CN114956456A - 一种利用微生物协同絮凝剂对制浆废水进行处理的方法 - Google Patents
一种利用微生物协同絮凝剂对制浆废水进行处理的方法 Download PDFInfo
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Abstract
本发明涉及一种利用微生物协同絮凝剂对制浆废水进行处理的方法，所述方法利用滤料上生物膜的强氧化降解能力对污水进行快速净化，可以对污染物进一步降解，以便达到排放及回用标准。
Description
技术领域
本发明涉及造纸领域，具体涉及一种利用微生物协同絮凝剂对制浆废水进行处理的方法。
背景技术
造纸工业在国民经济中的有着重要地位。常见的制浆方法主要包括化学法、半化学法以及化学机械法等。在制浆过程中，常涉及大量化学试剂尤其是碱的使用，从而使得废水的污染负荷较高，废水中通常包括还原类污染物、悬浮类污染物、可生物降解类污染物和色素类污染物。
造纸工业废水的处理工作是一项重要而又艰巨的任务。目前，处理制浆造纸废水的工艺主要集中在两处：一种是在制浆过程中降低化学药水的用量，例如使用微生物预处理替代和/或协同传统化学药水预处理以降低化学药品的使用量，发明人在前期的研发中发现经过微生物预处理的木材制备得到的制浆进行抄片后，与未经微生物处理的制浆相比，可以在降低碱用量的情况使抄片的纸张性能不下降，从而使得废水中污染物减少。
另一种降低废水污染的方法是对制浆后的废物进行处理，传统的处理方法主要有物化法和生化法，随着技术的发展，高级氧化技术、膜分离技术、超临界氧化技术、光催化技术、微生物絮凝剂等一系列技术被广泛应用。
近年来，张安龙等人以升流式曝气生物滤池处理草类碱法制浆的中段废水，其CODcr和SS的去除率分别达到31％、85％。孙萌萌利用小型上流式BAF实验装置对废纸制浆废水进行二级生化处理，大量的实验证明曝气生物滤池工艺处理废纸制浆废水可以实现良好的去除效果，将BAF工艺应用于废纸制浆废水的生化处理是可行的。
但是这一系列的技术对污水的处理效果仍然具有一定的局限性，二次污染、处理成本较高等问题也比较严重。因此，开发一种新型、高效的绿色环境友好型的废水处理技术已成为一项重要任务。
发明内容
针对现有技术的不足，本发明在对不同处理方式的制浆废水中的主要污染物进行检测分析后，利用絮凝沉淀进行了初步污染处理，并通过正交实验法摸索了最佳工艺条件。同时，发明人发现，将絮凝后的废水进行曝气生物滤池处理，利用滤料上生物膜的强氧化降解能力对污水进行快速净化，可以对污染物进一步降解，以便达到排放及回用标准。
本发明的技术方案如下：
一种利用微生物协同絮凝剂对制浆废水进行处理的方法；包括如下步骤：
(1)采取制浆后得到的废水进行絮凝沉淀处理；(2)将絮凝后的废水在曝气条件下通过滤料表面附着有微生物的滤池，进行微生物处理。
根据本发明优选，步骤(1)中，所述制浆后得到的废水是经过微生物处理或者未经过微生物处理的化学机械浆，当其经过微生物处理时，所述微生物优选朱红密孔菌。
优选的，步骤(1)中的絮凝剂任选自明矾、甲壳素、聚合氯化铝、壳聚糖、FeCL3.6H2O中的一种或几种；进一步地，所述絮凝剂的用量范围为1000-3000mg/L，絮凝时间为10-35min，絮凝温度为25-75℃，絮凝pH为5-10；进一步地，絮凝剂用量为2000mg/L，所述絮凝时间为25-35min，絮凝温度为45-75℃，絮凝pH为7-9；进一步地，絮凝时间为25min，絮凝温度为65-75℃，絮凝pH为7。
优选的，步骤(1)中的絮凝剂选自明矾/甲壳素、甲壳素/聚合氧化铝、甲壳素/壳聚糖、聚合氧化铝/FeCL3.6H2O、明矾/FeCL3.6H2O、甲壳素。
优选的，步骤(2)中的微生物选自白腐菌Trametes Hirsuta、白腐菌Coriolusversicolor或二者的组合，所述微生物的加入量为50-100ppm；优选的，所述微生物的加入量为50ppm，曝气温度为25-35℃，优选28℃。
优选的，步骤(2)中滤池底部安装有曝气头，改性聚氨酯泡沫载体分散填充于滤池内，所述微生物加入滤池后经过一定的曝气时长可以在载体表面形成挂膜；形成挂膜后，将步骤(1)中絮凝后经澄清的制浆废水加入池中，继续进行曝气培养，每隔2d测一次COD值。
优选的，所述形成挂膜的曝气时长为24h；挂膜后加入经絮凝处理的废水之后再经曝气培养的时长为6-14天，优选8-10天。
优选的，步骤(2)中的曝气是指通入氧气的条件下进行微生物处理。
采用本发明的利用微生物协同絮凝剂对制浆废水进行处理的方法具有如下优点：
(1)首次以明矾+FeCL3.6H2O的絮凝组合对杨木制浆废液进行处理，发现FeCL3.6H2O的加入能对明矾的絮凝起到促进作用，大幅度提高COD去除率。
(2)采用絮凝+好氧生化处理的组合技术对杨木制浆废液处理，使曝气处理后的废水中的COD约为73mg/L，满足制浆造纸废水回用的要求。
附图说明
图1为几种絮凝体系的COD去除效果比较；
图2为不同明矾用量对COD去除的影响；
图3为不同FeCl3.6H2O用量对COD去除的影响；
图4为不同温度对COD去除的影响；
图5为不同pH对COD去除的影响；
图6为不同搅拌时间对COD去除的影响；
图7为经微生物处理过的COD去除率。
具体实施方式
实施例1纸浆废水水质分析
将1kg绝干质量的杨木片用热水浸泡12h，浸泡的料液比为1:4，取出后放入蒸煮锅中，在蒸煮时间30min、蒸煮温度100℃条件下进行预汽蒸，汽蒸结束后将木片送至单螺杆挤碾机进行挤压疏解，然后将疏解后的木片置于高压灭菌锅中，120℃灭菌1h备用。
在固体培养基(马铃薯提取液1L、20g葡萄糖、3g KH2PO4、1.5g MgSO4·7H2O、微量维生素B1，琼脂20g)斜面上4℃保存的朱红密孔菌接种于已高温灭菌的种液培养基(与固体培养基相同，但不加琼脂)28℃、180rpm下培养7d左右。取出灭菌的杨木于工作台紫外灯照射下冷却，待完全冷却后，置入聚乙烯塑料袋中，再加入培养好的朱红密孔菌菌丝球种子液，适当加入液体发酵培养基(1L马铃薯浸提液、15g葡萄糖、1.0g KH2PO4、0.5g MgSO4·7H2O、0.01g CaCl2、2.5g天冬酰胺、0.1g Na2HPO4·5H2O、0.002g CuSO4·5H2O、0.001gFeSO4·7H2O和0.05g维生素B1)，充分混合均匀，放置于30℃的生化培养箱中进行培养，湿度保持在70％-80％。定期观察木片上菌丝的生长情况，并测定朱红密孔菌在木片上生长时所分泌的漆酶酶活。朱红密孔菌生物预处理25天后结束培养，将木片上的菌丝洗净，备用。
将经朱红密孔菌处理的杨木木片洗涤干净，置于于旋转式蒸煮锅中进行蒸煮，蒸煮时间为30min，处理条件为：氢氧化钠为碱，碱液浓度6％，料液比1:4、温度130℃。将经过蒸煮预处理后的木片用KRK-2500Ⅱ型高浓磨浆机进行磨浆，采用A型磨片浆浓20％左右，设定转速3000rpm，磨片间隙0.1mm，然后再用Somerville筛浆机进行筛浆，筛缝选择0.15mm，筛浆后用PFI磨浆机进行打浆。
取上述工艺过程中的筛浆洗涤工段的废水备用，采用重铬酸钾法测定其COD，采用UV-Vis吸光度法测定废水中的木质素含量，同时测定了废水的pH值，其结果如表1。
表1.制浆废液的水质指标
实施例2不同絮凝剂的絮凝效果比较
对多种絮凝剂及其组合的效果进行了探索，各组选用的絮凝剂：1.明矾/甲壳素、2.甲壳素/聚合氧化铝、3.甲壳素/壳聚糖、4.聚合氧化铝/FeCL3.6H2O、5.明矾/FeCL3.6H2O、6.甲壳素。测定了这6个体系在相同用量下废水处理的效果。通过测定未絮凝前后的COD去除率确定去除效果。
实验步骤：(1)取6个100ml或小烧杯，洗净并干燥，标号1至6；(2)称取一定的量的絮凝剂(1.明矾/甲壳素、2.甲壳素/聚合氧化铝、3.甲壳素/壳聚糖、4.聚合氧化铝/FeCL3.6H2O、5.明矾/FeCL3.6H2O、6.甲壳素)依次加入标号的烧杯中，使总的絮凝剂的用量为2000mg/L，并调节pH为8，然后在室温下搅拌20min，保持搅拌速度一致；(3)待絮凝废水澄清之后，测定上清液的CODcr值，计算出去除率，结果如图1所示。综合比较几种絮凝体系对制浆废水COD的去除效果来看，采用明矾/FeCL3.6H2O的絮凝组合的COD去除效果最佳，可达到40.08％，主要原因在三氯化铁的加入会对明矾的絮凝作用起到促进的作用，从而使COD去除率大幅度提高。
实施例3不同影响因素对COD去除率的影响
固定絮凝剂为明矾/FeCL3.6H2O，测定了不同影响因素对COD去除率的影响。图2-6的结果依次为：(1)固定FeCL3.6H2O用量为1000mg/L及其他参数不变，仅改变明矾用量对COD去除效果的影响；(2)固定明矾用量为1000mg/L及其他参数必变，仅改变FeCL3.6H2O用量对COD去除效果的影响；(3)改变温度对COD去除的影响；(4)改变pH对COD去除的影响；(5)改变搅拌时间对COD去除的影响。结果表明絮凝剂的用量、温度、pH值、搅拌时间等均会对絮凝去除COD的效果造成影响。
实施例4微生物曝气处理效果
按照实施例优化出的最优条件，对实施例1得到的制浆废水进行絮凝处理，絮凝条件为：明矾/FeCL3.6H2O为絮凝剂，总絮凝剂用量为2000mg/L，絮凝为温度为65℃，pH为7，搅拌时间为25min。
絮凝处理后的废水分别经白腐菌Trametes Hirsuta和白腐菌Coriolusversicolor菌进行曝气生物处理，曝气处理的过程为：
将改性聚氨酯泡沫载体分散填充于底部有曝气头的滤池内，所述微生物(白腐菌Trametes Hirsuta，命名为TH菌或白腐菌Coriolus versicolor菌，命名为CV菌)加入滤池后经过一定的曝气时长可以在载体表面形成挂膜，所述微生物的加入量为50ppm；形成挂膜后，将步骤(1)中絮凝后经澄清的制浆废水加入池中，继续进行曝气培养，曝气温度为28℃，每隔2d测一次COD值，处理效果如图7所示。从图中可以看出TH菌与CV菌每隔几天的COD去除率的具体数值，TH菌的最高去除率约74.6％，而CV菌的最高去除率则只有64.5％左右，TH的最高去除率明显优于CV菌。总体而言，经过絮凝和TH菌曝气处理后的出水COD约为73mg/L，满足制浆造纸废水回用的要求，为下一步制浆废水的循环回用建立了理论基础。
Claims (7)
1.一种利用微生物协同絮凝剂对制浆废水进行处理的方法，其特征在于，包括如下步骤：(1)采取制浆后得到的废水进行絮凝沉淀处理；(2)将絮凝后的废水在曝气条件下通过滤料表面附着有微生物的滤池，进行微生物处理。
2.一种如权利要求1所述的方法，其特征在于：步骤(1)中，所述制浆后得到的废水是经过微生物处理或者未经过微生物处理的化学机械浆，当其经过微生物处理时，所述微生物优选朱红密孔菌。
3.一种如权利要求1或2所述的方法，其特征在于，步骤(1)中的絮凝剂任选自明矾、甲壳素、聚合氯化铝、壳聚糖、FeCL3.6H2O中的一种或几种；所述絮凝剂的用量范围为1000-3000mg/L，絮凝时间为10-35min，絮凝温度为25-75℃，絮凝pH为5-10；进一步优选地，絮凝剂用量为2000mg/L，所述絮凝时间为25-35min，絮凝温度为45-75℃，絮凝pH为7-9；进一步优选的地，絮凝时间为25min，絮凝温度为65-75℃，絮凝pH为7。
4.一种如权利要求1所述的方法，其特征在于，步骤(2)中的微生物选自白腐菌Trametes Hirsuta、白腐菌Coriolus versicolor或二者的组合，所述微生物的加入量为50-100ppm；优选的，所述微生物的加入量为50ppm，曝气温度为25-35℃，优选28℃。
5.一种如权利要求4所述的方法，其特征在于，步骤(2)中滤池底部安装有曝气头，改性聚氨酯泡沫载体分散填充于滤池内，所述微生物加入滤池后经过一定的曝气时长可以在载体表面形成挂膜；形成挂膜后，将步骤(1)中絮凝后经澄清的制浆废水加入池中，继续进行曝气培养，每隔2d测一次COD值。
6.一种如权利要求5所述的方法，其特征在于，所述形成挂膜的曝气时长为24h；挂膜后加入经絮凝处理的废水之后再经曝气培养的时长为6-14天，优选8-10天。
7.一种如权利要求6所述的方法，其特征在于，步骤(2)中的曝气是指通入氧气的条件下进行微生物处理。
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