CN113501599A - 一种含氟废水的处理方法 - Google Patents
一种含氟废水的处理方法 Download PDFInfo
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- CN113501599A CN113501599A CN202110918549.9A CN202110918549A CN113501599A CN 113501599 A CN113501599 A CN 113501599A CN 202110918549 A CN202110918549 A CN 202110918549A CN 113501599 A CN113501599 A CN 113501599A
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- fluorine
- containing wastewater
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- cryolite
- water
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- 239000011737 fluorine Substances 0.000 title claims abstract description 106
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 106
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- 239000002351 wastewater Substances 0.000 title claims abstract description 79
- 238000000034 method Methods 0.000 title claims abstract description 44
- 239000000243 solution Substances 0.000 claims abstract description 45
- 239000003463 adsorbent Substances 0.000 claims abstract description 27
- 229920001661 Chitosan Polymers 0.000 claims abstract description 22
- 230000010355 oscillation Effects 0.000 claims abstract description 21
- 229910001610 cryolite Inorganic materials 0.000 claims abstract description 19
- 239000000706 filtrate Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 14
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
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- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052901 montmorillonite Inorganic materials 0.000 claims abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims abstract description 6
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- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 9
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 9
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 8
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
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- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 4
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
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- -1 fluorine ions Chemical class 0.000 abstract description 23
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- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 19
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- 239000003651 drinking water Substances 0.000 description 5
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- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical class [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
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- 230000002378 acidificating effect Effects 0.000 description 1
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- JYIBXUUINYLWLR-UHFFFAOYSA-N aluminum;calcium;potassium;silicon;sodium;trihydrate Chemical compound O.O.O.[Na].[Al].[Si].[K].[Ca] JYIBXUUINYLWLR-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
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- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
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Abstract
本发明公开了一种含氟废水的处理方法，步骤为：(1)将壳聚糖溶于酸溶液中，加入由椰壳炭，硅藻土和蒙脱石组成的混合物粉体并搅拌均匀后加入铁盐溶液制得壳聚糖联合铁盐改性的吸附剂；(2)往含氟废水中加入水溶性铝源除氟剂进行超声振荡除氟反应，控制反应过程中含氟废水的pH值，制得含冰晶石的混合液；(3)将含冰晶石混合液过滤回收冰晶石，往所得滤液中加入壳聚糖联合铁盐改性的吸附剂并进行超声振荡，过滤除去改性吸附剂后即可。本发明所提供的含氟废水的处理方法利用常见铝盐混合含氟废水，在室温下以结晶法去除水中氟离子并合成具经济价值的冰晶石，结晶后废液进一步采用吸附法降低氟浓度和杂质含量，从而达到废水回收利用标准。
Description
技术领域
本发明属于废水处理技术领域，尤其是涉及一种含氟废水的处理方法。
背景技术
氟是人体必需的微量元素之一，饮用水适宜的氟质量浓度为0.5～1mg/L(张小磊,何宽,马建华.氟元素对人体健康的影响[J].微量元素与健康研究,2016,23(06):66-67.)。当饮用水中氟含量不足时，易患龋齿病；但若长期饮用氟质量浓度高于1mg/L的水，则会引起氟斑牙病；长期饮用氟质量浓度为3～6mg/L的水会引起氟骨病。我国含氟地下水分布广泛，尤其是在西北干旱地区，约有7000万人饮用含氟量超标的水，导致不同程度的氟中毒。工业上，含氟矿石开采、金属冶炼、铝加工、焦炭、玻璃与陶瓷制造、半导体、电镀、化肥、农药等行业排放的废水中常含有高浓度的氟化物，造成环境污染。因此如何去除水中氟离子、降低氟污染是氟相关行业必须解决的问题之一(程秀绵.含氟废水处理工艺的技术改进[J].工业水处理,2007,6:84-86.)。
目前常见的含氟废水处理方法包含混凝沉淀法、吸附法、电化学法、膜法等，对于含氟废水处理方式目前大多使用钙盐混凝的方式，即向废水中投加石灰，使氟离子与钙离子生成CaF2沉淀而除去(郑丹阳,耿存珍.水体除氟方法的最新研究进展[J].环境科学与管理,2014,39(11):31-34.；Wu L,Forsling W.Surface Complexation of CalciumMinerals in Aqueous Solution:III.Ion Exchange and Acid-Base Properties ofHydrous Fluorite Surfaces[J].Journal of Colloid and Interface Science,2015,174(1):178-184.)。氟化钙在18℃时于水中的溶解度为16.3mg/L，按氟离子计为7.9mg/L，在此溶解度的氟化钙会形成沉淀物。氟的残留量为10～20mg/L时形成沉淀物的速度会减慢。该工艺具有方法简单、处理方便、费用低等优点，但存在处理后出水很难达标、泥渣沉降缓慢且脱水困难等缺点。同时此方法易产生大量的污泥，再加上产生的CaF2颗粒细小不易沉淀，在处理过程中通常需另外添加其他混凝剂促使CaF2沉淀，进而提高成本，且产物杂质含量高导致商业价值低、不易再利用。虽然有研究报道以电化学法、反渗透膜法可有效去除含氟废水中的氟化物，但处理过程耗能大、维护成本高、前处理技术水质要求严格，处理量小性价比低。用于除氟的常用吸附剂主要有活性氧化铝、斜发沸石、活性氧化镁，近年来还报道了氟吸附容量较高的羟基磷灰石、氧化锆等。利用这些吸附剂可将氟浓度为10mg/L的废水处理到1mg/L以下，达到饮用水的标准。通常作为低浓度含氟废水的深度处理。吸附法一般将吸附剂装入填充柱，采用动态吸附方式进行，操作简便，除氟效果稳定，但存在吸附容量低、频繁再生问题。
发明内容
本发明的目的在于提供一种含氟废水的处理方法。
为了达成上述目的，本发明的解决方案是：
一种含氟废水的处理方法，包括如下步聚：
(1)将壳聚糖溶于酸溶液中，加入由椰壳炭，硅藻土和蒙脱石组成的混合物粉体并搅拌均匀，然后加入铁盐溶液，调节溶液pH值，将所得混合物继续浸泡后过滤，用水洗涤所得固体，将所得固体烘干即可制得羧基化壳聚糖联合铁盐改性的吸附剂；
(2)往含氟废水中加入水溶性铝源除氟剂进行超声振荡除氟反应，控制反应过程中含氟废水的pH值，制得含冰晶石的混合液；
(3)将步骤(2)中制得的含冰晶石混合液过滤回收冰晶石，然后往所得滤液中加入步骤(1)制备的壳聚糖联合铁盐改性的吸附剂并进行超声振荡，过滤去改性吸附剂后即可。
进一步地，步骤(1)中所述的酸溶液为乙酸溶液。
进一步地，步骤(1)中所述的溶液pH值为5-6。
进一步地，步骤(1)中所述的铁盐为硫酸铁、氯化铁或硝酸铁中的一种或多种组合而成。
进一步地，步骤(2)中所述的水溶性铝源除氟剂由偏铝酸钠、硫酸铝或氯化铝中的一种或多种组合而成。
进一步地，步骤(2)中所述的超声振荡除氟反应的温度为0-40℃，超声振荡的时间为5-30min。
进一步地，步骤(2)中所述的含氟废水的pH值为5-7。
进一步地，步骤(2)中所述水溶性铝源除氟剂的用量为200-20000mg/L废水。
进一步地，步骤(3)中所述的超声振荡温度为0-40℃，超声振荡的时间为5-30min。
进一步地，步骤(3)中所述的壳聚糖联合硫酸铁改性的吸附剂的用量为50-10000mg/L废水。
相对于现有的含氟废水的处理方法，本发明的原理和增益效果如下：
1.本发明所提供的含氟废水的处理方法利用常见铝盐混合含氟废水，在室温下以结晶法去除水中氟离子并合成具经济价值的冰晶石，结晶后废液进一步采用吸附法降低氟浓度和杂质含量，达到废水回收利用标准，以解决含氟废水污染问题且达到资源再利用的目标。
2.本发明所提供的含氟废水的处理方法通过羧基改性的壳聚糖和三价铁盐联合对由椰壳炭，硅藻土和蒙脱石组成的复合吸附剂进行改性，所提供的改性吸附剂是一种具有耐酸性、高机械强度及强吸附除氟性能的新型除氟吸附剂。具体的吸附原理如下：壳聚糖分子中存在的大量质子化的羟基和氨基可通过静电吸引氟离子、重金属及染料等污染物质，但未改性的壳聚糖由于吸附容量低、易流失等缺点不适宜直接作为水体中除氟吸附剂，因此使用羧酸对其进行改性；然后利用三价铁离子和由椰壳炭，硅藻土和蒙脱石组成的复合吸附剂与羧基化的壳聚糖联合反应合成新的复合除氟剂，其中，在复合吸附剂中椰壳炭和硅藻土作为传统污水处理吸附剂主要利用其吸附效率高且价格便宜的优点，而蒙脱石是由颗粒极细的含水铝硅酸盐构成的层状矿物，蒙脱石所含的铝硅酸盐可对废水中的氟离子进行吸附、离子交换及络合沉降从而有效降低废水中氟离子的浓度使其达到排放标准。
3.本发明所提供的含氟废水的处理方法创造性地采用了超声处理，可以明显缩短加了水溶性铝源除氟剂的含氟废水溶液的结晶时间；这主要是利用了超声处理的空化效应以及超声空化产生的局部高温和高压产生结晶核，从而进一步加速促进冰晶石晶体的生成，因此极大地提高了含氟废水的处理效率。此外，在对回收了冰晶石的滤液加吸附剂进一步物理吸附除氟的过程中，超声处理也可以明显缩短吸附时间。
4.本发明所提供的含氟废水的处理方法还具有工艺简单、条件温和、重复性好以及利于工业化推广等优点，为工业含氟废水的处理提供了一种新方法，开拓了新思路。
具体实施方式
下面进一步结合实施例以详细说明本发明。同样应理解，以下实施例只用于对本发明进行进一步说明，不能理解为对本发明保护范围的限制，示例中具体的质量、反应时间和温度、工艺参数等也仅是合适范围中的一个示例，本领域的技术人员根据本发明的上述内容做出的一些非本质的改进和调整均属于本发明的保护范围。
所用试剂如无特别指出均为商品化试剂，使用前均未进行进一步纯化。
本发明实施例部分所使用超声波发生器为昆山舒美超声波发生器KQ250DA(功率在0-350w可调)。
本发明实施例部分所使用的含氟废水为使用分析纯的氢氟酸配制含氟浓度为2000mg/L的溶液来模拟工业含氟废水，这是因为工业生产过程中排放的含氟废水以酸性为主。
本发明实施例部分氟离子浓度的测定根据中华人民共和国国家标准GB7484—87《水质氟化物的测定：离子选择电极法》进行测定。
实施例1：
含氟废水的处理步聚如下：
(1)将3g壳聚糖溶于250mL的9％乙酸溶液，搅拌反应2h，加入由0.6g椰壳炭，3.0g椰壳炭和3g蒙皂石组成的混合物粉体，继续搅拌1h，然后加入质量浓度为25g/L的氯化铁溶液200mL，用NaOH调节溶液pH至5.0，浸泡2h，过滤后将所得固体用去离子水洗涤至收集的洗脱液pH值接近7，将洗涤后的固体在110℃烘干制备得到氯化铁联合羧酸化的壳聚糖改性吸附剂；
(2)往500ml氟离子浓度为2000mg/L的废水中加入330ml偏铝酸钠(1000mg/L)组成的水溶液和158ml氢氧化钠(1000mg/L)，将所得混合物溶液移入至超声反应器中在25℃超声振荡(功率50w)20min除氟反应，控制反应过程中含氟废水的pH值为5，超声振荡一开始就能立即观察到废水溶液开始产生沉淀变混浊，随着除氟反应的进行可以观察到废水溶液中的沉淀不断长大并逐渐砂状化，这是因为加入的偏铝酸钠和氢氧化钠与废水中的氟离子反应生成了冰晶石，这样就可制得含冰晶石的混合液，取样测量此时含氟废水溶液中的氟离子浓度，结果氟离子浓度已经降至361mg/L；
(3)将步骤(2)中制得的含冰晶石混合液过滤回收冰晶石，然后往所得滤液中加入步骤(1)制备的壳聚糖联合铁盐改性的吸附剂后将滤液并移入至超声反应器中在25℃超声振荡，取样测量滤液中的氟离子浓度，13min后滤液中的氟离子浓度降至10mg/L以下，停止超声振荡，过滤除去吸附剂后即得到氟离子浓度达到排放标准的含氟废水溶液。将回收的冰晶石烘干后称量一共制得冰晶石691mg。
实施例2：
含氟废水的处理步聚参考实施例1，不同之处在于将步骤(1)中的氯化铁溶液换成硝酸铁溶液(25g/L)，硝酸铁溶液的用量为298ml，其余步骤均同实施例1；步骤(2)结束后含氟废水溶液中的氟离子浓度为365mg/L，步骤(3)中需要16min后滤液中的氟离子浓度才能降至10mg/L以下。
实施例3：
含氟废水的处理步聚参考实施例1，不同之处在于将步骤(2)中的偏铝酸钠溶液换成硫酸铝(1000mg/L)溶液，硫酸铝溶液的用量为1361ml，其余步骤均同实施例1；步骤(2)结束后含氟废水溶液中的氟离子浓度为411mg/L，步骤(3)中需要34min后滤液中的氟离子浓度才能降至10mg/L以下。
实施例4：
含氟废水的处理步聚参考实施例1，不同之处在于将步骤(2)中的偏铝酸钠溶液换成氯化铝(1000mg/L)溶液，氯化铝溶液的用量为530ml，其余步骤均同实施例1；步骤(2)结束后含氟废水溶液中的氟离子浓度为387mg/L，步骤(3)中需要19min后滤液中的氟离子浓度才能降至10mg/L以下。
实施例5：
含氟废水的处理步聚参考实施例1，不同之处在于将步骤(2)中的除氟反应温度调整为0℃，超声振荡的时间调整为45min；步骤(3)中的反应温度调整为0℃，其余步骤均同实施例1；步骤(2)结束后含氟废水溶液中的氟离子浓度为376mg/L，步骤(3)中需要40min后滤液中的氟离子浓度才能降至10mg/L以下。
实施例6：
含氟废水的处理步聚参考实施例1，不同之处在于将步骤(2)中反应过程中含氟废水的pH值为6，其余步骤均同实施例1；步骤(2)结束后含氟废水溶液中的氟离子浓度为369mg/L，步骤(3)中需要17min后滤液中的氟离子浓度才能降至10mg/L以下。
对比例1：
含氟废水的处理步聚参考实施例1，不同之处在于将步骤(2)中在25℃超声振荡20min除氟反应调整为在25℃磁力搅拌2h除氟反应，其余步骤均同实施例1；步骤(2)结束后含氟废水溶液中的氟离子浓度为370mg/L，步骤(3)中需要18min后滤液中的氟离子浓度才能降至10mg/L以下。
对比例2：
含氟废水的处理步聚参考实施例1，不同之处在于将步骤(3)中在25℃超声振荡调整为在25℃磁力搅拌，其余步骤均同实施例1；步骤(2)结束后含氟废水溶液中的氟离子浓度为366mg/L，步骤(3)中需要1小时12分钟后滤液中的氟离子浓度才能降至10mg/L以下。
对比例3：
含氟废水的处理步聚参考实施例1，不同之处在于将步骤(1)调整为：将由0.6g椰壳炭，3.0g椰壳炭和3g蒙皂石组成的混合物粉体加入到200mL质量浓度为25g/L的氯化铁溶液中，用NaOH调节溶液pH至5.0，所得混合物搅拌均匀后浸泡2h，过滤后将所得固体用去离子水洗涤至收集的洗脱液pH值接近7，将洗涤后的固体在110℃烘干制备得到氯化铁改性的吸附剂；其余步骤均同实施例1；步骤(2)结束后含氟废水溶液中的氟离子浓度为365mg/L，步骤(3)中需要42min后滤液中的氟离子浓度才能降至10mg/L以下。
对比例4：
含氟废水的处理步聚参考实施例1，不同之处在于将步骤(1)调整为：将由3g壳聚糖，0.6g椰壳炭，3.0g椰壳炭和3g蒙皂石组成的混合物粉体，继续搅拌1h，然后加入质量浓度为25g/L的氯化铁溶液200mL，用NaOH调节溶液pH至5.0，所得混合物搅拌均匀后浸泡2h，过滤后将所得固体用去离子水洗涤至收集的洗脱液pH值接近7，将洗涤后的固体在110℃烘干制备得到氯化铁和壳聚糖联合改性吸附剂；其余步骤均同实施例1；步骤(2)结束后含氟废水溶液中的氟离子浓度为367mg/L，步骤(3)中需要37min后滤液中的氟离子浓度才能降至10mg/L以下。
对比例5：
含氟废水的处理步聚参考实施例1，不同之处在于将步骤(3)中的氯化铁联合羧酸化的壳聚糖换为普通市售活性炭，其余步骤均同实施例1；步骤(2)结束后含氟废水溶液中的氟离子浓度为366mg/L，步骤(3)中需要2小时21分钟后滤液中的氟离子浓度才能降至10mg/L以下。
Claims (10)
1.一种含氟废水的处理方法，其特征在于，包括如下步聚：
(1)将壳聚糖溶于酸溶液中，加入由椰壳炭，硅藻土和蒙脱石组成的混合物粉体并搅拌均匀，然后加入铁盐溶液，调节溶液pH值，将所得混合物继续浸泡后过滤，用水洗涤所得固体，将所得固体烘干即可制得羧基化壳聚糖联合铁盐改性的吸附剂；
(2)往含氟废水中加入水溶性铝源除氟剂进行超声振荡除氟反应，控制反应过程中含氟废水的pH值，制得含冰晶石的混合液；
(3)将步骤(2)中制得的含冰晶石混合液过滤回收冰晶石，然后往所得滤液中加入步骤(1)制备的壳聚糖联合铁盐改性的吸附剂并进行超声振荡，过滤去改性吸附剂后即可。
2.根据权利要求1所述的含氟废水的处理方法，其特征在于，步骤(1)中所述的酸溶液为乙酸溶液。
3.根据权利要求1所述的含氟废水的处理方法，其特征在于，步骤(1)中所述的溶液pH值为5-6。
4.根据权利要求1所述的含氟废水的处理方法，其特征在于，步骤(1)中所述的铁盐为硫酸铁、氯化铁或硝酸铁中的一种或多种组合而成。
5.根据权利要求1所述的含氟废水的处理方法，其特征在于，步骤(2)中所述的水溶性铝源除氟剂由偏铝酸钠、硫酸铝或氯化铝中的一种或多种组合而成。
6.根据权利要求1所述的含氟废水的处理方法，其特征在于，步骤(2)中所述的超声振荡除氟反应的温度为0-40℃，超声振荡的时间为5-30min。
7.根据权利要求1所述的含氟废水的处理方法，其特征在于，步骤(2)中所述的含氟废水的pH值为5-7。
8.根据权利要求1所述的含氟废水的处理方法，其特征在于，步骤(2)中所述水溶性铝源除氟剂的用量为200-20000mg/L废水。
9.根据权利要求1所述的含氟废水的处理方法，其特征在于，步骤(3)中所述的超声振荡温度为0-40℃，超声振荡的时间为5-30min。
10.根据权利要求1所述的含氟废水的处理方法，其特征在于，步骤(3)中所述水的羧基化壳聚糖联合铁盐改性的吸附剂的用量为50-10000mg/L废水。
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