CN105254068A - 一种铬鞣废水处理及铬回收系统及处理工艺 - Google Patents
一种铬鞣废水处理及铬回收系统及处理工艺 Download PDFInfo
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- CN105254068A CN105254068A CN201510733274.6A CN201510733274A CN105254068A CN 105254068 A CN105254068 A CN 105254068A CN 201510733274 A CN201510733274 A CN 201510733274A CN 105254068 A CN105254068 A CN 105254068A
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- regulator
- chrome tanning
- reverse osmosis
- tanning wastewater
- recovery
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N chromium Chemical compound data:image/svg+xml;base64,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 data:image/svg+xml;base64,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 [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 40
- 238000011084 recovery Methods 0.000 title claims abstract description 12
- 239000011651 chromium Substances 0.000 title abstract description 28
- 229910052804 chromium Inorganic materials 0.000 title abstract description 21
- 238000004065 wastewater treatment Methods 0.000 title abstract description 4
- 239000002351 wastewater Substances 0.000 claims abstract description 57
- 238000001223 reverse osmosis Methods 0.000 claims abstract description 32
- 238000005342 ion exchange Methods 0.000 claims abstract description 13
- 230000001105 regulatory Effects 0.000 claims abstract description 3
- 238000001914 filtration Methods 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 12
- 239000002699 waste material Substances 0.000 claims description 9
- 239000003957 anion exchange resin Substances 0.000 claims description 8
- 239000012528 membrane Substances 0.000 claims description 7
- 238000009298 carbon filtering Methods 0.000 claims description 6
- 230000026676 system process Effects 0.000 claims description 6
- 238000002203 pretreatment Methods 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound 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[C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 2
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[OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 description 1
- 230000037250 Clearance Effects 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 230000000903 blocking Effects 0.000 description 1
- 230000003197 catalytic Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound 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Abstract
本发明公开了一种用于铬鞣废水处理及铬回收的方法。该方法包括铬鞣废水预处理系统、pH调节系统、反渗透系统和离子交换系统。本发明工艺过程简单，不需要额外添加化学药剂，降低了废水的矿化度，经处理后的回用水中Cr总含量小于0.1mg/L，达到国家标准。同时本发明耗电量小，大大节约了成本，利于工业化操作。
Description
技术领域
[0001] 本发明属于水处理领域，具体涉及一种用于铬鞣废水处理及铬回收的方法系统及处理工艺，适用于制革企业铬鞣废水的处理以及铬的回收再利用。
背景技术
[0002] 铬鞣法广泛应用于皮革工业，但铬的利用率很低，有30% -40%的铬最终未被皮革吸收、固定，而是被废弃成为污染物。重金属铬是这类工业所排放的废水和污泥中的主要污染物质，铬鞣废水的任意排放，会使铬盐在土壤、植物、水生物中积聚，对环境造成巨大的污染，若铬通过食物链进入人体中，将极大地危害人体健康。同时，这些铬直接排放还会造成铬资源得不到合理利用，给皮革企业造成损失。因此，铬鞣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、毒性大的铬鞣废水、脱毛含硫废水分别进行处理，去除废水中铬离子和硫化物，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]目前对皮革行业铬鞣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、铬泥分离难度大、易造成二次污染等；特别是沉淀法产生的大量铬泥，不仅含有铬，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铬废水进行处理，对制革废水中的铬进行回收利用，减少资源的浪费显得十分紧迫。
[0006] 专利CN103922521A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。虽然该回收处理方法能将铬进行有效的回收处理，但是过程过于复杂，程序繁琐，同时耗电量巨大，处理成本过高，不利于工业化操作。
发明内容
[0007] 针对上述问题，本发明提供了一种铬鞣废水处理及铬回收系统及其处理工艺，该系统及处理工艺操作简单，易于工业化操作。
[0008] 为了达到上述目的，本发明提供的技术方案为:
[0009] 一种铬鞣废水处理及铬回收系统，所述系统依次包括铬鞣废水预处理系统、pH调节系统、反渗透系统和离子交换系统。
[0010] 所述铬鞣废水预处理系统包括过滤网和调节池。
[0011] 所述pH调节系统包括pH调节池，因所述铬鞣废水中含有大量的三价铬，如果在中性条件下，三价铬易从离子状态转化为氢氧化铬沉淀，会引起膜的严重堵塞，膜分离系统无法正常运行，故在进入反渗透系统前需要先进行pH调节。
[0012] 所述反渗透系统包括机械过滤装置、活性炭过滤装置、精密过滤装置和反渗透膜，在进行反渗透过程前需要对废水中的固体杂质以及悬浮颗粒进行过滤除杂，以免堵塞反渗透膜。
[0013] 所述离子交换系统包括除酸阴离子交换树脂和pH调节装置，经反渗透除铬以后的废水中还会存在其他酸根离子，影响再生液的纯度，因此需要将这些酸根离子出去。
[0014] 一种如权利要求1-5任一项所述的回收系统的回收处理工艺，所述处理工艺包括如下步骤:
[0015] (I)将收集铬鞣废水进行铬鞣废水预处理系统，依次经过滤网和调节池进行预处理；所述过滤网彡20目，调节池水力停留时间彡8h，例如8h、10h、12h、14h或16h等。
[0016] (2)经预处理系统预处理后的铬鞣废水于进入pH调节系统，调节pH值为2〜3，例如2、2.1,2.2,2.3,2.4,2.5,2.6,2.7,2.8,2.9或3等，在偏酸性条件下不会发生三价铬的金属沉淀物，从而防止了由此引起的结垢和污堵。
[0017] (3)将经pH调节系统pH调节pH后的铬鞣废水送入反渗透系统，进行反渗透处理；
[0018] (4)经反渗透系统处理后的废水进入离子交换系统进行处理后回用。
[0019] 所述步骤⑵中pH调节系统包括pH调节池。
[0020] 所述步骤(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。
[0021] 所述步骤(3)中反渗透系统包括机械过滤装置、活性炭过滤装置、精密过滤装置和反渗透膜。
[0022] 所述步骤(3)中反渗透处理包括机械过滤、活性炭过滤、精密过滤和反渗透。
[0023] 所述步骤(4)中离子交换系统包括除酸阴离子交换树脂和pH调节装置。
[0024] 所述步骤(4)中进入离子交换系统进行处理包括在除酸阴离子交换树脂中进行离子交换和经PH调节装置调节pH。
[0025]所述步骤(4)中调节 pH为 6 〜7，例如 6、6.1、6.2、6.3、6.4、6.5、6.6、6.7、6.8、6.9
或7等。
[0026] 与现有技术相比，本发明的有益效果为:
[0027] (I)本发明工艺过程简单，不需要额外添加化学药剂，降低了废水的矿化度，经处理后的回用水中Cr总含量小于0.lmg/L，达到国家标准。
[0028] (2)同时本发明耗电量小，大大节约了成本，利于工业化操作。
具体实施方式
[0029] 实施例1
[0030] 针对某一皮革厂的废水，铬鞣废水水量30m3/h，废水中主要污染物为总铬，并含有少量的COD，其处理方法如下
[0031] (I)将收集铬鞣废水进行铬鞣废水预处理系统，依次经过滤网(多20目)和调节池进行预处理，其在调节池水力停留时间为10h。
[0032] (2)经预处理系统预处理后的铬鞣废水于进入pH调节系统，调节pH为2.5。
[0033] (3)将经pH调节系统pH调节pH后的铬鞣废水送入反渗透系统，依次机械过滤装置、活性炭过滤装置、精密过滤装置除去杂质和悬浮颗粒物后，经反渗透膜进行处理。
[0034] (4)经反渗透系统处理后的废水进入除酸阴离子交换树脂除去酸根离子，然后调节pH为6.5后进行回用。
[0035] 经过处理后的回用水中Cr总含量为0.09mg/L，达到国家标准。
[0036] 实施例2:
[0037] 针对某一皮革厂的废水，铬鞣废水水量45m3/h，废水中主要污染物为总铬，并含有少量的COD，其处理方法如下
[0038] (I)将收集铬鞣废水进行铬鞣废水预处理系统，依次经过滤网(多20目)和调节池进行预处理，其在调节池水力停留时间为8h。
[0039] (2)经预处理系统预处理后的铬鞣废水于进入pH调节系统，调节pH为2。
[0040] (3)将经pH调节系统pH调节pH后的铬鞣废水送入反渗透系统，依次机械过滤装置、活性炭过滤装置、精密过滤装置除去杂质和悬浮颗粒物后，经反渗透膜进行处理。
[0041] (4)经反渗透系统处理后的废水进入除酸阴离子交换树脂除去酸根离子，然后调节PH为6后进行回用。
[0042] 经过处理后的回用水中Cr总含量为0.087mg/L，达到国家标准。
[0043] 实施例3:
[0044] 除步骤⑵中国调节pH为3，步骤⑷中调节pH为7夕卜，其他过程均与实施例1相同。
[0045] 经过处理后的回用水中Cr总含量为0.094mg/L，达到国家标准。
[0046] 对比例:
[0047] 为专利CN103922521A中实施例1，经过处理后的回用水中Cr总含量为0.32mg/L。
[0048] 综上所述，本发明通过对铬鞣废水进行反渗透处理和用除酸阴离子交换树脂处理后，提高了水中Cr的去除率，同时该方法工艺过程简单，节约成本，易于大规模生产操作。
[0049] 申请人声明，本发明通过上述实施例来说明本发明的详细方法，但本发明并不局限于上述详细方法，即不意味着本发明必须依赖上述详细方法才能实施。所属技术领域的技术人员应该明了，对本发明的任何改进，对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本发明的保护范围和公开范围之内。
Claims (9)
1.一种铬鞣废水处理及铬回收系统，其特征在于，所述系统依次包括铬鞣废水预处理系统、pH调节系统、反渗透系统和离子交换系统。
2.如权利要求1所述的回收系统，其特征在于，所述铬鞣废水预处理系统包括过滤网和调节池。
3.如权利要求1或2所述的回收系统，其特征在于，所述pH调节系统包括pH调节池。
4.如权利要求1-3所述的回收系统，其特征在于，所述反渗透系统包括机械过滤装置、活性炭过滤装置、精密过滤装置和反渗透膜。
5.如权利要求1-4所述的回收系统，其特征在于，所述离子交换系统包括除酸阴离子交换树脂和pH调节装置。
6.一种如权利要求1-5任一项所述的回收系统的回收处理工艺，其特征在于，所述处理工艺包括如下步骤: (1)将收集铬鞣废水进行铬鞣废水预处理系统，依次经过滤网和调节池进行预处理；所述过滤网彡20目，调节池水力停留时间彡8h ; (2)经预处理系统预处理后的铬鞣废水进入pH调节系统，调节pH值为2〜3 ; (3)将经pH调节系统调节pH后的铬鞣废水送入反渗透系统，进行反渗透处理； (4)经反渗透系统处理后的废水进入离子交换系统进行处理后回用。
7.如权利要求6所述的方法，其特征在于，所述步骤(2)中pH调节系统包括pH调节池； 优选地，所述步骤(2)中络縣废水在pH调节池内的反应时间多3h，pH调节池内的搅拌速率为15rpm。
8.如权利要求6或7所述的方法，其特征在于，所述步骤(3)中反渗透系统包括机械过滤装置、活性炭过滤装置、精密过滤装置和反渗透膜； 优选地，所述步骤(3)中反渗透处理包括机械过滤、活性炭过滤、精密过滤和反渗透。
9.如权利要求1-3任一项所述的方法，其特征在于，所述步骤(4)中离子交换系统包括除酸阴离子交换树脂和pH调节装置； 优选地，所述步骤(4)中进入离子交换系统进行处理包括在除酸阴离子交换树脂中进行离子交换和经pH调节装置调节pH ; 优选地，所述步骤⑷中调节pH为6〜7。
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