CN110102246B - 一种磁性层状双金属氢氧化物吸附剂及其除磷除铬应用 - Google Patents
一种磁性层状双金属氢氧化物吸附剂及其除磷除铬应用 Download PDFInfo
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Abstract
一种磁性层状双金属氢氧化物吸附剂,所述吸附剂为磁性层状双金属氢氧化物MnFe2O4/ZnFe‑LDH。所述吸附剂的制备方法包括,将适量Fe(NO3)3·9H2O和KMnO4溶解于乙二醇中;在磁力搅拌下滴加NH4Ac,搅拌均匀后转移至反应釜中反应;冷却至室温后进行磁分离,将固体沉淀物用去离子水和乙醇洗涤;烘干后获得MnFe2O4;称取适量MnFe2O4于去离子水中;超声得均匀悬浮液;称取适量ZnSO4和FeSO4·7H2O,溶解于蒸馏水中;磁力搅拌,滴加MnFe2O4均匀悬浮液和NaOH溶液;搅拌,向混合溶液中滴加双氧水;抽滤,固体沉淀物洗涤,烘干,研磨。本发明吸附剂用于处理含磷、铬废水,能解决含磷、铬废水对环境的污染问题。
Description
技术领域
本发明涉及一种磁性层状双金属氢氧化物吸附剂及其除磷除铬应用,属环境保护废水处理技术领域。
背景技术
在吸附剂的应用中,吸附剂的回收再利用一直是核心关键,近年来虽然有大量吸附效果很好的纳米吸附剂的报道,但是回收难的问题大大限制了纳米吸附剂的应用。层状双金属氢氧化物(LDH),具有比表面积大、层间阴离子交换能力强、热稳定性好等优点,是一种具有广阔应用前景的吸附材料。铁氧体尖晶石具有热稳定性高、制备简单、耐腐蚀、磁性强等特点,近年来已成为功能材料领域的研究热点之一。在众多铁氧体尖晶石中,MnFe2O4具有较强磁性、吸附活性、化学性质稳定等优点,在低温煅烧或者水热合成下仍可保留磁性,从而可以从水中快速分离,因此在水处理领域得到了广泛的应用。
发明内容
本发明的目的是,为了解决吸附剂的回收再利用的问题,本发明提出一种磁性层状双金属氢氧化物吸附剂及其除磷除铬应用。
本发明实现的技术方案,一种磁性层状双金属氢氧化物吸附剂,所述吸附剂为磁性层状双金属氢氧化物MnFe2O4/ZnFe-LDH。
一种磁性层状双金属氢氧化物吸附剂制备方法,其具体步骤如下:
(1)准确称取4.04g Fe(NO3)3·9H2O和0.79g KMnO4(摩尔比Fe3+/Mn2+=2:1)溶解于80ml乙二醇中;
(2)在300r/min磁力搅拌下缓慢滴加3.854g NH4Ac,搅拌均匀后转移至反应釜中;
(3)200℃下反应12h;
(4)冷却至室温后进行磁分离,将固体沉淀物用去离子水和乙醇洗涤数次;
(5)60℃烘干,获得MnFe2O4;
(6)准确称取0.2g MnFe2O4于100ml去离子水中;
(7)超声120min得均匀悬浮液;
(8)准确称取0.556g ZnSO4和1.7254g FeSO4·7H2O,溶解于30ml蒸馏水中;
(9)使用磁力搅拌器在持续搅拌的条件下,同时缓慢向混合溶液中滴加MnFe2O4均匀悬浮液和1.0mol/L的NaOH溶液,直至混合溶液pH达到7.5;
(10)在300r/min的转速下持续搅拌2小时;
(11)向混合溶液中滴加质量分数为6%的双氧水;
(12)在40℃条件下保存10小时;
(13)抽滤,并将获得的固体沉淀物使用去离子水洗涤至中性;
(14)60℃烘干,将固体沉淀物磁性分离后研磨过100目筛网。
所述Fe(NO3)3·9H2O与KMnO4的摩尔比Zn2+/Fe2+=3:1。
所述ZnSO4与FeSO4·7H2O的摩尔比Zn2+/Fe2+=3:1。
所述吸附剂适用于在pH为4~7的含磷、铬废水中吸附磷、铬。
所述吸附剂在不同浓度阴离子共存的条件下,对吸附磷的影响顺序为CO3 2—>SO4 2—>NO3 —>Cl—。
所述吸附剂在不同浓度阴离子共存的条件下,对吸附Cr(VI)的影响顺序为H2PO4 —>SO4 2—>NO3 —>Cl—。
本发明的有益效果是,本发明制备的磁性层状双金属氢氧化物MnFe2O4/ZnFe-LDH对磷和铬具有很好的吸附效果。将该吸附剂用于处理含磷铬废水,不仅能够很好地解决含磷铬废水对环境的污染问题,还提供了一种易回收吸附剂的制备方法,具有一定的经济效应和环境效应。
具体实施方式
实施例1
用水热法制备MnFe2O4。准确称取4.04g Fe(NO3)3·9H2O和0.79g KMnO4(摩尔比Fe3 +/Mn2+=2:1)溶解于80ml乙二醇中,在磁力搅拌下缓慢滴加3.854g NH4Ac,搅拌均匀后转移至反应釜中,200℃下反应12h,冷却至室温后进行磁分离,将固体沉淀物用去离子水和乙醇洗涤数次,60℃烘干,得目标产物MnFe2O4。
准确称取0.2g MnFe2O4于100ml去离子水中,超声120min得均匀悬浮液。再准确称取0.556g ZnSO4和1.7254g FeSO4·7H2O(摩尔比Zn2+/Fe2+=3:1)溶解于30ml蒸馏水中并持续搅拌,同时缓慢向混合溶液中滴加MnFe2O4均匀悬浮液和1.0mol/L的NaOH溶液,直至混合溶液pH达到7.5左右且基本保持不变,匀速搅拌2h,向混合溶液中滴加质量分数为6%的双氧水,将Fe2+氧化为Fe3+,40℃老化10h,将固体沉淀物磁性分离抽滤洗涤至中性,60℃烘干,研磨过100目得MnFe2O4/ZnFe-LDH。
取浓度为25mg/L的含磷模拟废水50ml放入具塞锥形瓶中,pH调为5,加入MnFe2O4/ZnFe-LDH 0.05g(1g/L),在25℃、180r/min磁力搅拌器中搅拌4h,吸附后上清液用0.22μm的针管滤头过滤,计算出去除率为97.76%,吸附量为48.88mg/g。
实施例2
操作方法同实施例1。
取50mg/L的含磷模拟废水50ml放入具塞锥形瓶中,Cl—、NO3 —、SO4 2—、CO3 2—离子浓度分别为5、50mmol/L,溶液pH调为5,分别加入MnFe2O4/ZnFe-LDH0.05g(1g/L),在25℃、180r/min磁力搅拌器中搅拌4h,吸附后上清液用0.22μm的针管滤头过滤,计算出不同浓度阴离子共存的条件下去除率分别为Cl—:94.2%,96.75%;NO3 —:88.41%,91.82%;SO4 2—:79.28%,88.59%;CO3 2—:91.56%,45.24%。得出共存阴离子对吸附磷的影响顺序为CO3 2—>SO4 2—>NO3 —>Cl—。
实施例3
操作方法同实施例1。
取20mg/L的含Cr(VI)模拟废水50ml于具塞锥形瓶中,pH调为7,加入MnFe2O4/ZnFe-LDH 0.05g(1g/L),在25℃、180r/min磁力搅拌器中搅拌4h,吸附后上清液用0.22μm的针管滤头过滤,计算出去除率为96.87%,吸附量为13.84mg/g。
实施例4
操作方法同实施例1。
取20mg/L的含Cr(VI)模拟废水50ml于具塞锥形瓶中,Cl—、NO3 —、SO4 2—、H2PO4 —浓度分别为2、20mM,溶液pH调为7,分别加入MnFe2O4/ZnFe-LDH 0.07g(1.4g/L),在25℃、180r/min磁力搅拌器中搅拌4h,吸附后上清液用0.22μm的针管滤头过滤,计算出不同浓度阴离子共存的条件下去除率分别为Cl—:94.88%,92.57%;NO3 —:90.79%,89.27%;SO4 2—:82.52%,53.48%;H2PO4 —:52.33%,24.53%。得出共存阴离子对吸附Cr(VI)的影响顺序为H2PO4 —>SO4 2—>NO3 —>Cl—。
Claims (2)
1.一种用于含磷废水中吸附磷的磁性层状双金属氢氧化物吸附剂,其特征在于,所述吸附剂为磁性层状双金属氢氧化物MnFe2O4/ZnFe-LDH;
所述吸附剂制备方法步骤如下:
(1)准确称取4.04g Fe(NO3)3·9H2O和0.79g KMnO4,溶解于80ml乙二醇中;
(2)在300r/min磁力搅拌下缓慢滴加3.854g NH4Ac,搅拌均匀后转移至反应釜中;
(3)200℃下反应12h;
(4)冷却至室温后进行磁分离,将固体沉淀物用去离子水和乙醇洗涤数次;
(5)60℃烘干,获得MnFe2O4;
(6)准确称取0.2g MnFe2O4于100ml去离子水中;
(7)超声120min得均匀悬浮液;
(8)准确称取0.556g ZnSO4和1.7254g FeSO4·7H2O,溶解于30ml蒸馏水中;
(9)使用磁力搅拌器在持续搅拌的条件下,同时缓慢向混合溶液中滴加MnFe2O4均匀悬浮液和1.0mol/L的NaOH溶液,直至混合溶液pH达到7.5;
(10)在300r/min的转速下持续搅拌2小时;
(11)向混合溶液中滴加质量分数为6%的双氧水;
(12)在40℃条件下保存10小时;
(13)抽滤,并将获得的固体沉淀物使用去离子水洗涤至中性;
(14)60℃烘干,将固体沉淀物磁性分离后研磨过100目筛网;
所述吸附剂用于在pH为4~7的含磷废水中吸附磷。
2.根据权利要求1所述的一种用于含磷废水中吸附磷的磁性层状双金属氢氧化物吸附剂,其特征在于,所述吸附剂在不同浓度阴离子共存的条件下,对吸附磷的影响顺序为CO3 2—>SO4 2—>NO3 —>Cl—。
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