CN103145285B - 一种煤化工废水的集成膜深度处理方法 - Google Patents
一种煤化工废水的集成膜深度处理方法 Download PDFInfo
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- CN103145285B CN103145285B CN201310069654.5A CN201310069654A CN103145285B CN 103145285 B CN103145285 B CN 103145285B CN 201310069654 A CN201310069654 A CN 201310069654A CN 103145285 B CN103145285 B CN 103145285B
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- waste water
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- 150000002989 phenols Chemical class 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylenes Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Chemical compound 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C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- 239000008091 pyridine Substances 0.000 description 1
- SMWDFEZZVXVKRB-UHFFFAOYSA-N quinoline Chemical compound 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Abstract
本发明涉及一种煤化工废水的集成膜深度处理方法，将经过生化处理后的废水经混凝沉淀处理后去除大部分的胶体、悬浮物以及部分大分子有机物，再通过活性焦吸附去除大部分难降解的有机物；对经过活性焦吸附后的废水采用超滤处理去除细小的悬浮物，经超滤后的出水经高压泵加压后采用反渗透处理去除无机盐离子及残留的有机物；最后对经过反渗透处理后的浓水采用膜蒸馏浓缩。该方法采用集成膜技术深度处理煤化工废水，并将活性焦吸附首次用于膜系统的前处理，可有效缓解膜污染，并提高产水水质，而且反渗透浓水采用膜蒸馏技术进行处理，可提高水的回收率，实现水资源的再利用及近“零排放”的目标，具有一定的应用前景。
Description
技术领域
[0001] 本发明涉及一种煤化工废水处理方法，尤其涉及一种煤化工废水的集成膜深度处理方法，属于废水处理和再利用领域。
背景技术
[0002] 煤化工废水是在原煤的高温干馏、煤气净化等过程中产生的一种难处理工业废水，不仅含有大量的酚类、多环芳烃、吡啶、喹啉等难降解有机污染物，还含有氨、氰化物、硫氰酸盐、氟等有毒有害物质，是一种高CODcr、高色度的难降解有毒有害废水。煤化工废水经过传统的生物处理工艺后一般难以达到回用标准，因此有必要对煤化工废水进行深度处理。
[0003] 传统的深度处理方法主要有电化学法、高级氧化法、混凝沉淀法、吸附法以及膜分离法等。电化学法和高级氧化法虽然效果显著，但操作复杂、成本耗能高；混凝沉淀法可有效去除悬浮物，但对溶解性有机物的去除效果不明显；吸附法操作简单、可有效去除多种有机物，但常用的活性炭价格昂贵、再生困难；膜分离法对CODcr具有较高的去除率，出水水质好，但膜污染问题严重影响系统的稳定性及处理效果。煤化工废水水质成分复杂，从实际运行效果看，上述单一的处理技术只能在一定程度上解决废水深度处理过程中某一方面的问题，但很难保证废水处理的全面达标和稳定运行。
发明内容
[0004] 本发明所要解决的技术问题是提供一种煤化工废水的集成膜深度处理方法，克服单一的处理技术处理成分复杂的废水导致设备运行不稳定及处理水质难以达标的缺陷。
[0005] 本发明解决上述问题的技术方案如下:一种煤化工废水的集成膜深度处理方法，包括以下步骤，将经过生化处理后的废水经混凝沉淀处理后去除大部分的胶体、悬浮物以及部分大分子有机物，再通过活性焦吸附去除所述上清液中的大部分难降解的有机物；对经过活性焦吸附后的废水采用超滤处理去除细小的悬浮物，经超滤后的出水经高压泵加压后采用反渗透处理去除无机盐离子及残留的有机物；最后对经过反渗透处理后的浓水采用膜蒸馏浓缩。
[0006] 本发明所用的煤化工废水水质分析表明，废水中含有大量的悬浮物和溶解性有机物，也具有一定的含盐量，其中溶解性有机物的分子量主要在>30，OOODa和〈10，OOODa。
[0007] 混凝沉淀可去除绝大部分的悬浮物及>30，OOODa的溶解性有机物，对〈10，OOODa的溶解性有机物去除率极低；
[0008] 活性焦吸附对〈10，OOODa的溶解性有机物具有很好的去除效果，出水中有机物浓度较低，且分子量范围主要<650Da，初步较好的除去溶解性有机物。
[0009] 超滤膜截留分子量较大(20，000Da-30, OOODa),主要去除活性焦吸附出水中的细小悬浮物，保证反渗透进水的浊度要求。
[0010] 反渗透主要去除废水中的无机盐离子，同时去除残留的有机物。
[0011] 膜蒸馏主要对反渗透的浓水进一步浓缩，明显提高水的回收率，实现近“零排放”。
[0012] 本发明的有益效果是:采用集成膜技术深度处理煤化工废水，并将活性焦吸附作为膜系统的前处理，可有效缓解膜污染，并提高产水水质，而且反渗透浓水采用膜蒸馏技术进行处理，提高水的回收率，实现水资源的再利用及近“零排放”的目标，具有一定的应用前景。
[0013] 在上述技术方案的基础上，本发明还可以做如下改进。
[0014] 进一步，所述混凝沉淀处理中使用的混凝剂为聚合氯化铝PAC，助凝剂为聚丙烯酰胺PAM，混凝剂PAC的投加量为150-250ppm，助凝剂PAM的投加量为0.5-1.0ppm。
[0015] 采用上述进一步方案的有益效果是:采用上述混合沉淀处理工艺后，可去除绝大部分的悬浮物及>30，OOODa的溶解性有机物，混凝沉淀后的上清液水质指标为C0Dcr<250mg/L, T0C〈100mg/L，浊度〈15NTU，电导率 <1850us/cm。
[0016] 进一步，活性焦吸附中所使用的活性焦粒径范围为0.03-1.0mm,吸附时间为l_6h，投加量为 5-15g/Lo
[0017] 采用上述进一步方案的有益效果是:投加量为5-15g/L、粒径范围为0.03-1.0mm活性焦吸附l_6h后，活性焦吸附对〈10，OOODa的溶解性有机物具有很好的去除效果，出水中有机物浓度较低，且分子量范围主要<650Da，出水水质指标为C0Dra〈120mg/L，T0C<50mg/L，浊度〈7NTU，电导率 <1850us/cmo
[0018] 进一步，所述超滤处理采用的超滤膜为中空纤维膜，操作方式为错流过滤，工作压力为0.05-0.20MPa，运行温度在20_40°C。优选聚砜(PS)中空纤维超滤膜，可截留分子量>20, OOODa的细小悬浮物。
[0019] 采用上述进一步方案的有益效果是:超滤出水的水质指标为COD。/ 100mg/L，T0C〈45mg/L，浊度〈1NTU，电导率 <1800us/cm。
[0020] 进一步，所述反渗透处理采用的反渗透膜脱盐率为95%_98%，操作方式为错流过滤，工作压力1.0-2.0Mpa,反渗透处理后的浓水占处理水量的20%-30%。优选为BW30-4040
反渗透膜。
[0021] 采用上述进一步方案的有益效果是:反渗透出水的水质指标为C0Dra〈5mg/L，T0C〈2mg/L，电导率<80us/cm，浊度检测不到。
[0022] 进一步，所述膜蒸馏操作方式为直接接触式，热侧温度为55-65Ό，冷侧温度为20-250C。膜蒸馏用膜采用H)VF、PTFE等中空纤维膜。
[0023] 采用上述进一步方案的有益效果是:膜蒸馏出水的水质指标为C0Dra〈10mg/L，T0C〈5mg/L，电导率 <120us/cm。
附图说明
[0024] 图1为本发明一种煤化工废水的集成膜深度处理方法流程图；
具体实施方式
[0025] 以下结合附图对本发明的原理和特征进行描述，所举实例只用于解释本发明，并非用于限定本发明的范围。
[0026] 实施例1
[0027] I)废水中含有大量的悬浮物和溶解性有机物，也具有一定的含盐量，其中溶解性有机物的分子量主要在>30，OOODa和〈10，OOODa,向SBR (生化处理)出水中加入混凝剂PAC250ppm，快搅lmin，然后加入助凝剂PAM1.0ppm,中搅lmin，再慢搅15min，最后静置20min，可去除90%的悬浮物及>30，OOODa的溶解性有机物。经混凝沉淀后上清液水质指标为 C0Der〈250mg/L，T0C〈100mg/L，浊度〈15NTU，电导率 <1850us/cm。
[0028] 2)混凝后的上清液采用活性焦吸附，活性焦的投加量为5g/L，粒径范围为0.03-0.15um，吸附2h后进行固液分离，活性焦吸附可以除去〈10，OOODa的溶解性有机物。经活性焦吸附后出水的水质指标为C0Dra〈120mg/L，T0C〈50mg/L，浊度〈8NTU，电导率<1850us/cm。
[0029] 3)活性焦吸附后的出水进入超滤膜系统，运行压力为0.05MPa，温度为25°C，pH值为8.5，超滤膜采用聚砜(PS)中空纤维超滤膜，可截留分子量>20，OOODa的细小悬浮物。超滤产水的水质指标为C0Dra〈100mg/L，TOC〈45mg/L，浊度〈1NTU，电导率<1800us/cm。
[0030] 4)超滤产水经高压泵加压后进入反渗透膜系统，运行压力为1.0Mpa,温度为250C，pH值为8，反渗透产水的水质指标为CODra〈5mg/L，TOC〈2mg/L，电导率<80us/cm，反渗透浓液的水质指标为C0Dra〈280mg/L，T0C<200mg/L,电导率<4600us/cm。
[0031] 5)反渗透浓液采用膜蒸馏进一步浓缩，热侧温度为50°C，冷侧温度为25°C，膜蒸馏产水的水质指标为C0Dra〈10mg/L，TOC〈5mg/L，电导率<120us/cm。实施例2
[0032] I)废水中含有大量的悬浮物和溶解性有机物，也具有一定的含盐量，其中溶解性有机物的分子量主要在>30，OOODa和〈10，OOODa,向废水经SBR (生化处理)后的出水中加入混凝剂PAC250ppm，快搅Imin，然后加入助凝剂PAM1.0ppm,中搅Imin，再慢搅15min，最后静置20min，可去除95%的悬浮物及>30，OOODa的溶解性有机物。经混凝后上清液水质指标为 C0Der〈250mg/L，T0C〈100mg/L，浊度〈15NTU，电导率 <1850us/cm。
[0033] 2)混凝后的上清液采用活性焦吸附，活性焦的投加量为15g/L，粒径范围为0.20-0.35un，吸附2h后进行固液分离，活性焦吸附可以除去大部分〈10，OOODa的溶解性有机物。经活性焦吸附后出水的水质指标为CODe/35mg/L，TOC〈12mg/L，浊度〈7NTU，电导率<1850us/cm。
[0034] 3)活性焦吸附后的出水进入超滤膜系统，运行压力为0.05MPa，温度为25°C，pH值为8.5，超滤膜采用聚砜(PS)中空纤维超滤膜，可截留分子量>20，OOODa的细小悬浮物。超滤产水的水质指标为C0Dra〈30mg/L，T0C〈10mg/L，浊度〈1NTU，电导率<1800us/cm。
[0035] 4)超滤产水经高压泵加压后进入反渗透膜系统，运行压力为1.0Mpa,温度为250C，pH值为8，反渗透产水的水质指标为CODra〈5mg/L，TOC〈lmg/L，电导率<80us/cm，反渗透浓液的水质指标为C0Dra〈80mg/L，T0C〈40mg/L，电导率<4600us/cm。
[0036] 5)反渗透浓液采用膜蒸馏进一步浓缩，热侧温度为50°C，冷侧温度为25°C，膜蒸馏产水的水质指标为CODra〈7mg/L，TOC〈3mg/L，电导率<120us/cm。
[0037] 以上所述仅为本发明的较佳实施例，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。
Claims (1)
1.一种煤化工废水的集成膜深度处理方法，其特征在于，将经过生化处理后的废水经混凝沉淀处理后去除大部分的胶体、悬浮物以及部分大分子有机物，再通过活性焦吸附去除上清液中的大部分难降解的有机物；对经过活性焦吸附后的出水采用超滤处理去除水中的细小悬浮物；经超滤后的出水经高压泵加压后采用反渗透处理去除无机盐离子及残留的有机物；最后对经过反渗透处理后的浓水采用膜蒸馏浓缩； 所述混凝沉淀处理去除85%以上的悬浮物及>30，OOODa的溶解性有机物；所述活性焦吸附去除〈10，OOODa的溶解性有机物，出水中有机物浓度较低分子量范围主要<650Da ;超滤膜截留分子量>20，OOODa的细小悬浮物；所述混凝沉淀处理中使用的混凝剂为聚合氯化铝PAC，助凝剂为聚丙烯酰胺PAM，混凝剂PAC的投加量为150-250ppm，助凝剂PAM的投加量为0.5-1.0ppm ;活性焦吸附中所使用的活性焦粒径范围为0.03-1.0mm，吸附时间为l_6h，投加量为5-15g/L;所述超滤处理采用的超滤膜为中空纤维膜，操作方式为错流过滤，工作压力为0.05-0.20MPa，运行温度在20_40°C ;所述反渗透处理采用的反渗透膜脱盐率为95% -98%，操作方式为错流过滤，工作压力1.0-2.0Mpa，反渗透处理后得到的浓水占处理水量的20% -30% ;所述膜蒸馏操作方式为直接接触式，热侧温度为55-65°C，冷侧温度为20-25。。。
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| CN103894066B (zh) * | 2014-03-27 | 2016-08-17 | 金发科技股份有限公司 | 一种用于纯化后处理母液的膜分离装置和方法 |
| CN104445714B (zh) * | 2014-11-04 | 2017-08-25 | 深圳能源资源综合开发有限公司 | 煤化工清净废水高倍回用工艺及其专用装置 |
| CN105668846A (zh) * | 2016-01-15 | 2016-06-15 | 中国石油大学(华东) | 一种煤化工含芳烃废水的精细处理工艺 |
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| CN108467140A (zh) * | 2018-04-09 | 2018-08-31 | 武汉钢铁有限公司 | 一种焦化废水组合脱盐工艺 |
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