生物预处理工艺—催化铁与混凝协同处理工业废水的研究

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摘要

浙江某污水处理厂废水以印染废水和化工废水为主。该厂印染废水 pH 较高，

且SS 较高；化工废水 pH 较低，水质复杂，可生化性差，处理难度很大。针对目

前废水处理工艺优化通常侧重于改善具体某一单元处理效果的情况，开展了混凝

法协同生物法处理印染废水的连续流小试。针对该厂化工废水酸度大特点，开展

了催化铁法预处理酸性化工废水以及利用其产生的亚铁离子进行混凝处理的序批

式试验。考虑到该厂印染废水碱性大的特点，开展了酸性化工废水经催化铁预处

理后和碱性印染废水混合，进行混凝反应，最后进行生物处理的小试研究，考察

了各影响因素对处理效果的影响，并进行了原因分析。以期实现缓冲酸性废水，

充分利用产生的亚铁离子的混凝作用，达到降低费用和提高效果的双重目的，同

时为同类废水处理提供参考。

混凝生物法处理印染废水试验表明，在较高 pH 条件下，整个系统的各项废

水指标可以达标排放，在较低 pH 条件下，系统的 COD、总氮、氨氮难以达标排

放。对整个系统来说，混凝 pH 为7.9-8.2 时，整个系统对 COD 的处理效果最优，

平均去除率为 91.3%，平均出水 COD为103mg/L，其他指标也可达标排放。机械

和曝气两种混凝搅拌方式比较，在混凝 pH 为5.9-6.5 的条件下，曝气搅拌效果较

好，在混凝 pH为6.5-7.2 的条件下，机械搅拌效果较好。

催化铁/混凝法预处理试验表明，pH 值是催化铁预处理酸性化工废水 Fe2+产

生量和混凝效果的关键因素。催化铁法预处理化工废水的最适宜条件为：催化铁

反应初始 pH 为2.75，反应时间为 1h；混凝反应最佳条件为：Fe2+浓度为

120mg/L，pH 控制在 8.0-8.5；总体 COD 去除率为 56.8%，色度去除率为 92%。

催化铁处理后的化工废水与印染废水混合进行混凝反应的最佳比例为 1:6，其处

理效果与投加亚铁盐混凝相当。

催化铁/混凝与生物法连续流试验表明，该系统是可行的，对 COD 去除率约

为80-92%。延长停留时间、增大回流比、提供曝气都可以提高催化铁处理化工废

水出水 pH、产生的 Fe2+浓度、COD 去除，增强处理效果。为了有利于后续混凝

处理，选择停留时间为 3h，回流比为 2，并提供曝气的工况下进行催化铁处理化

工废水的试验。混合废水的混凝的适宜条件是 Fe2+浓度为 120mg/L，pH 为8-8.5，

搅拌强度为 39.3s-1。投加 PAM 对混凝处理有极其积极的影响，可以大大减小构

筑物体积。在一定容积负荷内，生化处理效果稳定，COD去除率为 70%左右。

关键词：催化铁化工废水印染废水混凝生物接触氧化

ABSTRACT

ZheJiang sewage treatment plant received mostly printing and dyeing wastewater,

as well as chemical wastewater.The printing and dyeing wastewater were high in pH

and SS.Owing to low pH,complex component,poor biodegradability,chemical wastewa-

ter treatment was very difficult. In view of the current wastewater treatment process

optimization which usually focused on improving the specific unit treatment,the conti-

nuous experiment that printing and dyeing wastewater treated by coagulation and

biological process was carried out. According to big acidity of chemical wastewater, the

Sequencing Batch experiment that acidic Chemical Wastewater preconditioned by catal-

yzed iron and coagulation process was carried out. In view of big alkalinity of printing

and dyeing wastewater, coagulation and subsequent biological experiment of printing

and dyeing wastewater and chemical wastewater preconditioned by catalyzed iron were

carried out.The effect of various influence factors on the treatment effect was investi-

gated,as well as the reason analysis.The purpose of this experiment were to buffer acidic

waste water, make full use of the ferrous ion coagulation effect, reduce cost and impro-

ve the effect,and provide a reference for the similar wastewater treatment at the same

time.

The experience that coagulation and biological method treated printing and dyeing

wastewater showed that the effluent indexes of the system could reach discharge

standards at higher pH conditions,and COD, total nitrogen, ammonia nitrogen were diff-

icult to reach discharge standards in the condition of low pH. When coagulation pH was

7.9-8.2, the treatment effect on COD was optimal for the entire system,and the other

indexes also could reach discharge standards. The average effluent COD was

103mg/L,and the average removal rate was 91.3%.Compared with mechanical agitation

and Aeration mixing，aeration mixing effect was good in under 5.9-6.5 of coagulation

pH, mechanical agitation effect was better in under 6.5-7.2 of coagulation pH.

The pretreatment experience of catalyzed iron and coagulation process showed that

pH was the key factor of Fe2+ generation and coagulation effect. The optimum conditi-

ons of the catalyzed iron pretreatment were 2.75 of initial pH and 1 hour of reaction

time, and the optimum conditions of coagulation reaction were 120 mg/L of Fe2+ con-

centration, 8.0-8.5 of pH valure.The system removal rates of COD and colority were

56.8% and 92%, respectively.when the pretreated chemical industrial wastewater and

printing and dyeing wastewater were mixed at the ratio of 1:6,the treatment effect was

similar to adding ferrous salt.

The continuous experience of catalyzed iron —coagulation—biological process

showed that the system was feasible,and the removal rate of COD was about 80-

92%.Prolongation of residence time, enlargement of reflux ratio, aeration could all

increase pH, the Fe2+ concentration, COD removal of the catalyzed iron treatment

effluent,and enhanced treatment effect. In order to conducive to subsequent coagulation

treatment, 3 hour of reaction time, 2 of reflux ratio and aeration conditions were

selected to conduct chemical wastewater treatment by catalyzed iron. The optimum

coagulation conditions of mixed wastewater were 120 mg/L of Fe2+ concentration,8.0-

8.5 of pH valure, 39.3s-1 of stirring intensity.The addition of PAM on coagulation

treatment had a positive impact which could greatly reduce the volume of sedimentation

tank.Wastewater biotreatment effect was stable in certain volume loading,and the

removal rate of COD was about 70%.

Key Word：Catalyzed Iron, Chemical Wastewater, Printing and

Dyeing Wastewater, Coagulation, Biological Contact Oxidation

中文摘要

ABSTRACT

第一章绪论 .................................................................................................................. 1

1.1 化工废水处理研究现状........................................................................................ 1

1.1.1 化工废水概述 ................................................................................................. 1

1.1.2 化工废水处理技术 ......................................................................................... 2

1.1.3 化工废水处理技术的进展 ............................................................................. 4

1.2 催化铁内电解技术................................................................................................ 4

1.2.1 催化铁内电解法处理废水的原理 ................................................................. 5

1.2.2 催化铁内电解法在处理工业废水中的应用 ................................................. 6

1.3 混凝法.................................................................................................................... 9

1.3.1 混凝机理 ......................................................................................................... 9

1.3.2 影响混凝沉淀的主要因素 ........................................................................... 10

1.4 课题研究的目的和内容...................................................................................... 12

1.4.1 课题研究的目的和意义 ............................................................................... 12

1.4.2 课题研究的内容 ........................................................................................... 13

1.4.3 课题来源 ....................................................................................................... 14

第二章试验材料与方法 .............................................................................................. 15

2.1 试验材料与试剂.................................................................................................. 15

2.1.1 废水来源及水质 ........................................................................................... 15

2.1.2 试验材料及主要试剂 ................................................................................... 15

2.2 试验设备与分析方法.......................................................................................... 16

2.2.1 试验主要仪器设备 ....................................................................................... 16

2.2.2 试验分析方法 ............................................................................................... 16

2.3 试验方法.............................................................................................................. 17

2.3.1 混凝法协同生物法处理印染废水的连续流小试 ....................................... 17

2.3.2 催化铁协同混凝法预处理酸性化工废水的序批式试验 ........................... 18

2.3.3 催化铁与混凝协同及生物法工艺处理工业废水的连续流小试 ............... 19

第三章混凝法协同生物法处理印染废水的小试研究 .............................................. 21

3.1 生物处理工艺的确定.......................................................................................... 21

3.1.1 反应器的启动 ............................................................................................... 21

3.1.2 温度的影响 ................................................................................................... 22

3.1.3 停留时间和容积负荷的影响 ....................................................................... 22

3.2 有机物的去除...................................................................................................... 23

3.2.1 连续运行效果 ............................................................................................... 23

3.2.2 不同 pH值范围下的去除效果 .................................................................... 23

3.3 总磷的去除.......................................................................................................... 25

3.4 总氮的去除.......................................................................................................... 26

3.5 氨氮的去除.......................................................................................................... 26

3.6 硝酸盐氮和亚硝酸盐氮的去除.......................................................................... 27

3.7 混凝采用机械搅拌和曝气两种方式对比.......................................................... 28

3.7.1 混凝 pH为5.9-6.5 ........................................................................................ 29

3.7.2 混凝 pH为6.5-7.2 ........................................................................................ 30

3.8 本章小结.............................................................................................................. 30

第四章催化铁协同混凝法预处理酸性化工废水的序批式试验研究 ...................... 32

4.1 催化铁处理化工废水序批试验.......................................................................... 32

4.1.1 反应时间对 pH值变化和 Fe2+产生的影响................................................. 32

4.1.2 废水初始 pH的影响 .................................................................................... 33

4.1.3 适宜催化铁/混凝处理的废水 pH范围 ....................................................... 34

4.2 酸性化工废水的混凝试验.................................................................................. 35

4.2.1 混凝 pH的选择 ............................................................................................ 35

4.2.2 混凝亚铁离子浓度的选择 ........................................................................... 36

4.2.3 催化铁/混凝处理酸性化工废水最适宜 pH和反应时间的选择 ............... 37

4.3 催化铁出水与印染废水混合共同混凝试验...................................................... 37

4.3.1 混凝 pH对处理效果的影响 ........................................................................ 37

4.3.2 混合比例对混凝效果的影响 ....................................................................... 38

4.4 本章小结.............................................................................................................. 39

第五章催化铁与混凝协同及生物法工艺处理工业废水的小试研究 ...................... 40

5.1 催化铁处理化工废水的因素研究...................................................................... 40

5.1.1 水力停留时间的影响 ................................................................................... 40

5.1.2 回流比的影响 ............................................................................................... 41

5.1.3 曝气的影响 ................................................................................................... 41

5.1.4 曝气回流的影响 ........................................................................................... 42

5.1.5 反应器冲洗的影响 ....................................................................................... 43

5.2 混合废水混凝的因素研究.................................................................................. 44

5.2.1 亚铁离子浓度的影响 ................................................................................... 44

5.2.2 pH值的影响 ................................................................................................. 45

5.2.3 搅拌强度的影响 ........................................................................................... 46

5.2.4 沉淀时间的影响 ........................................................................................... 47

5.2.5 阴离子型 PAM 投加的影响......................................................................... 47

5.3 生物接触氧化法处理.......................................................................................... 48

5.4 本章小结.............................................................................................................. 49

第六章结论与建议 ...................................................................................................... 50

6.1 结论...................................................................................................................... 50

6.1.1 混凝法协同生物法处理印染废水的小试研究 ........................................... 50

6.1.2 催化铁协同混凝法预处理酸性化工废水的序批式试验研究 ................... 50

6.1.3 催化铁与混凝协同及生物法工艺处理工业废水的小试研究 ................... 50

6.2 建议...................................................................................................................... 51

参考文献 ........................................................................................................................ 52

在读期间公开发表的论文和承担科研项目及取得成果 ............................................ 57

致谢 ............................................................................................................................ 58

第一章绪论

1.1 化工废水处理研究现状

1.1.1 化工废水概述

化学工业是一个行业多，品种多的工业部门，包括化肥、涂料、染料、农药、

纯碱、硫酸、炭黑、无机盐、有机化工、橡胶等二十几个行业，生产了多种产品。

化学工业在国民经济中既是用水大户，也是一个“工业三废”排放量大、容易产生

污染、危害环境的“污染大户”，化工行业在全国工业废水排放总量中名列前茅[1]。

1.1.1.1 化工废水的来源和分类

化工废水来自化工生产过程，主要包括物料在开采、运输过程中被雨水冲刷

流失而形成的废水，副反应和反应不完全形成的废料，生产过程排出的废水，冷

却水以及设备清洗用水。

图1-1 化工废水来源图

根据废水中污染物的主要成分，可分为有机废水，无机废水和综合废水。有

机废水主要来自合成材料、有机化工及农药、染料行业废水；无机废水主要来自

无机盐，无机肥、无机酸碱等行业的废水；综合废水既含有机物又含无机物的废

水，如氯碱、感光材料、涂料、及颜料行业的废水[2]。

1.1.1.2 化工废水的特点和危害

由于化学工业是对各种物料进行化学处理和转化加工的生产部门，具有多原

料、多工艺、多产品、多方式的特点，因此，化工废水有以下特点和危害。

(1)有毒性和刺激性，不易生物降解。化工废水中含有多种污染物，有些是有

毒的物质，如氰及腈化物、酚类和砷、汞、镉、铅等重金属；有的物质难以降解，

化工厂

农药厂

有机

化工厂

化肥厂

石油

化工厂

无机

化工厂

冷却设备

水源

有毒物质

好氧物质

植物营

养物质

高温废水

酸碱物质

油类物质

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摘要：

摘要浙江某污水处理厂废水以印染废水和化工废水为主。该厂印染废水pH较高，且SS较高；化工废水pH较低，水质复杂，可生化性差，处理难度很大。针对目前废水处理工艺优化通常侧重于改善具体某一单元处理效果的情况，开展了混凝法协同生物法处理印染废水的连续流小试。针对该厂化工废水酸度大特点，开展了催化铁法预处理酸性化工废水以及利用其产生的亚铁离子进行混凝处理的序批式试验。考虑到该厂印染废水碱性大的特点，开展了酸性化工废水经催化铁预处理后和碱性印染废水混合，进行混凝反应，最后进行生物处理的小试研究，考察了各影响因素对处理效果的影响，并进行了原因分析。以期实现缓冲酸性废水，充分利用产生的亚铁离子的混凝作用，达...

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