CN102050554B - 一种基于深度净化废水后树脂高浓脱附液的处置方法 - Google Patents
一种基于深度净化废水后树脂高浓脱附液的处置方法 Download PDFInfo
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Abstract
本发明公开了一种基于深度净化废水后树脂高浓脱附液的处置方法,属于树脂脱附液处理领域。其步骤为:经过阴离子交换树脂处理的高浓脱附液经过纳滤膜截留后分为高浓纳滤截留液以及纳滤透过液,纳滤透过液经氧化以后可以作为脱附剂重复利用;在产生的高浓纳滤截留液中加入混凝剂,进行混凝沉淀;对混凝沉淀后的上清液进行Fenton氧化或臭氧氧化;反应后的溶液中加入碱液,进一步混凝沉淀;将混凝沉淀后的液体返回到生化尾水段的生化系统进一步进行生物降解。经本发明处理后的高浓截留液,可返回进行生物降解,实现了高浓脱附液的循环处理。本方法节约了处理成本,避免了二次污染,实现了树脂脱附液的无害化、减量化、资源化。
Description
技术领域
本发明涉及的是一种树脂脱附液的处置方法,具体而言,是一种基于阴离子交换树脂深度净化废水后树脂高浓脱附液的处置方法。
背景技术
改革开放以来,我国精细化工飞速发展,为国民经济的腾飞作出了重要贡献, 但该行业排放的废水往往具有成分复杂、浓度高、毒性大、色泽深、难以生物降解等特点,这些废水给生态系统和环境造成了严重的污染。寻求适合的方法对这些废水进行有效地处理已成当务之急。
生物技术是废水处理最经济的技术,但生物技术后,废水中还残留微生物代谢及分解的产物、不能被微生物降解的有毒物质以及各种无机物等,还需深度处理达到环境标准后才能排放。在各类废水的深度处理技术中,树脂技术是被广泛使用的处理技术。树脂吸附法具有吸附容量大、机械性能强、可重复利用等优点。然而生化尾水经树脂处理后脱附下来的脱附液具有成分复杂、浓度高、毒性大、色泽深、难以生物降解等特点,这就使得脱附液的处理成为环保界公认的治理难题,也成为限制树脂在各行各业应用的一个“瓶颈” 问题。因此,脱附液如何进行高效经济的处理,是急需解决的一个难题。
常用的脱附液的处理方法主要有强化混凝、催化氧化、催化还原、膜滤等。混凝法通常对大分子疏水性物质去除效果较好,然而其具有混凝剂用量大,污泥产生量大,难直接达标,对极性小分子有机物去除效果差等缺点。催化氧化技术是一种高级氧化技术,具有降解完全、无二次污染、能耗和原材料消耗低的优点。然而Fenton氧化对pH要求较高,臭氧氧化具有建设投资大,运行费用高等缺点。膜滤也具有膜制作成本高、容易污染等缺点。因此,单一的处理工艺很难对脱附液进行高效经济的处理,采用各种工艺的组合工艺就很有必要。
发明内容
1、 发明要解决的技术问题
由于树脂技术的广泛应用,产生了大量的树脂脱附液,现有的处理工艺很难对脱附液进行高效经济的处理,本发明提供一种基于深度净化废水后树脂高浓脱附液的处置方法,将混凝和高级氧化组合工艺用于磁性阴离子交换树脂对生化尾水进行处理时树脂脱附液的回收与处置,可以对纳滤截留液的TOC和UV254都有较大程度上的去除,提高了其BOD5/CODcr,生化出水基本稳定,解决树脂高浓脱附液的处理难题。
2、 技术方案
一种基于深度净化废水后树脂高浓脱附液的处置方法,其步骤如下:
1)将阴离子交换树脂处理生化尾水后的树脂高浓脱附液,进入纳滤膜系统进行分离,操作压力在1.0-2.5MPa,主要分为含有小分子物质的纳滤膜透过液及主要含有大分子有机物的纳滤膜截留液两部分;其中纳滤膜截留液的体积为高浓脱附液体积的1/7左右,产生的纳滤膜透过液进行氧化后可作为脱附剂重复利用;;
2)对步骤1)产生的纳滤截留液用一定浓度的混凝剂进行混凝,混凝剂有FeCl3·6H2O、FeSO4·7H2O、Al2(SO4)3·18H2O、聚合氯化铝、PAC等;加入的混凝剂的质量百分比为1%-5%,混凝沉淀后的溶液的pH在2-5之间,TOC去除率达到35%-55%;
3)取步骤2)获得的混凝上清液,进行Fenton氧化或臭氧氧化;加入FeSO4·7H2O的质量百分比为0.1%-2%,加入的30%的过氧化氢溶液的质量百分比为1%-4%;通入的臭氧的浓度为3mg/L-10mg/L,反应1-5h后,TOC去除率达到60%-80%;
4)将步骤3)获得的氧化液用氢氧化钠或氢氧化钙溶液调节其pH至8.5-10.5,进一步混凝沉淀,经处理后,废水的BOD5/CODcr提高至0.4以上;
5)将步骤4)获得的溶液进入模拟的活性污泥生化系统进一步处理。
步骤5)进水COD为200-400mg/L,加入的经碱液混凝后的溶液的体积为1‰-5‰,经过12-18h处理后,出水COD的去除率在40%-65%。活性污泥对废水仍有较好的处理能力;处理液可返回到生化尾水段生化系统进一步生物降解,实现了高浓脱附液的循环处理。
步骤2)所用的混凝剂为FeCl3·6H2O、FeSO4·7H2O、Al2(SO4)3·18H2O、聚合氯化铝或PAC。加入的混凝剂在溶液中的质量百分比为1%-5%。混凝沉淀后的溶液的pH值在2-5之间。
步骤3)加入的FeSO4·7H2O的所占溶液?质量百分比为0.1%-2%。所用Fenton试剂,其中加入的重量百分比含量30%的过氧化氢溶液的质量百分比为1%-4%。通入的臭氧的浓度为3mg/L-10mg/L。
步骤4)所用的碱液为氢氧化钠或氢氧化钙溶液。
3、有益效果
本发明一种基于深度净化废水后树脂高浓脱附液的处置方法,利用纳滤膜对树脂脱附液进行截留,可分为纳滤膜透过液及纳滤膜截留液两部分;其中纳滤膜透过液可经氧化后作为脱附剂重复利用,纳滤截留液可通过混凝、氧化、再混凝组合工艺对其进行预处理,经处理后的纳滤截留液TOC、UV254均有很大程度上的去除,BOD5/CODcr提高至0.4以上,然后将处理液用活性污泥法进行进一步处理。因此,纳滤截留液经上述工艺处理后,可返回到生化尾水段的生化系统中,从而得到很好的处理。该方法可广泛使用于各类利用阴离子交换树脂技术对生化尾水进行处理时产生的高浓脱附液的处理。
具体实施方式
以下通过具体实施实例进一步说明本发明
实施例1
印染废水经生化处理后的生化尾水经阴离子交换树脂深度处理后产生大量的树脂脱附液,将树脂脱附液经纳滤膜后得到的纳滤截留液(TOC含量为3000mg/L,pH=9.0-10.5)用1%(w/w)的FeCl3·6H2O溶液,进行混凝沉淀,取混凝上清液进行Fenton氧化,加入FeSO4·7H2O的量为0.1%(w/w),30%的过氧化氢溶液的量为1%(w/w),反应3h,再将Fenton氧化后的氧化液用氢氧化钙乳浊液进行混凝沉淀,调节pH=8.5后沉淀0.5h,经处理后溶液的TOC的去除率为60%。将氢氧化钙混凝后的得到的处理液进入活性污泥系统中进行进一步处理。进水COD为200mg/L,加入的处理液的重量为生化尾水的1‰,经过12h处理后,出水COD的去除率为40%。经多次重复实验后证明,处理液可返回到生化尾水段生化系统进一步生物降解,实现高浓脱附液的循环处理。
实施例2
将树脂脱附液经纳滤膜后得到的纳滤截留液(TOC含量为3500mg/L,pH=9.0-10.5)用5%(w/w)的Al2(SO4)3·18H2O溶液,进行混凝沉淀,取混凝上清液进行Fenton氧化,加入FeSO4·7H2O的量为0.5%(w/w),30%的过氧化氢溶液的量为1%(w/w),反应3h,再将Fenton氧化后的氧化液用氢氧化钠溶液调节pH=9.5后沉淀0.5h,经处理后溶液的TOC的去除率为80%。将氢氧化钠混凝后的得到的处理液进入活性污泥系统中进行进一步处理。进水COD为200mg/L,加入的处理液的体积为1‰,经过12h处理后,出水COD的去除率为40%。经多次重复实验后证明,处理液可返回到生化尾水段生化系统进一步生物降解,实现高浓脱附液的循环处理。
实施例3
将树脂脱附液经纳滤膜后得到的纳滤截留液(TOC含量为3000mg/L,pH=9.5-10)用1%(w/w)的FeSO4·7H2O溶液,进行混凝沉淀,取混凝上清液进行臭氧氧化,通入的臭氧的浓度为3mg/L,反应3h,再将臭氧氧化后的氧化液用氢氧化钙乳浊液进行混凝沉淀,调节pH=10.5后沉淀0.5h,经处理后溶液的TOC的去除率为65%,BOD5/CODcr提高至0.41。将氢氧化钙混凝后的得到的处理液进入活性污泥系统中进行进一步处理。进水COD为400mg/L,加入的处理液的体积为5‰,经过18h处理后,出水COD的去除率为65%。经多次重复实验后证明,处理液可返回到生化尾水段生化系统进一步生物降解,实现高浓脱附液的循环处理。
实施例4
将树脂脱附液经纳滤膜后得到的纳滤截留液(TOC含量为3500mg/L,pH=9.5-10)用2%(w/w)的PAC溶液,进行混凝沉淀,取混凝上清液进行臭氧氧化,通入的臭氧的浓度为10mg/L,反应5h,再将臭氧氧化后的氧化液用氢氧化钠溶液进行混凝沉淀,调节pH=9.0后沉淀0.5h,经处理后溶液的TOC的去除率为70%,BOD5/CODcr提高至0.45。将氢氧化钠混凝后的得到的处理液进入活性污泥系统中进行进一步处理。进水COD为400mg/L,加入的处理液的体积为5‰,经过18h处理后,出水COD的去除率为65%。经多次重复实验后证明,处理液可返回到生化尾水段生化系统进一步生物降解,实现高浓脱附液的循环处理。
Claims (9)
1.一种基于深度净化废水后树脂高浓脱附液的处置方法,其步骤为:
a)经过阴离子交换树脂处理的高浓脱附液经过纳滤膜截留后分为高浓纳滤截留液以及纳滤透过液,纳滤透过液经氧化以后可以作为脱附剂重复利用;
b)在步骤a)产生的高浓纳滤截留液中加入混凝剂,进行混凝沉淀;
c)对混凝沉淀后的上清液进行Fenton氧化或臭氧氧化1-5h;
d)将c)反应后的溶液,加入碱液,调节至pH值为8.5-10.5,进一步混凝沉淀;
e)将d)混凝沉淀后的液体返回到生化尾水段的生化系统进一步进行生物降解。
2.根据权利要求1所述的一种基于深度净化废水后树脂高浓脱附液的处置方法,其特征在于步骤b)所用的混凝剂为FeCl3·6H2O、FeSO4·7H2O、Al2(SO4)3·18H2O或聚合氯化铝。
3.根据权利要求2所述的一种基于深度净化废水后树脂高浓脱附液的处置方法,其特征在于步骤b)加入的混凝剂在溶液中的质量百分比为1%-5%。
4.根据权利要求3所述的一种基于深度净化废水后树脂高浓脱附液的处置方法,其特征在于步骤b)混凝沉淀后的溶液的pH值在2-5之间。
5.根据权利要求1~3中任一项所述的一种基于深度净化废水后树脂高浓脱附液的处置方法,其特征在于步骤c)加入的FeSO4·7H2O的所占溶液质量百分比为0.1%-2%。
6.根据权利要求1~3中任一项所述的一种基于深度净化废水后树脂高浓脱附液的处置方法,其特征在于步骤c)所用Fenton试剂,其中加入的重量百分比含量30%的过氧化氢溶液的质量百分比为1%-4%。
7.根据权利要求1~3中任一项所述的一种基于深度净化废水后树脂高浓脱附液的处置方法,其特征在于步骤c)通入的臭氧的浓度为3mg/L-10mg/L。
8.根据权利要求1~3中任一项所述的一种基于深度净化废水后树脂高浓脱附液的处置方法,其特征在于步骤d)所用的碱液为氢氧化钠或氢氧化钙溶液。
9.根据权利要求1~3中任一项所述的一种基于深度净化废水后树脂高浓脱附液的处置方法,其特征在于步骤e)的混凝沉淀后的液体进行生物降解,其在活性污泥系统中的停留时间为12-18h。
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