CN107758958B - 一种印染混排废水的处理方法及系统 - Google Patents
一种印染混排废水的处理方法及系统 Download PDFInfo
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Abstract
本发明涉及废水处理技术领域,尤其涉及一种印染混排废水的处理方法及系统,该处理方法包括依次对废水进行冷冻处理、MVR蒸发浓缩处理、卤水除杂处理和生物氧化处理的步骤,本发明将冷冻结晶法、MVR蒸发浓缩和卤水除杂相结合,很好的实现了对印染混排废水的深度处理,结晶制得的固体硫酸钠和得到的氯化钠水溶液可再次利用,实现了资源的重复利用,且本发明所述的方法操作简单,易于大规模对印染混排废水进行处理。
Description
技术领域
本发明涉及废水处理技术领域,尤其涉及一种印染混排废水的处理方法及系统。
背景技术
印染废水和电厂脱硫废水都属于高盐难降解废水,其内含有大量的SO4 2-和Cl-,且都不适合用传统生化方法来处理。大多数印染产业园由于用电量较大,市政供电不能全部满足生产需求,一般会建设自备电厂,电厂脱硫废水与园区印染废水混合形成的废水成为高盐难降解废水的主要来源。
处理印染厂废水的传统方法是热法盐硝联产工艺。该工艺具体为:原卤经过净化处理制得精卤(其成分含量为:NaCl 290-305g/L,Na2SO4 15-25g/L,其他杂质为钙、镁离子及不溶物,均以ppm计)送入EV201蒸发析盐,顺流排经EV202、EV203蒸发结晶后再送入EV304(料温47.9℃),析盐母液送入EV301(料温为100℃)析硝。析硝母液返回EV304,实现高温析硝,低温析盐,将盐硝分离,制成产品。该工艺对洗涤后卤水加盐量难以控制,致使盐析时一次硝中氯化钠含量过多或过少;此外,卤水中的钙、镁、铁、铜等杂质在盐析时会大量带入一次硝中,严重影响一次硝的质量;而且传统热联产方法芒硝回收率低。
冷冻结晶法生产芒硝过程中,将含硫酸钠和氯化钠的废水经过冷冻,硫酸钠浓度达过饱和,以十水硫酸钠结晶析出。采用冷却结晶法分离硫酸钠可使制盐工业的能耗和建设投资及两碱工业的生产成本大大降低,分离获得的芒硝则是一种重要的轻工、化工工业原料。
冷冻结晶处理后的溶液存在硫酸根杂质。传统除硝法有氯化钙法、氯化钡法等。其中,氯化钙法存在以下缺点:1、在精制过程中引入了对离子膜有害的Ca2+,这将导致在一次精制过程中辅助精制剂(纯碱)费用的上升;2、虽然除硝卤水中SO4 2-很少,但在一次卤水精制过程中还须进一步除去SO4 2-,导致精制费用的增加。氯化钡法的缺点是碳酸钡溶解度较小,碳酸钡的转化率将直接影响盐水精制的费用。除此之外,采用这两种方法去除硫酸根杂质的同时会较多的引入Cl-,继而会引起精制费用上升。
有鉴于此,提出一种处理印染混排废水的方法很有必要。
发明内容
本发明的目的是针对现有技术存在的缺陷和不足,提供一种印染混排废水的处理方法,该方法能够实现污水的深度处理和资源化利用。
为了实现上述目的,本发明采用如下技术方案:
一种印染混排废水的处理方法,包括先对所述印染混排废水进行冷冻处理,再经MVR蒸发浓缩的步骤。
具体地,所述步骤的具体操作为:冷冻所述废水使其中的Na2SO4浓度达到过饱和,析出Na2SO4·10H2O晶体,收集晶体;将除去晶体后的废水通入MVR蒸发器浓缩。
由于Na2SO4的溶解度随着温度降低而降低,因此采用冷冻法使废水中的Na2SO4达到过饱和状态,以Na2SO4·10H2O状态析出。其中,收集晶体的操作可在沉降池中进行,优选地,废水在沉降池的停留时间为2-3h,此时,能够最大程度回收Na2SO4·10H2O晶体。
冷冻废水时,如果冷冻温度较高(如0℃左右),则只有较少晶体析出,冷冻温度过低(如-20℃左右),虽然有助于晶体析出,但会提高设备运行成本。因此,本发明优选的冷冻温度为-5℃~-10℃,在此温度下冷冻析晶,得到的Na2SO4·10H2O晶体,可直接作为副产进行销售,可实现资源的充分回收利用,并且温度适中,成本较低。
MVR蒸发器的工作原理为本领域技术人员所知晓,本发明利用MVR蒸发器对废水中的氯化钠进行浓缩。废水可直接进入MVR蒸发器,也可经过预热后再通入MVR蒸发器,本发明优选将废水先经预热后再进行蒸发,进一步优选预热后废水的温度为30-40℃。废水预热后有助于蒸发的顺利进行,且可降低蒸发所需的能耗。
具体而言,将废水导入MVR蒸发器的加热室进行预热,然后将预热后的废水导入蒸发室蒸发,蒸发出的水蒸气经过管道导入加热室作为加热废水的热源,加热后水蒸气转变为清洁的冷凝水,收集备用;经过蒸发室蒸发后即可得到氯化钠的浓缩废水。
本发明优选地,将冷冻过程中释放的热量导入MVR蒸发器,作为预热废水的能量,充分实现能量的回收利用,节约能源。
优选地,所述处理方法还包括向浓缩后的废水中加入氯化钙和碳酸钡以除去废水中剩余的SO4 2-的步骤。
本发明在除去剩余SO4 2-时采用氯化钙和碳酸钡两种试剂,能够有效减少Cl-的引入,减少精制费用;此外,由于采用碳酸钡,使得氯化钙的用量相对减少,减少了Ca2+的引入,降低了Ca2+对后续膜的损害程度,减少了辅助精制剂(纯碱)的费用。
进一步优选地,氯化钙与碳酸钡的重量比为(35-40):(15-20),最优选为38:17。
优选地,本发明所述的方法还包括除去析出的BaSO4和CaSO4沉淀,再对除沉后的废水进行生物氧化处理的步骤。
其中,除去BaSO4和CaSO4沉淀可在沉降池中进行,废水在沉降池的停留时间为2-3h。
其中,生物氧化法的目的是降低废水的COD值,使其能够达标排放。生物氧化法为本领域技术人员所知晓,即以生物膜吸附废水中的有机物,在有氧的条件下,有机物由微生物氧化分解,废水得到净化。生物氧化法采用的生物膜由菌胶团、丝状菌、真菌、原生动物和后生动物组成。本发明的生物氧化法优选采用聚乙烯丝网球填料,采用人工挂膜法进行。
进一步优选地,所述生物氧化法的具体操作为:调节废水的pH值为6.5-9,于10-35℃处理6-12h。
经过处理后,废水的COD小于20,该废水可以直接作为锅炉、染织行业的软化水回收利用,实现了资源的重复利用。
作为本发明较佳的技术方案,所述处理方法包括如下步骤:
(1)于-5℃~-10℃冷冻废水使废水中的Na2SO4浓度达到过饱和,析出Na2SO4·10H2O晶体,收集Na2SO4·10H2O晶体;
(2)将步骤(1)处理后的废水通入MVR蒸发器中浓缩;
(3)向浓缩后的废水中加入氯化钙和碳酸钡使其中的SO4 2-离子沉淀析出,除去BaSO4和CaSO4沉淀;
(4)调节步骤(3)所得废水的pH值为6.5-9,以聚乙烯丝网球为填料,采用人工挂膜法,于10-35℃对所述废水进行生物氧化处理,即可。
优选地,步骤(1)和(3)中,利用沉淀池收集晶体和沉淀,废水在沉淀池中的停留时间均为2-3h。
本发明所述的废水处理方法适用于处理含有的硫酸根、氯化物、钠离子浓度高的印染混排废水,一般而言,该方法对硫酸根浓度为4000-5000mg/L,氯化物浓度为2000-2500mg/L,钠离子浓度为3000-5000mg/L的印染混排废水具有极佳的处理效果,能够有效降低硫酸根、氯化物的浓度,实现资源的回收利用。
优选地,在具体应用时,可以先对印染混排废水进行反渗透处理,对废水中的溶解盐进行初步去除,然后再进行后续的冷冻处理、MVR蒸发等操作。其中,所述反渗透操作可采用本领域常规技术手段,本发明不做具体限定。
本发明还提供了一种用于处理印染混排废水的系统,按照废水流动方向,包括顺次连接的冷冻结晶装置、第一沉淀装置、MVR蒸发装置、第二沉淀装置和生物氧化装置。
优选地,所述MVR蒸发装置包括用于预热废水的加热器,所述加热器的加热介质入口与所述冷冻结晶装置的热量出口相连通。
本发明将冷冻结晶法、MVR蒸发浓缩和卤水除杂相结合,很好的实现了对印染混排废水的深度处理,能够有效除去废水中的硫酸根离子,且结晶制得的固体硫酸钠可再次利用,可作为锅炉或印染的软水使用,实现了资源的重复利用。
在符合本领域常识的基础上,上述各优选条件可以相互组合,即得本发明各较佳实施例。
附图说明
图1为本发明的工艺流程图。
具体实施方式
以下实施例用于说明本发明,但不用来限制本发明的范围。本发明涉及到的原料或试剂均为市售产品,涉及到的操作如无特殊说明,均为本领域常规操作。
实施例1
一种印染混排废水的处理方法,工艺流程如图1所示,包括如下步骤:
(1)将电厂脱硫废水和印染废水收集于废水收集池内,控制水力停留时间为1h;
(2)于-5℃~-10℃冷冻反渗透处理后的废水使废水中的Na2SO4浓度达到过饱和,析出Na2SO4·10H2O晶体,将冷冻结晶后的废水打入一沉池沉淀2.5h,收集Na2SO4·10H2O晶体;
(3)利用步骤(2)冷冻结晶释放出的热量预热沉淀后的废水,然后将其通入MVR蒸发器中蒸发浓缩,经浓缩后废水中NaCl的浓度达到96.2%;
(4)将浓缩后的废水导入二沉池,并向废水中加入重量比例为38:17的氯化钙和碳酸钡,使其中的SO4 2-离子沉淀析出,废水在二沉池的停留时间为3h;
(5)将步骤(4)所得废水导入氧化池,采用人工挂膜法进行生物氧化处理,调节废水的pH值为7,于25℃处理10h,即可。
该实施例中,反渗透处理后的印染混排废水指标如下表1所示,废水处理前、后,硫酸根、氯离子和COD值的对比数据如表2所示:
表1:待处理的印染混排废水指标
检测项目 | 单位 | 检测结果 | 检测项目 | 单位 | 检测结果 |
pH值 | 无量纲 | 8.37 | 镁 | mg/L | 16.4 |
COD | mg/L | 77.9 | 钠 | mg/L | 3540.2 |
氨氮 | mg/L | 1.65 | 钾 | mg/L | 67.8 |
钙 | mg/L | 45.2 | 氯化物 | mg/L | 2222.5 |
硝酸根 | mg/L | 77.6 | 硫酸根 | mg/L | 4376.5 |
表2:处理前后废水的指标变化数据
SO<sub>4</sub><sup>2-</sup>浓度 | Cl<sup>-</sup>浓度 | COD值 | |
处理前 | 4.37g/l | 2.22g/l | 77.9 |
处理后 | 0.009g/l | 0.01g/l | 15 |
虽然,上文中已经用一般性说明、具体实施方式及试验,对本发明作了详尽的描述,但在本发明基础上,可以对之作一些修改或改进,这对本领域技术人员而言是显而易见的。因此,在不偏离本发明精神的基础上所做的这些修改或改进,均属于本发明要求保护的范围。
Claims (2)
1.一种印染混排废水的处理方法,其特征在于:
(1)于-5℃~-10℃冷冻废水使废水中的Na2SO4浓度达到过饱和,析出Na2SO4·10H2O晶体,收集Na2SO4·10H2O晶体;
(2)将步骤(1)冷冻过程中释放的热量导入MVR蒸发器,作为预热废水的能量,将步骤(1)处理后的废水通入MVR蒸发器中浓缩;
(3)向浓缩后的废水中加入氯化钙和碳酸钡,使其中的SO4 2-离子沉淀析出,除去BaSO4和CaSO4沉淀;其中,氯化钙与碳酸钡的重量比为(35-40):(15-20);
(4)调节步骤(3)所得废水的pH值为6.5-9,以聚乙烯丝网球为填料,采用人工挂膜法,于10-35℃对所述废水进行生物氧化处理6-12h。
2.根据权利要求1所述的处理方法,其特征在于:步骤(1)和(3)中,分别利用沉淀池收集晶体和沉淀,废水在所述沉淀池中的停留时间均为2-3h。
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