CN114887593B - 一种可逆有机膨润土及其制备方法与应用 - Google Patents
一种可逆有机膨润土及其制备方法与应用 Download PDFInfo
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Abstract
本发明公开了一种可逆有机膨润土及其制备方法与应用,所述的可逆有机膨润土制备方法与应用包括:以钠基膨润土为原料,以酸碱响应型表面活性剂为改性剂进行改性,调节混合液pH在3.5~6.5之间,经水浴磁力搅拌后抽滤,烘干,研磨过筛即可,制得的可逆有机膨润土对工业废水中酚类污染物进行去除。本发明的优点在于将酸碱响应型的表面活性剂通过离子交换作用插层到钠基膨润土层间,调控混合液pH值使表面活性剂上基团的亲‑疏水性发生变化,改变钠基膨润土层间的表面活性剂形成的胶束形态,从而实现有机膨润土层间污染物吸附‑释放可逆循环调控,降低有机膨润土再生利用成本,减少固体废物产出。
Description
技术领域
本发明属于膨润土加工领域,特别是涉及一种可逆有机膨润土及其制备方法与应用。
背景技术
膨润土在我国储量丰富,其矿物成分以蒙脱石为主,比表面积大且吸附能力出众,在国内外常作环境修复材料使用。众所周知,我国水体污染问题一直存在,其中一类废水有机废水成分复杂,多含多环芳烃、杂环类化合物、有机农药、酚类、苯胺和染料等毒性物质,这些毒性物质危害巨大,严重影响生态安全和人体健康。国内外研究中常用有机改性剂对天然膨润土进行改性,以提高膨润土处理有机废水的处理能力。有机膨润土吸附法成本低,操作简便,吸附效率高等特性,属于处理有机废水比较有效的方法之一,而吸附污染物达到饱和后,需要进一步处理,饱和的有机膨润土如何处理才能不造成二次污染成为有机膨润土吸附法应用的一大难题。处理方法有填埋和再生。填埋不能解决污染物去除的问题,还会造成填埋场地的污染。再生属于比较有效的一类方法,目前有机膨润土再生的方法有酸碱法、高温加热法、微生物法和化学氧化法。酸碱法是在过酸或者过碱的条件下改变膨润土表面的电荷,通过静电排斥作用将污染物与有机膨润土分离。高温加热法是利用高温将所吸附的污染物分解或者氧化。朱利中团队将已吸附有机污染物的有机膨润土在N2环境下进行高温碳化,处理后的有机膨润土对部分废水仍有吸附能力;微生物法是利用微生物新陈代谢作用去分解污染物,该方法清洁,对环境友好,但是所需时间过长,时间成本和维护成本过高,不利于实际的废水处理工程应用;有学者利用光化学氧化法对吸附了酚类污染物的有机膨润土进行再生,主要是利用光敏剂(如酞菁铝)嵌入有机膨润土层间,通过光照等方式将污染物氧化。虽然这些方法广为研究,但部分仍存在处理成本昂贵、所使用的再生化学药品对再生时间长、温度控制严格、制备过长复杂等问题,因而探究其他再生方法是大势所趋。
环境响应型表面活性剂是一类根据需要或环境变化动态改变其结构和性能,可以在“开”和“关”状态之间切换的材料,其组织结构含有可以对环境刺激作出巨大响应的功能基团,通过将电、光、热、pH等刺激因素转换成化学、物理化学信号来调节油/水界面附近表面活性剂分子的传输进而改变体系如润湿性等,其中,酸碱刺激响应属于一种比较容易控制的环境因素,通常在酸碱响应的表面活性剂体系中,表面活性剂含有-COOH、-NH2、-OPO3H2等pH刺激响应基团,这些基团能与酸或者碱相互作用,分子的有机聚体状态改变从而使表面活性剂胶束体系发生可逆转变。
环境响应型表面活性剂在许多关键领域都发挥着重要作用,如诊断、生物传感器、药物输送以及智能光学系统等,而利用环境响应型特别是酸碱响应型表面活性剂在环境修复这个大领域中应用不多,在有机膨润土再生技术领域应用更是甚少,这些都是有机膨润土再生研究中所欠缺的地方。为此,本发明研制开发一种可逆有机膨润的制备方法与在工业废水中的应用。
发明内容
本发明在于提供一种本发明针对已知再生技术问题存在的情况下提供了一种可逆有机膨润土及其制备方法与应用,可以利用酸碱响应型表面活性剂对钠基膨润土改性,依据酸碱响应型表面活性剂可逆可控原理,制备一种既能保持吸附性能效果,又能使再生工艺简便的可逆有机膨润土。利用该种可逆有机膨润土对酚类污染物吸附达到饱和后进行解吸,循环吸附-脱附多次后膨润土仍有吸附能力,同时所使用的酸碱响应表面活性剂价格低廉且具有较高的生物降解性,既能降低生产成本和处理成本,也能将其对环境的危害减小。
本发明是这样实现的,所述可逆有机膨润土的制备方法,该方法是以钠基膨润土为原材料,以酸碱响应型表面活性剂为改性剂对其进行改性,要点是钠基膨润土活化完成后加入酸碱表面活性剂,加入盐酸调节混合液的pH值为3.5~6.5之间,使表面活性剂分子插层到层间后自发组装成胶束,形成活性有机聚集体,经搅拌、水洗抽滤去离子后、干燥研磨制得可逆有机膨润土。制得的可逆有机膨润土,可应用于工业废水中酚类有机污染物的处理,要点是将酚类有机污染物与可逆有机膨润土混合在离心管中振荡,当达到吸附饱和之后,将混合液离心后去除上清液,加入同体积的去离子水,加入氢氧化钠调节体系pH在9~10之间,膨润土层间的表面活性剂分子组成的蠕虫胶束变为球形胶束或单分散体,使污染物从膨润土层间最大程度解吸出来,实现再生。
优选的,上述钠基膨润土是经过除杂的150~300目钠基膨润土,活化温度为100~110℃,活化时间为1~1.5h。
优选的,上述选用的酸碱响应型表面活性剂为十二烷基二甲基氧化胺(C12DMAO)、十四烷基二甲基氧化胺(C14DMAO)或长链二甲基叔胺((UC11AMPM)中任一种或多种。
优选的,本发明采用的酸碱响应型表面活性剂的浓度为10~30 wt%,以100g钠基膨润土为基准,用量为钠基膨润土阳离子交换量(CEC)的0.5~1.0倍。
优选的,上述搅拌类型为水浴磁力搅拌,搅拌时间3~6小时,温度为25℃~30℃,抽滤次数为2~4次,干燥温度为50℃~60℃,研磨过150~300目筛。
优选的,上述可逆有机膨润土用量为0.1~0.5g,酚类有机污染物为苯酚、甲酚或二硝基邻甲酚中任一种或多种,浓度范围为10~200mg/L,用量为20~30ml。
优选的,上述振荡温度为25~30℃,振荡时间为2~5h,离心条件为3000~4000rpm,离心时间10~15min。
优选的,所用调节溶液pH的试剂为0.2M的盐酸溶液和0.2M的氢氧化钠溶液。
所述的可逆有机膨润土在工业废水中酚类有机污染物处理中的应用。
优选的,所述的可逆有机膨润土的应用方法,包括以下步骤:
S1、取含酚类有机污染物的工业废水与制得的可逆有机膨润土混合在离心管中,于25~30℃下振荡2~5h,有机污染物浓度范围为10~200mg/L;
S2、当达到吸附饱和之后,将步骤1中的混合液在3000~4000rpm条件下离心10~15min,去除上清液后加入同上清液一样体积的去离子水,加入氢氧化钠调节体系pH在9~10之间,膨润土层间的表面活性剂分子组成的蠕虫胶束变为球形胶束或单分散体,使污染物从膨润土层间最大程度解吸,实现再生。
优选的,所述的含酚类有机污染物的工业废水为20~30ml,所用的可逆有机膨润土为0.1~0.5g;所述酚类有机污染物为苯酚、甲酚或二硝基邻甲酚中任一种或多种;所述的氢氧化钠为0.2M的氢氧化钠。
本发明具有以下有益效果:
(1)本发明与已知的再生技术相比,明显的特点是采用酸碱响应型表面活性剂改性膨润土,通过调节pH使层间污染物释放实现膨润土的可逆再生。在低pH环境下,酸碱响应型表面活性剂分子呈现阳离子性或弱阳离子性,插进膨润土层间域或者通过静电引力作用牢牢附着于膨润土表面,改性后膨润土疏水性增强,与传统的阳离子表面活性剂相比,在相同的表面活性剂负载量下,经过酸碱响应型表面活性剂改性的膨润土层间距更大且表面电荷增加,提高了其对有机污染物的吸附能力;而在溶液pH较高条件下,部分酸碱响应型表面活性剂分子不带电表现出非离子特性,因静电斥力的作用层间距减小,表面电荷减少,其层间表面活性剂胶束被改变,使有机污染物解吸出来,更易于有机膨润土与其层间污染物的分离;
(2)通过调节混合液中的pH值实现有机膨润土处理污染物吸附-脱附可逆循环,使得改性后的膨润土可以重复多次利用,有机膨润土再生成本和处理成本降低。
具体实施方式
为使本发明的目的、技术方案及效果更加清楚,明确,以下列举实例对本发明进一步详细说明。应当指出此处所描述的具体实施仅用以解释本发明,并不用于限定本发明。
实施例1
一种可逆有机膨润土及其制备方法与,该方法是以钠基膨润土为原材料,以酸碱响应型表面活性剂为改性剂对其进行改性,要点是钠基膨润土加入酸碱表面活性剂之后,加入盐酸调节混合液的pH值为3.5~6.5之间,使表面活性剂分子插层到层间后自发组装成胶束,经搅拌、水洗抽滤去离子后、干燥研磨得成品。制得的可逆有机膨润土处理工业废水中酚类有机污染物,要点是酚类有机污染物与可逆有机膨润土混合,达到吸附饱和之后离心去除上清液,加入同体积的去离子水,加入氢氧化钠调节体系pH在9~10之间,膨润土层间的表面活性剂分子组成的蠕虫胶束变为球形胶束或单分散体,使污染物从膨润土层间最大程度解吸出来,实现再生。具体步骤如下:
(1)可逆有机膨润土制备:称取100g钠基膨润土在100℃下活化1h,将0.5CEC、浓度为30wt%的C12DMAO和 1CEC、浓度为30wt%的C12DMAO分别加入到20g活化完成的钠基膨润土中,搅拌将其均匀混合,加入超200毫升去离子水,用0.2M的盐酸溶液将反应体系pH值调至4,然后在25℃下用水浴磁力搅拌器进行搅拌反应,水浴磁力搅拌3小时得到粗制产品;对搅拌完成的膨润土使用真空泵进行抽滤3次,去除多余的表面活性剂,待水分抽干,得到改性完的湿成品;将改性完成的湿成品置于鼓风干燥箱在50℃下烘干,研钵研磨2次,过200目筛即可得成品。
(2)可逆有机膨润土的应用:称取(1)中的可逆有机膨润土成品0.2g,加入20ml浓度为50、100、200mg/L的苯酚溶液,将两者混合振荡2h进行吸附,于3000rpm下离心10min,倒出上清液,加入同体积去离子水,将体系pH调至9.5,振荡2h进行解吸,于3000rpm下离心10min后倒出上清液。两次上清液均经0.45μm滤膜过滤,用紫外分光光度计与270nm处测量吸光度,计算苯酚吸附浓度和解吸率,实验结果表明,循环吸附-解吸4次,可逆有机膨润土尚有吸附能力,其吸附率和解吸率均在82%以上,有良好的吸附和解吸效果。
实施例2
本实施例与实施1的区别仅在于,活化温度为105℃,余同实施1。
实施例3
本实施例与实施1的区别仅在于,活化时间为1.5h,余同实施1。
实施例4
本实施例与实施1的区别仅在于,搅拌时间为5h,余同实施1。
实施例5
本实施例与实施1的区别仅在于,搅拌温度为30℃,余同实施1。
实施例6
本实施例与实施1的区别仅在于,烘干温度为60℃,余同实施1。
实施例7
本实施例与实施1的区别仅在于,可逆有机膨润土用量为0.5g,余同实施1。
实施例8
本实施例与实施1的区别仅在于,酸碱响应型表面活性剂为十四烷基二甲基氧化胺(C14DMAO),余同实施1。
实施例9
本实施例与实施1的区别仅在于,酸碱响应型表面活性剂为长链二甲基叔胺(UC11AMPM),余同实施1。
实施例10
本实施例与实施1的区别仅在于,酚类污染物为甲酚,余同实施1。
实施例11
本实施例与实施1的区别仅在于,酚类污染物为二硝基邻甲酚,余同实施1。
Claims (6)
1.一种可逆有机膨润土,其特征在于,所述的可逆有机膨润土的制备方法包括以下步骤:
S1、将钠基膨润土进行活化,活化温度为100~110℃,活化时间为1~1.5h;
S2、将经过步骤S1活化的钠基膨润土与酸碱响应型表面活性剂混合,加入盐酸调节混合液的pH值在3.5~6.5之间,经过搅拌,水洗抽滤去离子之后进行烘干,研磨过150~300目筛制得可逆有机膨润土;
所述酸碱响应型表面活性剂为十二烷基二甲基氧化胺C12DMAO、十四烷基二甲基氧化胺C14DMAO或长链二甲基叔胺UC11AMPM中任一种或多种;
所述搅拌为水浴磁力搅拌,时间为3~6h,温度为25℃~30℃,抽滤次数为2~4次,烘干温度为50~60℃。
2.根据权利要求1所述的可逆有机膨润土,其特征在于,所述钠基膨润土是经过除杂的150~300目钠基膨润土。
3.一种根据权利要求1-2任一所述的可逆有机膨润土的制备方法,其特征在于,包括以下步骤:
S1、将钠基膨润土进行活化,活化温度为100~110℃,活化时间为1~1.5h;
S2、将经过步骤S1活化的钠基膨润土与酸碱响应型表面活性剂混合,加入盐酸调节混合液的pH值在3.5~6.5之间,经过搅拌,水洗抽滤去离子之后进行烘干,研磨过150~300目筛制得可逆有机膨润土;
所述酸碱响应型表面活性剂为十二烷基二甲基氧化胺C12DMAO、十四烷基二甲基氧化胺C14DMAO或长链二甲基叔胺UC11AMPM中任一种或多种;
所述搅拌为水浴磁力搅拌,时间为3~6h,温度为25℃~30℃,抽滤次数为2~4次,烘干温度为50~60℃。
4.根据权利要求3所述的可逆有机膨润土的制备方法,其特征在于,所述盐酸为0.2M的盐酸。
5.一种根据权利要求1-2任一所述的可逆有机膨润土在工业废水中酚类有机污染物处理中的应用,其特征在于,包括以下步骤:
S1、取含酚类有机污染物的工业废水与所述的可逆有机膨润土混合在离心管中,于25~30℃下振荡2~5h,酚类有机污染物浓度范围为10~200mg/L;
S2、当达到吸附饱和之后,将步骤S1中的混合液在3000~4000rpm条件下离心10~15min,去除上清液后加入同上清液相同体积的去离子水,加入氢氧化钠溶液调节体系pH在9~10之间,膨润土层间的表面活性剂分子组成的蠕虫胶束变为球形胶束或单分散体,使污染物从膨润土层间最大程度解吸,实现再生。
6.根据权利要求5所述的应用,其特征在于,所述的含酚类有机污染物的工业废水为20~30ml,所述的可逆有机膨润土为0.1~0.5g;所述酚类有机污染物为苯酚、甲酚或二硝基邻甲酚中任一种或多种;所述的氢氧化钠溶液为0.2M的氢氧化钠溶液。
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3392048A (en) * | 1965-01-08 | 1968-07-09 | Gen Tire & Rubber Co | Pigment-coated paper products having a binder of protein and a conjugated diene polymer that can form a reversible colloidal solution |
WO1995003999A1 (en) * | 1993-07-30 | 1995-02-09 | University Of Delaware | Selective adsorption of organic material from water by modified clays |
KR20010001794A (ko) * | 1999-06-08 | 2001-01-05 | 김충섭 | 통신케이블 접속부 밀봉형 젤 충전물과 이의 제조방법 |
CN102908985A (zh) * | 2012-11-12 | 2013-02-06 | 湖北中非膨润土有限公司 | 一种膨润土复合多孔材料及其制备方法 |
CN106117859A (zh) * | 2016-08-04 | 2016-11-16 | 陈毅忠 | 一种可瓷化耐火电器开关材料的制备方法 |
-
2022
- 2022-04-24 CN CN202210449981.2A patent/CN114887593B/zh active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3392048A (en) * | 1965-01-08 | 1968-07-09 | Gen Tire & Rubber Co | Pigment-coated paper products having a binder of protein and a conjugated diene polymer that can form a reversible colloidal solution |
WO1995003999A1 (en) * | 1993-07-30 | 1995-02-09 | University Of Delaware | Selective adsorption of organic material from water by modified clays |
KR20010001794A (ko) * | 1999-06-08 | 2001-01-05 | 김충섭 | 통신케이블 접속부 밀봉형 젤 충전물과 이의 제조방법 |
CN102908985A (zh) * | 2012-11-12 | 2013-02-06 | 湖北中非膨润土有限公司 | 一种膨润土复合多孔材料及其制备方法 |
CN106117859A (zh) * | 2016-08-04 | 2016-11-16 | 陈毅忠 | 一种可瓷化耐火电器开关材料的制备方法 |
Non-Patent Citations (3)
Title |
---|
Adsorption behavior of phenol by reversible surfactant-modified montmorillonite: Mechanism, thermodynamics, and regeneration;Yingjie Li,et al.;《Chemical Engineering Journal》;第334卷;第1214-1221页 * |
pH-Tunable wormlike micelles based on an ultra-long-chain ‘‘pseudo’’ gemini surfactant;《Soft Matter》;第11卷(第23期);第4614-4620页 * |
一种氧化胺表面活性剂pH 响应蠕虫状胶束流变行为研究;张萌等;《日用化学工业》;第47卷(第6期);第301-306页 * |
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