摘 要
本文以驻马店市某皮革废水治污中心运行工况为例。在历时 7 个月的跟踪调研中可以看出，由于含铬废水中悬浮物浓度值较高，若仅采用加碱沉淀工艺难以使废水中总铬浓度满足国标中不大于 1.5mg/L 的排放标准限值，而综合废水经过格栅、预沉、加药絮凝等一级处理后，水质有了较大改善，各项污染物浓度相对稳定。再经二级生化处理后，水质中除 CODCr浓度仅能满足国标中间接排放标准限值外，其它污染物浓度均能满足直接排放标准限值。因此，探索出高效、稳定、运行费用低的制革废水处理工艺已经成为皮革行业亟待解决的问题。
首先，本文针对含铬废水分别采用加碱沉淀工艺、加碱-絮凝剂联用工艺、先加碱沉淀后使用絮凝剂助沉工艺、先加碱沉淀后砂滤罐过滤工艺四种方法处理。从实验结果可以看出，后三种工艺均可以使废水中总铬含量降低至国标中排放标准限值之下，但加碱-絮凝剂联用工艺运行费用最高，其次为先加碱沉淀后使用絮凝剂助沉工艺，而先加碱沉淀后砂滤罐过滤工艺运行费用最低，适合处理含铬废水水量大，需要长期运行的皮革废水处理企业。
针对皮革废水二级生化出水，本文首先采用填料法处理工艺，结果表明填料对CODCr的去除效果不太理想，去除率仅维持在 12%~13%之间，未使 CODCr浓度降低至国标中直接排放标准限制之下。其次，研究采用臭氧氧化、次氯酸钠氧化、Fenton 氧化三种高级氧化工艺处理，结果表明三种工艺对水质色度的去除率均在 90%以上；仅次氯酸钠氧化工艺对氨氮的去除效果最佳，去除率接近 100%;臭氧氧化和次氯酸钠氧化这两种工艺对 CODCr的去除效果较差，但在初始 pH 值为 4,H2O2投加量为 600mg/L,Fe2+投加量为 400mg/L,反应时间为 50min 的条件下，采用 Fenton 氧化工艺 CODCr的去除率可以达到 50%以上，CODCr的浓度值可以满足国标中连续排放限值要求。同时，设计单因素实验验证，在 Fenton 氧化工艺中，采用 PVC 穿孔曝气管进行曝气搅拌和在反应终止时将 pH 值调节到 8 以终止反应两种方式，对 Fenton 氧化工艺效果不会产生影响。
采用这两种方式不仅可以减少设备资金投入和维修成本，也可减少药品的投加量，降低企业的运行费用。
最后，以焦作某皮革公司废水治理项目为例，通过实际运行结果可以看出，含铬废水经加碱沉淀后上清液再通过砂滤罐工序处理，出水总铬浓度可以满足国标的排放标准；综合废水经过先物化后生化，最终由 Fenton 工艺氧化后出水水质稳定，色度倍数仅有 2倍，同时 CODCr及氨氮浓度值远低于国标中直接排放浓度限值。
综上所述，采用上述两种改进工艺对皮革废水处理后，出水水质更加稳定，故非常适合长期运行。
关键词：皮革废水；砂滤罐；填料；高级氧化
Abstract
The operating state of a tannery wastewater treatment center in Zhumadian was taken asan example in this paper. From the seven months tracking research, it can be seen that if thealkali precipitation process was used only, it was difficult to make the total chromium contentto meet the national standard, which requires the emission of chromium cannot more than1.5mg/L, for the concentration of suspended matter in chromium-containing wastewater had ahigh value. It can be seen that water quality had greatly improved and the pollutantconcentration maintained stable after the integrated wastewater went through the firsthandling processes, such as grille, primary sedimentation, and flocculation. After the waterwent through the second biochemistry handling process, besides CODCr, the concentration ofother pollutants in the water could meet the direct emission standard limits. In this situation,the concentration of CODCrcould only meet indirect emission standard limit of the nationalstandard. Therefore, it is urgency of finding a efficient, stable, low operating costs tannerywastewater treatment process for leather industry.
Firstly, alkali sedimentation process, alkali - flocculent combined process, alkaliprecipitation followed coagulant aids precipitation co-precipitation process and alkaliprecipitated followed sand filtration tank filter process were used to handle thechromium-containing wastewater. As can be seen from the experimental results, the last threeprocesses could reduce the total chromium content in wastewater to emission standard limit.
But at the same time, the cost of alkali - flocculent combined process was the highest. Thealkali precipitation followed coagulant aids precipitation co-precipitation process followed.
And alkali precipitated followed sand filtration tank filter process was the last. So the alkaliprecipitated followed sand filtration tank filter process was suitable to treat the large amountchromium- containing wastewater and for the enterprises which needed long-term treatmentof leather wastewater.
For secondary biochemical leather wastewater, filler treatment process was used at first.
The results showed that removal effect of the filler to the CODCrwas not good. And theremoval efficiency was between 12% and 13%. The concentration of CODCrwas still largerthan the direct emission standard limit of the national standard. Secondly, ozone oxidation,sodium hypochlorite oxidation and Fenton oxidation were used. The results showed thatremoval effects of these three kinds of processes on the water chromaticity were lager than90%. The removal effects on ammonia nitrogen were the best when the sodium chlorateoxidation process was used. And the removal efficiency of ammonia nitrogen could reach100%. Ozone oxidation process and sodium chlorate oxidation process had little effect on theconcentration of CODCr. When the value of pH was 4, the addition amount of H2O2was600mg/L, the addition amount of Fe2+was 400mg/L, and the reaction time was 50min, theremoval efficiency of CODCrby Fenton oxidation process was larger than 50%. Theconcentration of CODCrcould meet the direct emission standard limit of the national standard.
At the same time, single factor experiment was designed during Fenton oxidation process.
Two measures were tried. One was aeration stirring used PVC perforated aeration tube. Theother was to adjust the value of pH to 8 when the reaction was terminated. Using these twomeasures could not only reduce the capital investment of equipment and the costs ofmaintenance, but also reduce the dosage of drugs and the operating cost.
Finally, the wastewater treatment project of a leather industry in Jiaozuo was taken asanother example in this paper. It could be seen from the actual operating result that after thewastewater was treated by the alkali precipitated followed sand filtration tank filter process.
The effluent concentration of total chromium could meet the direct emission standard limit.
After the integrated wastewater went through physicochemical treatment at first, thenbiochemical treatment, finally Fenton oxidation process, the quality of resulting water wasstable. The value of color multiple was just 2. And the concentration of CODCrand ammonianitrogen far bellowed the direct emission standard limits.
To sum up, after the two improved leather wastewater treatment processes were used,thequality of resulting water was more stable. So the improved processes were suitable forlong-term operation.
Key words: Leather wastewater;Sand filtration tank;Filler;Advanced oxidation process
目 录
摘 要
Abstract
目 录
第一章 绪论
1.1 研究背景
1.2 皮革废水的来源及水质特性
1.2.1 皮革废水来源
1.2.2 皮革废水的水质特性
1.3 皮革废水处理技术国内外研究现状
1.3.1 含铬废水处理
1.3.2 含硫废水预处理
1.3.3 综合废水处理
1.4 课题研究的内容
1.4.1 本课题的提出
1.4.2 课题研究内容
1.4.3 课题研究意义
第二章 驻马店市某皮革废水治污中心运行工况的调研
2.1 治污中心简介
2.2 水污染物排放标准
2.3 治污中心运行监测
2.3.1 实验试剂
2.3.2 实验仪器
2.3.3 检测方法
2.3.4 治污中心各单元运行工况
2.4 本章小结
第三章 含铬废水工艺研究
3.1 实验材料及检测方法
3.1.1 实验用水
3.1.2 实验试剂
3.1.3 实验仪器
3.1.4 检测方法
3.2 实验方法及结果分析
3.2.1 加碱沉淀工艺
3.2.2 加碱-聚合氯化铝联用工艺
3.2.3 加碱-硫酸亚铁联用工艺
3.2.4 加碱沉淀后聚合氯化铝絮凝助沉工艺
3.2.5 加碱沉淀后硫酸亚铁絮凝助沉工艺
3.2.6 加碱沉淀后砂滤罐（上进水式）过滤工艺
3.2.7 加碱沉淀后砂滤罐（下进水式）过滤工艺
3.3 药剂成本分析
3.4 本章小结
第四章 填料法处理皮革废水二级生化出水的研究
4.1 实验材料及检测方法
4.1.1 实验用水
4.1.2 实验填料
4.1.3 实验试剂
4.1.4 实验仪器
4.1.5 检测方法
4.2 实验方法及结果分析
4.2.1 实验方法
4.2.2 实验结果
4.3 本章小结
第五章 高级氧化法处理皮革废水二级生化出水的研究
5.1 实验材料及检测方法
5.1.1 实验用水
5.1.2 实验试剂
5.1.3 实验仪器
5.1.4 检测方法
5.2 实验方法及结果分析
5.2.1 臭氧氧化皮革废水二级生化出水
5.2.2 次氯酸钠氧化皮革废水二级生化出水
5.2.3 Fenton 氧化皮革废水二级生化出水
5.3 本章小结
第六章 焦作某皮革公司废水治理中心运行工况
6.1 项目介绍
6.2 污水处理中心各单元运行工况
6.2.1 实验试剂
6.2.2 实验仪器
6.2.3 检测方法
6.2.4 各单元运行工况
6.3 工艺创新性
6.4 本章小结
总 结
参考文献
致 谢
