CN103922521B - 一种用于铬鞣废水处理及铬回收的方法 - Google Patents
一种用于铬鞣废水处理及铬回收的方法 Download PDFInfo
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- CN103922521B CN103922521B CN201410190245.5A CN201410190245A CN103922521B CN 103922521 B CN103922521 B CN 103922521B CN 201410190245 A CN201410190245 A CN 201410190245A CN 103922521 B CN103922521 B CN 103922521B
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Chemical compound data:image/svg+xml;base64,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 data:image/svg+xml;base64,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 [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 22
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- 239000000126 substance Substances 0.000 description 3
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound 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- 241000276438 Gadus morhua Species 0.000 description 1
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[OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical class 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- 235000019516 cod Nutrition 0.000 description 1
- 230000035617 depilation Effects 0.000 description 1
- 230000001627 detrimental Effects 0.000 description 1
- 238000009297 electrocoagulation Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
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- VTLYFUHAOXGGBS-UHFFFAOYSA-N fe3+ Chemical compound 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[S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- Y02W30/54—
Abstract
本发明公开了一种用于铬鞣废水处理及铬回收的方法。该方法包括预处理、pH调节、电絮凝处理、曝气沉淀处理、污泥反应池处理、电催化氧化处理等步骤。本发明为皮革水处理领域提供一种全新的电化学法处理含铬废水的方法，并研究开发回收污泥中铬的工艺，降低铬资源消耗，实现含铬废水的达标排放和铬资源的回收再利用，同时解决了废水处理中大量铬泥的后处理问题。
Description
技术领域
[0001] 本发明属于水处理领域，具体设及一种用于铭踩废水处理及铭回收的方法，适用 于制革企业铭踩废水的处理W及铭的回收再利用。
背景技术
[0002] 铭踩法广泛应用于皮革工业，但铭的利用率很低，有30% -40%的铭最终未被皮 革吸收、固定，而是被废弃成为污染物。重金属铭是该类工业所排放的废水和污泥中的主要 污染物质，铭踩废水的任意排放，会使铭盐在上壤、植物、水生物中积聚，对环境造成巨大的 污染，若铭通过食物链进入人体中，将极大地危害人体健康。同时，该些铭直接排放还会造 成铭资源得不到合理利用，给皮革企业造成损失。因此，铭踩废水的处理是制革污水处理中 一个最为突出的问题。
[0003] 对于制革废水处理，国内外较为成熟的工艺方法均采用"分隔+集中、物化+生化" 的方法，即在处理综合废水前，对制革废水中的污染物浓度较高、毒性大的铭踩废水、脱毛 含硫废水分别进行处理，去除废水中铭离子和硫化物，处理后的废液再和其他制革废水混 合，进行集中二级处理，达标后排放。
[0004] 目前对皮革行业铭踩废水的处理方法有碱沉淀法、直接循环法、萃取回收法等。各 种方法都有一定的优点，也有其不足之处，如需投加大量的化学药剂、费用昂贵、铭泥分离 难度大、易造成二次污染等；特别是沉淀法产生的大量铭泥，不仅含有铭，还含有油脂及蛋 白质等有机物，其中成分较复杂，属于危险废弃物，处理难度大，不能采取直接填埋的方式 进行处理处置，后期费用高。且污泥若采回用，其中油脂、蛋白质等杂质会影响成革质量，不 利于企业的发展。因此上述方法并没有得到较大的推广应用。
[0005] 随着工业的发展，我国重金属资源日益短缺。采取有效的手段对皮革含铭废水进 行处理，对制革废水中的铭进行回收利用，减少资源的浪费显得十分紧迫。
发明内容
[0006] 本发明旨在克服现有技术的不足，提供一种简单有效的用于铭踩废水处理及铭回 收的方法，并实现污泥资源化利用的效果。
[0007] 为了达到上述目的，本发明提供的技术方案为：
[000引所述用于铭踩废水处理及铭回收的方法包括如下步骤：
[0009] (1)将收集铭踩废水依次经网筛和调节池进行预处理；所述网筛>20目，调节池 水力停留时间> 她；
[0010] (2)将预处理后的铭踩废水于抑调节池中调节抑值为8~9 ;
[ocm] (3)将经抑调节后的铭踩废水送入电絮凝处理设备进行电解絮凝处理，电解处理 时间> 3min;电解絮凝设备阴极及阳极均采用铁极板，极板间距10~30mm，电源采用直流 周期换向电源，电源换向周期为15~30min;电流密度根据流量调节；
[0012] (4)将经电絮凝处理后的出水送入曝气-沉淀池进行曝气、沉淀处理；先进行曝气 氧化，曝气气水比为1 ;3至1 ;7,停留时间> 30min，沉淀池表面负荷《ImVm2 •h;
[0013] (5)将沉淀处理产生的污泥送至污泥反应池，调节污泥抑值《3,揽拌至污泥完全 转变为液体；
[0014] (6)将步骤（5)所得的液体送入电解氧化处理设备进行电解氧化处理，所述电解 氧化处理设备的阳极为活性炭，阴极为不诱钢板，极板间距为20~50mm;电流密度根据流 量调节；
[001引 （7)将电解氧化处理后的出水于抑调节池中调节抑值为7~8 ;
[0016] (8)将经抑调节后的出水送入沉淀池进行铁泥和铭液的分离，沉淀池表面负荷 《•h。
[0017] 优选地，步骤似中所述铭踩废水在抑调节池内的反应时间> 3h，抑调节池内的 揽拌速率为15rpm。
[0018] 步骤（3)所述电絮凝处理设备进行电解絮凝处理时采用曝气揽拌，曝气强度为气 水比1 ;1至1 ;5。
[0019] 步骤（4)所述曝气气水比为1:5。
[0020] 步骤（5)污泥在污泥反应池中的停留时间> 3h，揽拌速率> 15rpm。
[0021] 步骤（6)所述电解氧化处理设备进行电解氧化处理时采用曝气揽拌，曝气强度为 气水比1 ;1~1 ;5 ;电解氧化处理时间> 30min。
[002引步骤（7)所述出水在抑调节池内的反应时间为25~35min，抑调节池内的揽拌 速率为15rpm。
[0023] 步骤巧）中所述沉淀池沉淀形成的铁泥中铁含量高（可高达80%，干重计），可 作为化工原料出售；沉淀池上清液为铭液，其中主要成分为六价铭，六价铭含量高达lOOg/ LW上，可回用于制革工艺。
[0024] 本发明方法中所述沉淀池为斜管沉淀池。所述调节池、抑调节池、电絮凝处理设 备、污泥反应池、电解氧化处理设备等设备均为现有技术设备，为本领域技术人员所熟知。
[0025] 与现有技术相比，本发明的有益效果为：
[0026] 1)本发明所设及的该种工艺，通过电化学方法处理皮革废水，工艺流程简单、自动 化程度高、反应时间短、去除率高等优点，因电化学系统包括了电凝聚、电气浮、电氧化、电 还原等过程，处理能力很全面。
[0027] 2)电化学法除铭是由于在电解过程中铁阳极不断溶解，产生亚铁离子使废水中的 六价铭还原成S价铭，同时亚铁离子被氧化成S价铁离子，并与水中的助r形成氨氧化铁 起到了凝聚和吸附作用。因此，它不需投加处理试剂，从而避免增添其他离子和带入其他污 染物造成二次污染。
[002引 3)电化学方法的污泥质量较好，主要物质为铭、铁氨氧化物沉淀物质及部分油脂 等有机物，污泥后续通过电解氧化工艺进行回收处理，电解氧化工艺不仅将=价铭氧化为 六价铭，而且还实现了将污泥中的油脂等有机物进行了氧化分解，使得污泥中的成分更加 单一，有利于铭资源的回收利用。
[0029] 4)本发明将污泥作为一种廉价的二次可再生资源，回收其中的铭、铁等物质，不仅 可W避免环境污染，同时通过回收利用重金属，节约了成本，实现了清洁生产、循环经济。工 艺处理后无铭泥产生，有效解决了铭泥的处理处置问题。
[0030] 5)铭回收后的废水也可部分用于制革生产的用水。
[0031] 6)整合的电化学重金属深度处理系统设备一体化程度高，装置结构简单紧凑，占 地面积小，管理成本低，可广泛应用于中小型皮革厂，对于铭踩废水具有良好实际应用价 值。
[0032] 总之，本发明提供了一种铭踩水处理及铭资源回收的工艺，为皮革水处理领域提 供一种全新的电化学法处理含铭废水的方法，并研究开发回收污泥中铭的工艺，降低铭资 源消耗，实现含铭废水的达标排放和铭资源的回收再利用，同时解决了废水处理中大量铭 泥的后处理问题。
具体实施方式 [003引实施例1
[0034] 针对某一皮革厂的废水，铭踩废水水量30mVh，废水中主要污染物为总铭，并含有 少量的COD，其处理方法如下（所述调节池、抑调节池、电絮凝处理设备、污泥反应池、电解 氧化处理设备等设备均为现有技术设备，为本领域技术人员所熟知）：
[0035] (1)将收集铭踩废水依次经网筛和调节池进行预处理；所述网筛>20目，调节池 水力停留时间> 她；
[0036] (2)将预处理后的铭踩废水于抑调节池中调节抑值为8~9 ;所述铭踩废水在抑 调节池内的反应时间 > 化，抑调节池内的揽拌速率为15rpm ;
[0037] (3)将经抑调节后的铭踩废水送入电絮凝处理设备进行电解絮凝处理，电解处理 时间> 3min;电解絮凝设备阴极及阳极均采用铁极板，极板间距15mm，电源采用直流周期 换向电源，电源换向周期为15min;电流密度为100~120A/m2,设备内采用曝气强度为气水 比 1 ;3。
[003引 （4)将经电絮凝处理后的出水先后送入曝气池、斜管沉淀池进行曝气、沉淀处理： 先进行曝气氧化，曝气气水比为1 ;3至1 ;7,停留时间> 30min，沉淀池表面负荷《m2 •h;
[0039] (5)将沉淀处理产生的污泥送至污泥反应池，调节污泥抑值《3,揽拌至污泥完全 转变为液体；污泥在污泥反应池中的停留时间> 化，揽拌速率> 15rpm。
[0040] (6)将步骤（5)所得的液体送入电解氧化处理设备进行电解氧化处理，所述电解 氧化处理设备的阳极为活性炭，阴极为不诱钢板，极板间距为50mm，内部填充表面改性活性 碳颗粒，粒径大小3~5mm，填充比例70%，电流密度为20~50A/m2,处理停留时间45min， 采用曝气进行揽拌，曝气强度控制气水比1 ;5;
[0041] (7)将电解氧化处理后的出水于抑调节池中调节抑值为7~8;所述出水在抑 调节池内的反应时间为25~35min，抑调节池内的揽拌速率为15巧m;
[0042] (8)将经抑调节后的出水送入斜管沉淀池进行铁泥和铭液的分离，沉淀池表面负 荷《WV•ho
[0043] 本发明方法中所述沉淀池为斜管沉淀池。
[0044] 处理效果如表1所示（S个月累计监测数据的平均情况）：
[0045]表1
[0046]
[0047] 污泥经过电解氧化处理并采用沉淀法进行铁分离后，产生的铭液纯度较高，杂质 少，其中铭含量高达110~120g/L，回用于制革工艺或作为化工原料出售。整个工艺几乎不 产生铭泥，解决了污泥的处理处置问题。
Claims (8)
1. 一种用于铬鞣废水处理及铬回收的方法，其特征在于，所述方法包括如下步骤： (1) 将收集铬鞣废水依次经网筛和调节池进行预处理；所述网筛多20目，调节池水力 停留时间彡8h; (2) 将预处理后的铬鞣废水于pH调节池中调节pH值为8~9 ; (3) 将经pH调节后的铬鞣废水送入电絮凝处理设备进行电解絮凝处理，电解处理时间 彡3min ;电絮凝处理设备阴极及阳极均采用铁极板，极板间距10~30mm，电源采用直流周 期换向电源，电源换向周期为15~30min ; (4) 将经电絮凝处理后的出水送入曝气-沉淀池进行曝气、沉淀处理：先进行曝气氧 化，曝气气水比为1 :3至1 :7,停留时间彡30min，沉淀池表面负荷< lm3/m2 • h ; (5) 将沉淀处理产生的污泥送至污泥反应池，调节污泥pH值< 3,搅拌至污泥完全转变 为液体； (6) 将步骤（5)所得的液体送入电解氧化处理设备进行电解氧化处理，所述电解氧化 处理设备的阳极为活性炭，阴极为不锈钢板，极板间距为20~50mm ; (7) 将电解氧化处理后的出水于pH调节池中调节pH值为7~8 ; (8) 将经pH调节后的出水送入沉淀池进行铁泥和铬液的分离，沉淀池表面负荷< Im3/ m2 • h〇
2. 如权利要求1所述的方法，其特征在于，步骤（2)中所述铬鞣废水在pH调节池内的 反应时间彡3h，pH调节池内的搅拌速率为15rpm。
3. 如权利要求2所述的方法，其特征在于，步骤（3)所述电絮凝处理设备进行电解絮凝 处理时采用曝气搅拌，曝气强度为气水比1 :1至1 :5。
4. 如权利要求3所述的方法，其特征在于，步骤（4)所述曝气气水比为1:5。
5. 如权利要求4所述的方法，其特征在于，步骤（5)污泥在污泥反应池中的停留时间 彡3h，搅拌速率多15rpm。
6. 如权利要求5所述的方法，其特征在于，步骤（6)所述电解氧化处理设备进行电解氧 化处理时采用曝气搅拌，曝气强度为气水比1 :1~1 :5 ;电解氧化处理时间彡30min。
7. 如权利要求6所述的方法，其特征在于，步骤（7)所述出水在pH调节池内的反应时 间为25~35min，pH调节池内的搅拌速率为15rpm。
8. 如权利要求1至7任一项所述的方法，其特征在于，所述沉淀池为斜管沉淀池。
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