶液与步骤(a)中的醇类溶剂可以选择相同的醇,也可以为不同的醇。
(c)将步骤(b)获得的水醇溶液滴入A液中,然后以100~300rpm的速率搅拌30-60min,通过A液中的有机配体控制水解速度获得凝胶;
(d)将步骤(c)获得的凝胶置于室温或干燥炉中(不超过60℃)老化至恒重或置于冻干机中冻干(-45~-15℃下冻干24~72h),即获得所述钛氧簇凝胶吸附剂。
进一步,本发明中,步骤(c)所述滴入是指,将水醇溶液以0.5-1.5mL/min的滴加速率逐滴滴入A液中,以防止滴加速率过快导致的反应剧烈。
进一步,本发明中,将有机配体与有机钛源的摩尔比为1:2~64,优选1:2~8。
其次,本发明提供了上述钛氧簇凝胶吸附剂在饮用水处理中的应用;该应用具体步骤如下;将水样以5-30BV/h的流速通过该钛氧簇凝胶吸附剂,以吸附去除水样中所含重金属,所述重金属包括铅、汞、砷、镉、铬、锑、锰、铝中的一种或多种,吸附后的水样达到《生活饮用水卫生标准》(GB5749-2006)的要求;所述水样包括地下水等天然水体;在具体实施中,也可以将该吸附剂固定于过滤器中,便于操作。
第三,本发明还提供了上述钛氧簇凝胶吸附剂在废水处理中的应用,该应用具体步骤如下:将废水以5~100BV/h的速度通过含有钛氧簇凝胶吸附剂的固定床,以吸附去除废水中重金属污染物;所述重金属污染物包括铅、汞、砷、镉、铬、锑、锰、铝中的一种或多种。
本申请中,技术术语“废水”包括工业废水和生活污水,如文献“高廷耀,顾国维,周琪.水污染控制工程(下册)[J].1999.高等教育出版社”中的介绍。
本申请采用溶胶-凝胶法,以有机钛源(钛酸四丁酯、钛酸异丙酯)为前驱体,加入富含螯合电子的有机配体(乙酰丙酮、乙酸、EDTA、草酸、乙二胺)作为抑制剂,与钛醇盐的反应随后形成能够在室温下稳定存在的单取代二聚(烷氧基桥联)钛化合物溶胶,前驱体的不同物理性质导致不同的分解机理,钛烷氧基团最初被有机配体基团取代,控制引发较慢的水解反应,钛盐的水解和缩合的顺序发生以最终形成聚合物凝胶。相较于现有技术,具有以下有益效果:
(1)本发明的钛氧簇凝胶吸附剂的制备方法步骤简单,所获得的钛氧簇凝胶吸附剂吸附重金属的效果好、稳定性高;
(2)本发明制备的钛氧簇凝胶吸附剂,可直接装柱,用于固定床吸附;
(3)本发明制备的钛氧簇凝胶吸附剂,通过抑制剂的添加控制钛盐的水解速度,有利于钛羟基水解产物的可控生成,从而提高了对砷等重金属的吸附效果。
附图说明
图1是实施例1中钛氧簇凝胶吸附剂吸附亚砷酸盐的动力学曲线示意图;
图2是实施例1中钛氧簇凝胶吸附剂与纳米金属氧化物复合树脂对含As(III)模拟水的固定床吸附效果对比示意图;
图3是实施例1-4中通过添加不同比例乙酰丙酮和由不同方式干燥所得钛氧簇凝胶吸附剂对含As(III)模拟水的吸附效果比较示意图。
具体实施方式
下面结合实施例和应用例对本发明做进一步说明,但本发明所保护的范围不限于此。
实施例中所涉及的试剂来源:
钛酸四丁酯(TBT,C16H36O4Ti,CAS号:5593-70-4,购自麦克林,AR,货号:T818869-500ml);
电感耦合等离子体发射光谱仪(ICP-OES,iCAP 7400,赛默飞世尔,USA);
复合树脂HFO@D201或HZO@D201柱购自江苏南大环保科技有限公司;
其他试剂,除非特殊说明,均通过市售途径购买获得。
实施例1制备钛氧簇凝胶吸附剂及水样砷去除测试
(1)制备钛氧簇凝胶吸附剂
a.将10mL钛酸四丁酯滴入到醇类溶剂(10mL)与乙酰丙酮(1.5mL)的混合液中,常温下以100rpm的速率搅拌30分钟,所获得的透明溶液即为A液;
本实施例中乙酰丙酮与Ti的摩尔比为1:2;
本实施例中,醇类溶剂选择乙醇,该醇类溶剂在反应中仅作为有机钛源的载体,可以选择目前常见的各种醇,如甲醇、乙醇、丙醇、丁醇、辛醇、戊醇、己醇、庚醇、葵醇、乙二醇、丙三醇、丙二醇、季戊四醇、丙烯醇、乙烯醇中的任意一种或多种。
b.10mL醇溶液与3mL去离子水充分混合,获得水醇溶液,即水醇溶液(在具体实施中,将去离子水与醇溶液按照体积比1:1~24混合,皆可实现发明之目的);
本实施例中,醇溶液为乙醇,在具体实施中,可以选择目前常见的各种醇,如甲醇、乙醇、丙醇、丁醇、辛醇、戊醇、己醇、庚醇、葵醇、乙二醇、丙三醇、丙二醇、季戊四醇、丙烯醇、乙烯醇中的任意一种或多种。
c.将水醇溶液以1mL/min的速率滴入A液中(具体实施中,滴加速率可以控制在0.5-1.5mL/min的范围内),然后以100rpm的速率持续搅拌溶液30min,得到稳定的凝胶。
d.将获得的凝胶置于30℃通风橱中老化至恒重(约7d),即得钛氧簇凝胶吸附剂。
(2)钛氧簇凝胶吸附剂处理其他重金属模拟水样
以亚砷酸钠、砷酸钠、硝酸铅、硝酸钴、硝酸镍、硝酸亚铜、重铬酸钾配制0.5mM浓度的重金属离子溶液,所获得的重金属模拟水样水质指标:As(III),As(V),Pb(II),Cd(II),Ni(II),Cu(II),Cr(VI)初始浓度为0.5mM;pH为6.5±0.1。
本实施例中钛氧簇凝胶吸附剂的投加量为0.2g/L,在150rpm转速下振荡,测定水中重金属含量。除非另有说明,批量实验的温度设定在298K振荡48小时以达到平衡。
采用电感耦合等离子体发射光谱仪检测溶液中的金属离子浓度,根据公式(Q=(C0-Ce)/ML)计算了金属吸附量,并列入表1.公式中C0和Ce分别是初始和终了时污染物浓度,ML是吸附剂的投加量,采用电感耦合等离子体发射光谱仪测量金属离子浓度。
表1钛氧簇凝胶吸附剂对模拟水样中重金属污染物的吸附量检测结果
如表1所示,除了砷之外,钛氧簇凝胶吸附剂还能有效去除其它重金属,如Pb(II),Cd(II),Ni(II),Cu(II),Cr(VI)。
(3)钛氧簇凝胶吸附剂处理含砷水样的pH值影响实验
将20mg的本实施例获得的钛氧簇凝胶吸附剂投入7个含有100mL的As(III)(10mg/L)和As(V)(10mg/L)的250mL锥形瓶中,用1M的NaOH或HNO3分别将pH值调节至3.0、4.0、5.0、6.0、7.0、8.0、9.0。使用机械摇床混合悬浮液和控制温度,并以不同的时间间隔收集样品以确定砷浓度。
在反应期间通过在非常短的时间内添加体积可以忽略不计NaOH或HNO3来保持pH恒定。通过将pH从3变为9来研究pH对As(III)和As(V)去除的影响。检测结果如表2所示。
表2不同pH值下钛氧簇凝胶吸附剂对模拟水中砷的吸附量检测结果
从表2中可以看出,在宽泛的pH(即3-9)范围中,钛氧簇凝胶吸附剂对As(V)的吸附能力随着pH增加而降低,而对As(III)的吸附能力不受pH的影响。钛氧簇凝胶吸附剂在实验pH范围内保持稳定的As(III)吸附容量。天然地下水的pH值范围为6.5至9.0,这意味着在广大地区净化地下水时钛氧簇吸附剂能稳定去除As(III),无需预氧化工艺,具有广阔的应用潜力。
(4)钛氧簇凝胶吸附剂处理含砷水样批量等温吸附实验
将20mg本实施例获得的钛氧簇凝胶吸附剂投入初始As(III)浓度为5~400mg/L的100mL水样中,确定吸附剂对As(III)的去除容量。
水样水质指标为:初始温度298K,初始pH 7.0±0.1。在150rpm转速下振荡,测定水中砷含量,并根据朗缪尔吸附等温方程(Qe=Qm KL Ce/(1+KL Ce))和弗兰德里希等温方程(Qe=KF Ce 1/n)计算材料对As(III)和As(V)的最大吸附量和吸附行为。其中Ce和Qe是吸附终了时平衡浓度(mg/L)和吸附量(mg/g),Qm是最大吸附量(mg/g),KL和KF是吸附剂与吸附剂之间的亲和力有关的速率常数。n与吸附剂表面的不均一性有关。等温线模型的适用性由相关系数的平方(R2)用来量化,检测结果如表3所示。
表3钛氧簇凝胶吸附剂对于含砷水样的批量等温吸附参数
从表3中可以看出,本实施例获得的钛氧簇凝胶吸附剂表现出对As(III)的高吸附容量,尤其是在中性条件下表现出相当惊人的对亚砷酸盐的吸附容量。
Langmuir吸附等温线拟合结果表明,钛氧簇凝胶吸附剂对As(III)的最大吸附量Qm高达255mg/g。
目前已报道的商业吸附剂对As(III)吸附的最大容量通常在2.1-39.2mg/g之间(D.Mohan,C.U.Pittman,Journal of Hazardous Materials 2007,142,1.),本实施例获得的钛氧簇凝胶吸附剂对砷吸附性能远超其他吸附材料,因此预期其在先进地下水水处理中的潜力。
(5)钛氧簇凝胶吸附剂对亚砷酸盐的吸附动力学
亚砷酸盐水样水质指标:[As(III)]初始浓度为10mg L-1,初始pH为7.0±0.1。本实施例中钛氧簇凝胶吸附剂的投加量为0.2g/L,在150rpm转速下振荡,测定不同时间下水中砷含量。并采用叶洛维奇吸附动力学方程(dQt/dt=αexp(-βQt))阐明钛氧簇凝胶吸附材料表面的除As(III)过程。其中Qt是表示t(h)时刻的吸附量,α是初始吸附速率(mg g-1h-1),β是与化学吸附的表面覆盖程度和活化能有关的常数。
图1为在溶液pH为7的情况下钛氧簇凝胶吸附剂吸附去除亚砷酸盐的动力学曲线示意图,可见钛氧簇凝胶吸附剂对于As(III)具有很好的去除效果。叶洛维奇吸附动力学方程拟合结果为α=36.1,β=0.11,R2=0.99,说明钛氧簇凝胶吸附As(III)过程涉及到亚砷酸盐与表面之间的配位键的形成或破裂的化学吸附过程。
(6)钛氧簇凝胶吸附剂去除As(Ⅲ)模拟水样溶液中共存物的影响
As(Ⅲ)模拟水样水质指标:初始As(Ⅲ)浓度为10.0±1.0mg/L,pH为7.0±0.1。
通过向试验溶液中加入预定量的NaCl,NaHCO3,Na2SO4,Na3PO4和Na2SiO3来检测一些普遍共存的阴离子的影响。通过向溶液中加入定量腐殖酸(HA)考察水中有机质对吸附过程的影响。本实施例中钛氧簇凝胶吸附剂的投加量为0.2g/L,在150rpm转速下振荡,测定水中砷含量。
表4共存污染物对钛氧簇凝胶吸附剂吸附As(III)的影响
如表4所示,可以看出,在7.0的固定pH下,仅有磷酸盐或硅酸盐会导致材料表面As(III)吸附量的明显降低。在实验条件下,即使在无机盐浓度为10mM,HA为50mg/L的水平下,硫酸盐、氯离子、碳酸盐和HA的作用也是可以忽略不计的。这归因于钛氧簇凝胶吸附剂表面吸附位点与As(III)之间的强亲和力。亚砷酸盐、磷酸盐和硅酸盐都是四面体阴离子。它们都倾向于与金属氧化物表面的官能团形成内球复合物。值得注意的是,砷污染地下水中磷酸盐和硅酸盐的典型浓度范围为0-0.15mM和0.17-1.24mM。表4显示,在1mM磷酸盐和和硅酸盐存在下,钛氧簇凝胶吸附剂上的As(III)吸附量仍高于30mg/g。这清楚地表明吸附剂在处理地下水中的As(III)方面的巨大潜力。
由(2)-(5)可以看出,在pH为3~9内,钛氧簇凝胶吸附剂对废水均具有较好的吸附效果。
(7)钛氧簇凝胶吸附剂处理模拟地下水
模拟地下水水质指标:As(III)初始浓度为200μg/L,SO4 2-为100mg/L,Cl-为100mg/L,HCO3 -为100mg/L,SiO3 2-为10mg/L,NO3 -为5mg/L,pH为7±0.1,流速为20BV/h。
将0.44g钛氧簇凝胶吸附剂装在在50mm高和5mm直径的塑料柱中,填充吸附床层大小为φ5mm×25mm(体积约0.5mL),模拟地下水通过蠕动泵以20BV/h的流速下流出构筑物,测定水中砷含量。经检测,本实施例获得的流出水样符合《生活饮用水卫生标准》(GB5749-2006)对水中砷的控制要求,穿透点设定为10ug/L,该流出水样可作为饮用水使用。
吸附床为本领域常见固定吸附剂的装置,液体通过吸附剂床层时,吸附剂保持静止。本实施例中所使用的吸附床参见中国专利“用于水处理的吸附床”(专利号:2009100033150)中所公开。
图2为钛氧簇凝胶吸附剂与纳米金属氧化物复合树脂对模拟地下水吸附效果对比示意图,钛氧簇凝胶吸附剂柱的处理地下水的能力要明显大于纳米金属氧化物复合树脂。
由图2所示,复合树脂HFO@D201或HZO@D201柱的有效可处理床体积(BV)仅为~450BV和~600BV。值得注意的是,本实施例中钛氧簇凝胶吸附剂(TAX)的有效可处理体积高达6000BV,几乎是这些商业树脂的10倍以上。柱实验的结果证明钛氧簇凝胶吸附剂通过固定床系统从真实的地下水中可持续去除痕量As(III)污染的巨大潜力。
在具体实施中,有机配体可以选择乙酰丙酮、乙酸、EDTA、草酸、乙二胺中的一种或多种,有机钛源可以选择钛酸四丁酯或钛酸异丙酯中的一种或两种,二者的摩尔比在1:2~64范围内,均可实现发明之目的。
实施例2
a.将10mL钛酸四丁酯滴入到叔丁醇(10mL)与乙酰丙酮(1.5mL)的混合液中,常温下以100rpm的速率搅拌30分钟,所获得的透明溶液即为A液;
本实施例中乙酰丙酮与Ti的摩尔比为1:2;
b.10mL叔丁醇与3mL去离子水充分混合,为水醇溶液;
c.将水醇溶液以1mL/min的速率滴入A液中,然后以100rpm的速率持续搅拌溶液30min,得到稳定的凝胶。
d.将获得的凝胶置于冻干机(冻干温度约-38℃)至恒重(约3d),即得钛氧簇凝胶吸附剂。在具体实施中,一般在-45~-15℃温度下冻干24~72h,皆可实现发明之目的。
实施例3
a.将10mL钛酸四丁酯滴入到乙醇(10mL)与乙酰丙酮(0.75mL)的混合液中,常温下以100rpm的速率搅拌30分钟,所获得的透明溶液即为A液;
本实施例中乙酰丙酮与Ti的摩尔比为1:4;
b.10mL乙醇与3mL去离子水充分混合,为水醇溶液;
c.将水醇溶液以1mL/min的速率滴入A液中,然后以100rpm的速率持续搅拌溶液30min,得到稳定的凝胶。
d.将获得的凝胶置于30℃通风橱中老化至恒重(约7d),即得钛氧簇凝胶吸附剂。
实施例4
a.将10mL钛酸四丁酯滴入到乙醇(10mL)与乙酰丙酮(0.375mL)的混合液中,常温下以100rpm的速率搅拌30分钟,所获得的透明溶液即为A液;
本实施例中乙酰丙酮与Ti的摩尔比为1:8;
b.10mL乙醇与3mL去离子水充分混合,为水醇溶液;
c.将水醇溶液以1mL/min的速率滴入A液中,然后以100rpm的速率持续搅拌溶液30min,得到稳定的凝胶。
d.将获得的凝胶置于30℃通风橱中老化至恒重(约7d),即得钛氧簇凝胶吸附剂。
实施例5
a.将10mL钛酸四丁酯滴入到乙醇(10mL)与乙酰丙酮(0.047mL)的混合液中,常温下以100rpm的速率搅拌30分钟,所获得的透明溶液即为A液;
本实施例中乙酰丙酮与Ti的摩尔比为1:64;
b.10mL乙醇与3mL去离子水充分混合,为水醇溶液;
c.将水醇溶液以1mL/min的速率滴入A液中,然后以100rpm的速率持续搅拌溶液30min,得到稳定的凝胶。
d.将获得的凝胶置于30℃通风橱中老化至恒重(约7d),即得钛氧簇凝胶吸附剂。
实施例6
a.将10mL钛酸四丁酯滴入到叔丁醇(10mL)与乙酰丙酮(0.375mL)的混合液中,常温下以100rpm的速率搅拌30分钟,所获得的透明溶液即为A液;本实施例中乙酰丙酮与Ti的摩尔比为1:8;
b.3mL乙醇与3mL去离子水充分混合,为水醇溶液;
c.将水醇溶液以1mL/min的速率滴入A液中,然后以100rpm的速率持续搅拌溶液30min,得到稳定的凝胶。
d.将获得的凝胶置于30℃通风橱中老化至恒重(约7d),即得钛氧簇凝胶吸附剂。
将实施例1-5制得的钛氧簇凝胶吸附剂应用于处理As(Ⅲ)模拟水样,并分析处理结果,结果如图3所示。
As(Ⅲ)模拟水样水质指标:初始As(Ⅲ)浓度为10.0±1.0mg/L,pH为7.0±0.1。钛氧簇凝胶吸附剂投加量为0.2g/L,在150rpm转速下振荡,测定水中砷含量。
图3显示了在前体液体中所引入的AA量和干燥方式对制备得到的钛氧簇凝胶吸附剂吸附As(III)能力的影响。在298K振荡6小时后,As(III)含量从AA/Ti摩尔比为1/4时的50%增加到AA/Ti摩尔比为1/2时的60%。吸附结果表明增加乙酰丙酮配体的量可以提高As(III)在钛干凝胶上的吸附性能。同样的,冻干可以减少钛干凝胶上乙酰丙酮的损失从而提高吸附量。
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及附图内容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 (10)
1.一种钛氧簇凝胶吸附剂,其特征在于,所述吸附剂是通过如下方法获得的:
a)将有机配体加入有机钛源与醇类溶剂的混合溶液中,获得A液,备用;
所述有机配体包括乙酰丙酮、乙酸、乙二胺四乙酸、丙二酸、丁二酸中的至少一种;
所述有机钛源包括钛酸四丁酯或钛酸异丙酯中的一种或两种;
有机配体与有机钛源的摩尔比为1:2~64;
b)将去离子水与醇溶液混合后获得水醇溶液,备用;
c)将水醇溶液滴入A液中,搅拌获得凝胶;
d)将凝胶置于不超过60oC的环境中老化或冻干至恒重,即获得所述钛氧簇凝胶吸附剂。
2.根据权利要求1所述的钛氧簇凝胶吸附剂,其特征在于,步骤b)所述的醇溶液包括甲醇、乙醇、丙醇、丁醇、辛醇、戊醇、己醇、庚醇、葵醇、乙二醇、丙三醇、丙二醇、季戊四醇、丙烯醇、乙烯醇中的至少一种。
3.根据权利要求1所述的钛氧簇凝胶吸附剂,其特征在于,步骤a)所述的醇类溶剂包括甲醇、乙醇、丙醇、丁醇、辛醇、戊醇、己醇、庚醇、葵醇、乙二醇、丙三醇、丙二醇、季戊四醇、丙烯醇、乙烯醇中的至少一种。
4.根据权利要求1所述的钛氧簇凝胶吸附剂,其特征在于,步骤c)所述滴入是指以0.5-1.5 mL/min的速率滴入。
5.根据权利要求1所述的钛氧簇凝胶吸附剂,其特征在于,步骤c)所述的冻干是指于-45~-15℃温度下下冻干。
6.如权利要求1-5任一所述的钛氧簇凝胶吸附剂在饮用水处理中的应用。
7.如权利要求1-5任一所述的钛氧簇凝胶吸附剂在废水处理中的应用。
8.如权利要求6所述的应用,其特征在于,所述应用是指,将水样以5-30 BV/h的流速通过所述钛氧簇凝胶吸附剂,以吸附去除水样中的重金属。
9.如权利要求7所述的应用,其特征在于,所述应用是指,将废水以5-100 BV/h的速度通过所述钛氧簇凝胶吸附剂,以吸附去除废水中的重金属污染物;所述重金属污染物包括铅、汞、砷、镉、铬、锑、锰、铝中的一种或多种。
10.如权利要求9所述的应用,其特征在于,所述废水包括工业废水和生活污水。
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111790451A (zh) * | 2020-08-04 | 2020-10-20 | 江苏师范大学 | 一种异金属钛氧簇合物晶态材料、其制备方法及其在染料光降解中的应用 |
CN111804344A (zh) * | 2020-07-15 | 2020-10-23 | 江苏师范大学 | 基于杯芳烃的钛氧簇合物及其制备方法和在染料光降解中的应用 |
CN112225381A (zh) * | 2020-07-09 | 2021-01-15 | 桂林理工大学 | 一种含铬废水的处理方法 |
CN115041133A (zh) * | 2022-06-15 | 2022-09-13 | 中南大学 | 一种埃洛石基吸附材料及其制备方法与应用 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101172852A (zh) * | 2007-10-30 | 2008-05-07 | 景德镇陶瓷学院 | 一种采用溶胶-凝胶工艺制备钛酸铝薄膜的方法 |
CN102976402A (zh) * | 2012-12-04 | 2013-03-20 | 南京大学 | 一种光控可逆吸附偶氮染料的TiO2干凝胶及其制备方法和应用 |
EP2418238B1 (en) * | 2010-08-11 | 2013-04-17 | SIRAP-GEMA S.p.A. | Titanium dioxide-coated expanded polymer sheet having photocatalytic activity, container and packaging for foodstuffs obtained from such polymer sheet |
CN103691417A (zh) * | 2013-12-24 | 2014-04-02 | 南京大学 | 一种TiO2/ACF催化材料的制备方法与应用 |
CN110479204A (zh) * | 2019-08-13 | 2019-11-22 | 云南大学 | 一种高吸附性TiO2气凝胶的制备方法及其吸附水中重金属离子的应用 |
-
2020
- 2020-01-09 CN CN202010022918.1A patent/CN111151225A/zh not_active Withdrawn
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101172852A (zh) * | 2007-10-30 | 2008-05-07 | 景德镇陶瓷学院 | 一种采用溶胶-凝胶工艺制备钛酸铝薄膜的方法 |
EP2418238B1 (en) * | 2010-08-11 | 2013-04-17 | SIRAP-GEMA S.p.A. | Titanium dioxide-coated expanded polymer sheet having photocatalytic activity, container and packaging for foodstuffs obtained from such polymer sheet |
CN102976402A (zh) * | 2012-12-04 | 2013-03-20 | 南京大学 | 一种光控可逆吸附偶氮染料的TiO2干凝胶及其制备方法和应用 |
CN103691417A (zh) * | 2013-12-24 | 2014-04-02 | 南京大学 | 一种TiO2/ACF催化材料的制备方法与应用 |
CN110479204A (zh) * | 2019-08-13 | 2019-11-22 | 云南大学 | 一种高吸附性TiO2气凝胶的制备方法及其吸附水中重金属离子的应用 |
Non-Patent Citations (2)
Title |
---|
武银银: "新型钛氧簇合物的合成及性质研究", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 * |
胡俊一: "钛氧簇合物的合成及性质研究", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 * |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112225381A (zh) * | 2020-07-09 | 2021-01-15 | 桂林理工大学 | 一种含铬废水的处理方法 |
CN112225381B (zh) * | 2020-07-09 | 2022-04-26 | 桂林理工大学 | 一种含铬废水的处理方法 |
CN111804344A (zh) * | 2020-07-15 | 2020-10-23 | 江苏师范大学 | 基于杯芳烃的钛氧簇合物及其制备方法和在染料光降解中的应用 |
CN111804344B (zh) * | 2020-07-15 | 2022-12-23 | 江苏师范大学 | 基于杯芳烃的钛氧簇合物及其制备方法和在染料光降解中的应用 |
CN111790451A (zh) * | 2020-08-04 | 2020-10-20 | 江苏师范大学 | 一种异金属钛氧簇合物晶态材料、其制备方法及其在染料光降解中的应用 |
CN111790451B (zh) * | 2020-08-04 | 2023-01-20 | 江苏师范大学 | 一种异金属钛氧簇合物晶态材料、其制备方法及其在染料光降解中的应用 |
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