CN110127892A - 一种含全氟辛酸废水的处理方法 - Google Patents
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Classifications
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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
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- C07C53/15—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen containing halogen
- C07C53/19—Acids containing three or more carbon atoms
- C07C53/21—Acids containing three or more carbon atoms containing fluorine
-
- 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
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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
- C02F1/26—Treatment of water, waste water, or sewage by extraction
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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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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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
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
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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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/04—Surfactants, used as part of a formulation or alone
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- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Extraction Or Liquid Replacement (AREA)
- Physical Water Treatments (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了一种含全氟辛酸废水的处理方法，包括：(1)将含全氟辛酸废水的pH值调节至6～10；(2)向步骤(1)得到的溶液中加入阳离子表面活性剂溶液，充分混合；(3)向步骤(2)得到的溶液中加入有机溶剂萃取2～5分钟，静止分层，分离萃取液，得到经处理后的废水。本发明具有工艺简单，处理效果好，成本低，绿色环保，适合工业化应用的优点。
Description
技术领域
本发明涉及废水处理技术，具体涉及一种含全氟辛酸废水的处理方法。
背景技术
含氟高分子生产中，因氟单体的特殊性质，难以在水中分散，一般用全氟辛酸铵作为分散剂，氟单体在水中或在水表面进行聚合，反应完成后全氟辛酸盐大部分留在水体中而形成废水。年产量千吨的PTFE生产企业，其含全氟辛酸废水排放量达1万立方米，全氟辛酸排放总量达0.6吨。
全氟辛酸是一种理化性质稳定并具有广泛应用的人工合成化学物质，研究表明，全氟辛酸LD50＞500kg/kg，急性中毒表现为颜面潮红，粘膜分泌物增多，产生功能性障碍，角膜混浊等表现，低剂量暴露可引起包括肝脏毒性、免疫毒性以及发育毒性等多种毒性效应，其中最为典型的效应是引起肝脏肿大以及脂类代谢紊乱，有中等毒性的肝致癌性，研究表明，全氟辛酸可改变心肌细胞表面动作电位及钙离子通道，引起心肌损伤，也可致甲状腺激素水平降低，引起甲状腺异常，造成易疲劳、头发脱落，大脑发育迟缓、听力受损等健康危害。
全氟辛酸类化合物具有难降解性、生物蓄积性和沿食物链在生物体内富集的作用，在环境中微生物不能降解，是持久性有机污染物，全氟辛酸类化合物潜在的健康效应引起了国际社会的普遍关注，发达国家已经列入禁排、禁用目录。
由于全氟辛酸中C-F键异常牢固，难以用一般的氧化、光降解等方法把C-F键破坏，多数采用回收法把全氟辛酸从工业废水中回收再利用，目前，主要有膜分离法、泡沫分离法、树脂吸附法、金属盐沉淀法、蒸馏浓缩法等。
如中国专利公开号CN107162250A提供了一种全氟辛酸铵废水处理方法。将清澈透明的含全氟辛酸铵废水泵入泡沫分离塔进行泡沫分离，将废水塔顶泡沫消泡后得到高浓度全氟辛酸铵水溶液，可再利用；塔底得到浓度较低的全氟辛酸铵水溶液；将泡沫分离塔塔底排出的全氟辛酸铵水溶液用第一级纳滤膜进行过滤，浓缩纳滤截留液，返回到泡沫分离塔再进行泡沫分离；第一级纳滤膜的透过液进入第二级纳滤膜；第二级纳滤膜的透过液达到了国家废水排放标准排出；第二级纳滤膜的浓缩液再返回到第一级纳滤膜；完成了废水的有用物的回收利用和废水的清洁处理。
如中国专利公开号CN 103406009 A公开了一种从含氟聚合物生产尾气中回收全氟辛酸的方法及装置。采用吸收塔利用吸收液对含有全氟辛酸蒸汽的尾气进行吸收，吸收全氟辛酸后的吸收液采用纳滤膜或反渗透膜浓缩其中的全氟辛酸盐，透过膜的吸收液返回至吸收工艺中重复利用，膜浓缩得到的全氟辛酸盐浓缩液进行后续酸化、精馏，回收全氟辛酸。
如中国专利公开号CN 103991948A公开了一种改性分子筛为催化剂处理含低浓度全氟辛酸铵废水的方法，改性分子筛的制备：配制含有硝酸铈、硝酸铅、硝酸锰或硝酸铁的混合溶液，将分子筛浸渍于混合溶液中，取出干燥、焙烧；臭氧催化氧化：将得到的改性分子筛和含全氟辛酸铵的废水倒入容器中，通入臭氧，同时开动搅拌30～120分钟；改性分子筛的回收：经过臭氧催化氧化得到混浊溶液，通过静置、离心或者过滤，将改性分子筛从溶液中分离出来。
如中国专利公开号CN 1935771A公开了一种聚四氟乙烯分散树脂生产废水中全氟辛酸铵的处理方法，属于聚四氟乙烯生产废水处理技术领域。该方法包括采用沉淀法对废水进行处理，以二价金属盐为沉淀剂、三价金属盐为絮凝剂，采用不同金属离子不同比例对废水处理，可使处理后的清液中全氟辛酸铵的浓度在10mg/L以下。
由于工业废水成分复杂，废水中胶粒对膜和树脂的空隙会堵塞，需要对废水进行预处理，充分消除悬浮物，否则会严重降低分离效果；泡沫分离法有处理量和能力的限制，应用较少；沉淀法有实验室的报道。因此，目前含全氟辛酸废水的处理技术由于涉及投资回报率、工艺技术难度、运行管理费用等多方面的因素，还有待深入研究，低成本、工艺简单的处理技术有待开发应用。
发明内容
本发明目的在于针对现有技术所存在的不足而提供一种工艺简单，效率高，成本低、绿色环保的含全氟辛酸废水的处理方法。
为解决上述技术问题，本发明采用的技术方案为：一种含全氟辛酸废水的处理方法，包括以下步骤：
(1)将含全氟辛酸废水的pH值调节至6～10；
(2)向步骤(1)得到的溶液中加入阳离子表面活性剂溶液，充分混合；
(3)向步骤(2)得到的溶液中加入有机溶剂萃取2～5分钟，静止分层，分离萃取液，得到经处理后的废水。
作为本发明的优选实施方式，所述阳离子表面活性剂优选为氯化十二烷基二甲基苄基铵、溴化十六烷基三甲基氯化铵、十六烷基二甲基苄基氯化铵、十二烷基三甲基氯化铵和十六烷基三甲基氯化铵中的一种。
作为本发明的优选实施方式，所述有机溶剂优选为二氯甲烷、三氯甲烷和二甲苯中的一种。
作为本发明的优选实施方式，所述阳离子表面活性剂溶液的浓度优选为1～10wt％。
(wt％质量百分含量)
作为本发明的优选实施方式，所述阳离子表面活性剂与含全氟辛酸废水中全氟辛酸的质量比优选为10～40:1。
作为本发明的优选实施方式，所述有机溶剂与含全氟辛酸废水的体积比优选为1:5～20。
作为本发明的优选实施方式，可将分离得到的萃取液蒸发浓缩得到全氟辛酸盐和有机溶剂。
目前，含全氟辛酸废水的成分复杂，废水的pH值也不尽相同，或为酸性，或为碱性。因此，本发明中根据含全氟辛酸废水的不同的pH值，用无机酸溶液或无机碱溶液调节pH值至6～10，所述无机酸优选为盐酸，所述无机碱优选为氢氧化钠。
由于采用了上述技术方案，本发明具有以下有益效果：
1、工艺简单，成本低，本发明所用原料易得，投资少，对设备要求低，操作简单，显著简化了工艺。
2、效率高，处理后废水中残余全氟辛酸含量可低至2ppm以下，完全达到国家规定10ppm的排放指标的要求。
3、绿色环保，将分离得到的萃取液浓缩得到全氟辛酸盐和有机溶剂，全氟辛酸盐可进一步精制回收全氟辛酸，有机溶剂可回收重复使用，有效减少了三废排放。
4、应用范围广，本发明对处理类似化合物具有通用性，有很好的经济和环保效益，易于工业化应用。
具体实施方式
以下通过实施例对本发明进行进一步详细说明，但本发明并不仅限于所述的实施例。
实施例1
在500毫升的梨型分液漏斗中加入全氟辛酸含量为50ppm的废水300毫升，用10wt％的盐酸调节废水pH至7，加入1wt％的十六烷基三甲基氯化铵水溶液，加入的十六烷基三甲基氯化铵与废水中全氟辛酸的质量比为10:1，盖上塞子，震荡5分钟，摇匀使充分混合，打开塞子，加入三氯甲烷20毫升，盖上塞子，震荡萃取2分钟，静止分层，将萃取液放入试剂瓶中，得到经处理后的废水。将分离得到的萃取液蒸馏浓缩，得到全氟辛酸盐和三氯甲烷，回收的三氯甲烷可反复多次使用。检测处理后的废水，全氟辛酸含量为2ppm。
实施例2
在500毫升的梨型分液漏斗中加入全氟辛酸含量为100ppm的废水300毫升，用10wt％的氢氧化钠水溶液调节废水pH至8，加入2wt％的氯化十二烷基二甲基苄基铵水溶液，加入的氯化十二烷基二甲基苄基铵与废水中全氟辛酸的质量比为20:1，盖上塞子，震荡10分钟，摇匀使充分混合，打开塞子，加入二氯甲烷30毫升，盖上塞子，震荡萃取3分钟，静止分层，将萃取液放入试剂瓶中，得到经处理后的废水。将分离得到的萃取液蒸馏浓缩，得到全氟辛酸盐和二氯甲烷，回收的二氯甲烷可反复多次使用。检测处理后的废水，全氟辛酸含量为1.5ppm。
实施例3
在500毫升的梨型分液漏斗中加入全氟辛酸含量为200ppm的废水300毫升，用10wt％的盐酸调节废水pH至6，加入5wt％的氯化十二烷基二甲基苄基铵水溶液，加入的氯化十二烷基二甲基苄基铵与废水中全氟辛酸的质量比为30:1，盖上塞子，震荡15分钟，摇匀使充分混合，打开塞子，加入二甲苯40毫升，盖上塞子，震荡萃取4分钟，静止分层，将萃取液放入试剂瓶中，得到经处理后的废水。将分离得到的萃取液蒸馏浓缩，得到全氟辛酸盐和二甲苯，回收的二甲苯可反复多次使用。检测处理后的废水，全氟辛酸含量为1.8ppm。
实施例4
在500毫升的梨型分液漏斗中加入全氟辛酸含量为451ppm的废水300毫升，用10wt％的氢氧化钠水溶液调节废水pH至9，加入8wt％的十六烷基二甲基苄基氯化铵水溶液，加入的十六烷基二甲基苄基氯化铵与废水中全氟辛酸的质量比为40:1，盖上塞子，震荡7分钟，摇匀使充分混合，打开塞子，加入三氯甲烷50毫升，盖上塞子，震荡萃取5分钟，静止分层，将萃取液放入试剂瓶中，得到经处理后的废水。将分离得到的萃取液蒸馏浓缩，得到全氟辛酸盐和三氯甲烷，回收的三氯甲烷可反复多次使用。检测处理后的废水，全氟辛酸含量为2ppm。
实施例5
在500毫升的梨型分液漏斗中加入全氟辛酸含量为500ppm的废水300毫升，用10wt％的氢氧化钠水溶液调节废水pH至10，加入10wt％的十二烷基三甲基氯化铵水溶液，加入的十二烷基三甲基氯化铵与废水中全氟辛酸的质量比为25:1，盖上塞子，震荡5分钟，摇匀使充分混合，打开塞子，加入三氯甲烷50毫升，盖上塞子，震荡萃取3分钟，静止分层，将萃取液放入试剂瓶中，得到经处理后的废水。将分离得到的萃取液蒸馏浓缩，得到全氟辛酸盐和三氯甲烷，回收的三氯甲烷可反复多次使用。检测处理后的废水，全氟辛酸含量为2ppm。
Claims (7)
1.一种含全氟辛酸废水的处理方法，其特征在于，包括以下步骤：
(1)将含全氟辛酸废水的pH值调节至6～10；
(2)向步骤(1)得到的溶液中加入阳离子表面活性剂溶液，充分混合；
(3)向步骤(2)得到的溶液中加入有机溶剂萃取2～5分钟，静止分层，分离萃取液，得到经处理后的废水。
2.根据权利要求1所述的含全氟辛酸废水的处理方法，其特征在于，所述阳离子表面活性剂为氯化十二烷基二甲基苄基铵、溴化十六烷基三甲基氯化铵、十六烷基二甲基苄基氯化铵、十二烷基三甲基氯化铵和十六烷基三甲基氯化铵中的一种。
3.根据权利要求1所述的含全氟辛酸废水的处理方法，其特征在于，所述有机溶剂为二氯甲烷、三氯甲烷和二甲苯中的一种。
4.根据权利要求1所述的含全氟辛酸废水的处理方法，其特征在于，所述阳离子表面活性剂溶液的浓度为1～10wt％。
5.根据权利要求1所述的含全氟辛酸废水的处理方法，其特征在于，所述阳离子表面活性剂与含全氟辛酸废水中全氟辛酸的质量比为10～40:1。
6.根据权利要求1所述的含全氟辛酸废水的处理方法，其特征在于，所述有机溶剂与含全氟辛酸废水的体积比为1:5～20。
7.根据权利要求1所述的含全氟辛酸废水的处理方法，其特征在于，将分离得到的萃取液蒸发浓缩得到全氟辛酸盐和有机溶剂。
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