CN104591459B - 一种钠皂化废水酸碱资源化处理工艺 - Google Patents
一种钠皂化废水酸碱资源化处理工艺 Download PDFInfo
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- CN104591459B CN104591459B CN201410835884.2A CN201410835884A CN104591459B CN 104591459 B CN104591459 B CN 104591459B CN 201410835884 A CN201410835884 A CN 201410835884A CN 104591459 B CN104591459 B CN 104591459B
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- water
- electrodialysis
- waste
- sedimentation tank
- tank
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- 238000000034 methods Methods 0.000 title claims abstract description 52
- 239000002351 wastewater Substances 0.000 title claims abstract description 39
- BVKZGUZCCUSVTD-UHFFFAOYSA-N Carbonic acid Chemical compound 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OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 239000002253 acids Substances 0.000 title claims abstract description 15
- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 14
- 239000011734 sodium Substances 0.000 title claims abstract description 14
- 238000007127 saponification reactions Methods 0.000 title claims abstract description 13
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound 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[Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 238000004064 recycling Methods 0.000 title claims abstract description 7
- 239000011780 sodium chloride Substances 0.000 claims abstract description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Chemical compound data:image/svg+xml;base64,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 data:image/svg+xml;base64,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 [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 9
- 229910001390 sodium chloride Inorganic materials 0.000 claims abstract description 9
- 150000007516 brønsted-lowry acids Chemical class 0.000 claims abstract description 3
- 150000007528 brønsted-lowry bases Chemical class 0.000 claims abstract description 3
- 239000011901 water Substances 0.000 claims description 39
- 238000000909 electrodialysis Methods 0.000 claims description 25
- 239000003921 oils Substances 0.000 claims description 21
- 238000004062 sedimentation Methods 0.000 claims description 17
- 238000001728 nano-filtration Methods 0.000 claims description 16
- 239000011499 joint compounds Substances 0.000 claims description 9
- 230000001105 regulatory Effects 0.000 claims description 9
- 238000000108 ultra-filtration Methods 0.000 claims description 9
- 229910001385 heavy metals Inorganic materials 0.000 claims description 7
- 239000000463 materials Substances 0.000 claims description 7
- 229910052751 metals Inorganic materials 0.000 claims description 7
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- 239000000920 calcium hydroxide Substances 0.000 claims description 6
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 6
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- 229920002981 polyvinylidene fluorides Polymers 0.000 claims description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Chemical compound 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[Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 3
- 239000011649 sodium carbonate Substances 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 239000000953 sodium hydroxide Substances 0.000 claims description 3
- 229910001856 sodium hydroxide Inorganic materials 0.000 claims description 3
- 239000000243 solutions Substances 0.000 claims description 3
- 239000012267 brine Substances 0.000 claims description 2
- 239000005416 organic matter Substances 0.000 claims description 2
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Abstract
本发明涉及一种稀土分离生产工艺中排放的钠皂化废水酸碱资源化处理工艺，主要包括废水的预处理、膜法处理、酸碱回收工艺三个步骤。本发明工艺能够将氯化钠含量较高的钠皂化废水生产稀土分离工艺过程中所需要的酸和碱，有效的实现了废水经处理后达到零排放与酸碱资源化的目的。
Description
技术领域
[0001] 本发明属于废水处理领域，具体涉及一种实现稀土分离工业钠皂化废水零排放及 酸碱资源化处理工艺。
背景技术
[0002] 稀土是中国最丰富的战略资源，是信息技术、生物技术、能源技术等高技术领域和 国防建设的重要基础材料，同时也对改造某些传统产业，如农业、化工、建材等起着重要作 用。然而，我国在长期稀土开采冶炼过程中累积的污染问题对生态环境和人民健康构成了 严重威胁。我国在2011年制定的《稀土工业污染物排放标准》中的规定值标准门槛较高，部 分规定甚至超过了西方国家的污染物排放标准。因此，对于稀土工业废水的处理技术研究 迫在眉睫，尤其是对于其废水零排放技术及资源循环回用技术的研究并且实现工业化具有 非常重要的实际意义，是我国稀土工业可持续发展的坚实基础。
[0003]稀土分离生产中萃取分离工序所排的钠皂化废水，是稀土湿法分离产生的一类工 艺废水，它由有机酸(油类）、工业液碱及氯化稀土料液先后混合反应产生的残液(水相）。
[0004] 钠皂化废水的主要特征为：
[0005] (1)废水中残留少量的油相；
[0006] (2)氯化钠含量高，可达到17%-20%浓度；
[0007] (3)其成分复杂，含有残留的多种稀土元素及〇8、1%、1(、211、附、？13等多种金属及重 金属元素；
[0008] (4)含有放射性。
[0009] 钠皂化废水处理方面，低水平处理工艺较多，有采用简单处理后再进行蒸发处理 的工艺，这种处理浪费能源较多，运行成本较高。
[0010] 近年来，一些新型的污水处理工艺已经广泛应用，结合传统与新型的工艺处理技 术，将稀土工业废水实现零排放及资源循环回用是其处理工艺的发展方向。
发明内容
[0011] 本发明的目的在于解决现有技术问题，提供一种稀土分离生产中排放的钠皂化废 水酸碱资源化处理工艺。本发明采用了以下方案：
[0012] -种钠皂化废水酸碱资源化处理工艺，包括以下处理步骤：
[0013] (1)将钠皂化废水排放至隔油调节池中停留4小时以上，用于去除残留在废水中的 浮油，以降低废水有机物含量，浮油从集油管中排放至储油槽中；
[0014] (2 )隔油调节池出水进入沉淀池 I中，加入浓度为1 -3%的氢氧化|丐，调节pH值为 8.5-9，用于除去废水中的部分重金属及放射性，污泥沉淀经污泥排放管排入污泥池；
[0015] (3)沉淀池 I出水进入沉淀池 Π 中，加入浓度为1-3%的氢氧化钙，调节pH值为ΙΟ-ΐ 1 ， 用于除去废水 中的部分重金属及放射性; 再加入碳酸钠溶液除去金属元素 ，污泥沉淀均 经污泥排放管排入污泥池，污泥池中的污泥经板式过滤机后清液回流，固废外排处理；
[0016] (4)沉淀池 Π 出水进入中和调节池，调节pH值后进入超滤单元，进行除杂；
[0017] (5)超滤单元产水进入纳滤单元，进一步去除废水中的微量金属元素及放射性；
[0018] (6)纳滤单元的浓水回流至沉淀池，将部分浓水排至蒸发系统，结晶物作为固废处 理；
[0019] (7)纳滤产水进入电渗析与双极膜电渗析相结合处理单元，进行酸和碱的回收。
[0020] 优选的，步骤3)中的pH值为10.5。
[0021] 优选的，步骤(4)选用的超滤膜材质为PVDF，过滤方式为死端过滤。
[0022]优选的，步骤(5)选用的纳滤膜材质为聚烯胺复合膜，纳滤膜截留分子量为200-400KDa〇
[0023] 优选的，步骤(6)中，纳滤单元95%的浓水回流至沉淀池，为保证整个工艺流程中对 重金属及放射性的去除效果，将5%的浓水排至蒸发系统。
[0024] 优选的，步骤(7 )中的双极膜电渗析用于将纳滤产水中所含的氯化钠转化为氢氧 化钠及盐酸溶液，电渗析装置采用合金膜，用于将经过双极膜电渗析处理后的氯化钠淡水 提浓，之后再进入双极膜电渗析装置生产酸、碱。
[0025] 更有选的，步骤(7)中电渗析装置中离子交换膜采用的是合金膜，采用带密封线高 浓盐水专用隔板。
[0026] 优选的，为保证双极膜电渗析装置的电流效率，将双极膜电渗析装置生产的酸、碱 浓度控制在6%。
[0027] 该处理工艺具有以下有益效果：
[0028] (1)通过将传统的废水处理技术与膜法技术相结合来处理钠皂化废水，既实现了 废水的零排放，又实现了将废水中高含量氯化钠酸碱资源化；
[0029] (2)隔油、沉淀与超滤、纳滤相结合的工艺可以有效的去除钠皂化废水中含有的油 类、多种稀土元素、重金属元素及放射性，以保证后续工艺的最佳运行条件；
[0030] (3)由于钠皂化废水中含有放射性，超滤单元采用死端过滤方式，没有浓水排放， 可以在整个处理工艺中尽可能减少排放含有放射性的污染源；
[0031] (4)电渗析装置中采用的合金膜优于普通电渗析离子交换膜，其膜面电阻低于普 通离子交换膜，其脱盐率高于普通离子交换膜，运行过程中可降低能耗；
[0032] (5)采用将5%纳滤浓水蒸发结晶的方式有效的保证了不能沉淀的放射性元素的去 除效果，避免此类放射性元素逐渐富集在废水中。
附图说明
[0033]图1:本发明钠皂化废水资源化处理工艺的工艺流程图。
具体实施方式
[0034] 下面结合实施例，对本发明做进一步说明：
[0035] 实施例1
[0036] 1、采用某公司稀土分离项目生产工艺中排放的钠皂化废水作为本实施例证的原 水，具体水质数据见表1。
[0037] 表1进水水质
[0039] 2、将钠皂化废水排放至隔油调节池中停留4小时以上，浮油从集油管中排放至储 油槽中。
[0040] 3、隔油调节池出水进入沉淀池 I中，加入氢氧化钙，调节pH值，污泥沉淀经污泥排 放管排入污泥池。
[0041 ] 4、沉淀池 I出水进入沉淀池 Π 中，加入氢氧化钙，调节pH值，再加入碳酸钠溶液，污 泥沉淀排入污泥池，污泥池中的污泥经板式过滤机后清液回流，固废外排处理。
[0042]经过沉淀后的产水水质如表2所示：
[0043]表2沉淀后水质
[0045] 5、沉淀池 Π 出水进入中和调节池，调节pH值后进入超滤单元，在超滤单元去除废 水中悬浮物等杂质;选用的超滤膜材质为PVDF，过滤方式为死端过滤。
[0046] 6、超滤单元产水进入纳滤单元，选用的纳滤膜材质为特种聚稀胺复合膜，纳滤膜 截留分子量为200_400KDa;纳滤单元95%的浓水回流至沉淀池，为保证整个工艺流程中对重 金属及放射性的去除效果，将5%的浓水排至蒸发系统，结晶物作为固废处理。
[0047] 经过纳滤系统的产水水质如表3所示：
[0048] 表3纳滤产水水质
[0050] 7、纳滤产水进入电渗析与双极膜电渗析相结合处理单元，双极膜电渗析用于将纳 滤产水中所含的氯化钠转化为浓度6%的氢氧化钠及盐酸溶液，电渗析装置采用合金膜，用 于将经过双极膜电渗析处理后的氯化钠淡水提浓，之后再进入双极膜电渗析装置生产酸、 碱。以上所述，仅为本发明的具体实施方式，但本发明的保护范围并不局限于此，任何不经 过创造性劳动想到的变化或替换，都应涵盖在本发明的保护范围之内。因此，本发明的保护 范围应该以权利要求书所限定的保护范围为准。
Claims (5)
1. 一种钠皂化废水酸碱资源化处理工艺，包括以下处理步骤： (1) 将钠皂化废水排放至隔油调节池中停留4小时以上，用于去除残留在废水中的浮 油，以降低废水有机物含量，浮油从集油管中排放至储油槽中； (2) 隔油调节池出水进入沉淀池 I中，加入浓度为1 -3%的氢氧化妈，调节pH值为8.5-9， 用于除去废水中的部分重金属及放射性，污泥沉淀经污泥排放管排入污泥池； (3) 沉淀池 I出水进入沉淀池 Π 中，加入浓度为1-3%的氢氧化妈，调节pH值为10-11，用 于除去废水中的部分重金属及放射性;再加入碳酸钠溶液除去金属元素，污泥沉淀均经污 泥排放管排入污泥池，污泥池中的污泥经板式过滤机后清液回流，固废外排处理； (4) 沉淀池 Π 出水进入中和调节池，调节pH值后进入超滤单元，进行除杂； (5) 超滤单元产水进入纳滤单元，进一步去除废水中的微量金属元素及放射性； (6) 纳滤单元的浓水回流至沉淀池 I，将部分浓水排至蒸发系统，结晶物作为固废处理； (7) 纳滤产水进入电渗析与双极膜电渗析相结合处理单元，进行酸和碱的回收； 步骤(4)选用的超滤膜材质为PVDF，过滤方式为死端过滤； 步骤(6)中，纳滤单元95%的浓水回流至沉淀池，为保证整个工艺流程中对重金属及放 射性的去除效果，将5%的浓水排至蒸发系统； 步骤(7)中电渗析装置中离子交换膜采用的是合金膜，采用带密封线高浓盐水专用隔 板。
2. 根据权利要求1所述的处理工艺，其特征在于，步骤(3)中的pH值为10.5。
3. 根据权利要求1所述的处理工艺，其特征在于，步骤(5)选用的纳滤膜材质为聚烯胺 复合膜，纳滤膜截留分子量为200_400KDa。
4. 根据权利要求1所述的处理工艺，其特征在于，步骤(7)中的双极膜电渗析用于将纳 滤产水中所含的氯化钠转化为氢氧化钠及盐酸溶液，电渗析装置采用合金膜，用于将经过 双极膜电渗析处理后的氯化钠淡水提浓，之后再进入双极膜电渗析装置生产酸、碱。
5. 根据权利要求1所述的处理工艺，其特征在于，为保证双极膜电渗析装置的电流效 率，将双极膜电渗析装置生产的酸、碱浓度控制在6%。
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