CN111320332B - 一种皮革污水减排处理方法 - Google Patents
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Abstract
本发明提出一种皮革污水减排处理的方法，目的之一在于实现皮革废弃物处理的零污染排放，目的之二在于有效回收利用资源，提高整体经济效益，提供一种环保型废水处理工艺，不仅实现废气废水一体化处理，还能够对皮革制备的原料进行高效再利用，对污泥进行深度加工利用。通过将鞣制剂进行膜分离回收再利用，不仅减轻了后续污染物的处理压力，还节省了皮革制备工艺的用料，降低了生产成本；将废气废水进行一体化协同处理，并将不同工序的废水首先进行预处理然后在汇总共同处理，更佳针对性的并且全面消除各方面存在的污染物，实现资源的有效配置，符合循环经济的理念极大提高了污染治理效率；对污泥实现资源化利用，减少了资源浪费和环境污染，符合可持续发展和清洁生产的要求。
Description
技术领域
本发明涉及化工废弃物处理领域。具体的说，本发明是一种环保型皮革三废一体处理再利用工艺。
背景技术
近年来，皮革行业的迅速发展也带来大量的环境污染问题，随着社会经济的发展以及人们对环保要求的提高，皮革制造厂产生三废的处理越来也越来越受到人们的广泛关注。皮革废气主要来自于车间和污水处理站，包含大量的酸性气体和挥发性有机成分，而皮革废水来自各个制备工序，污染物种类繁多，通常表现为高浓度的铬和硫化物以及COD，氨氮化合物以及盐等。
一直以来，目前，皮革行业现有的废气废水污泥处理大都是分成几道工序分开进行，从而导致人力和时间的浪费，在皮革加工过程中，较为常用的铬鞣制剂中有大量的制剂没有被皮革吸收而进入到废水中，不仅造成革资源的浪费，而且带来严重的水污染问题。
皮革综合废水中污染物种类较多且复杂，通过单一处理方式很难将废水处理达到国家水质标准，如果将所有种类的污水首先经过汇合而后再进行统一处理势必效率低下并会造成处理药剂和能源设备的浪费，不符合生产要求，且废水处理过程中产生的污泥直接排放或者填埋处理也会对环境和人类带来极大的危害性，制革污泥的处理也引起人们的广泛关注。
因此，如何从有效控制污染源头以及废气废水处理工序的角度来综合设计以提高试剂的利用效率，对不同废水进行分类前处理，并加强废气和废水处理工序的协同配合以及对污泥进行有效利用，一直是人们亟待解决的问题。
发明内容
针对上述技术问题，本发明提出一种皮革污水减排处理方法，本发明的目的之一在于实现皮革废弃物处理的零污染排放，目的之二在于有效回收利用资源，提高整体经济效益，提供一种环保型废水处理工艺，不仅实现废气废水一体化处理，还能够对皮革制备的原料进行高效再利用，对污泥进行深度加工利用。
为实现上述目的，本发明是通过以下技术方案实现的：
一种皮革污水减排处理方法的具体步骤如下：
1）将收集的车间废气和/或污水处理工序产生的废气送入喷淋塔，来自皮革制备工序的含碱废水对其喷淋，除去废气中的水溶性酸性气体以及固体颗粒，然后将废气经过低温等离子体发生器，降解废气中的挥发性有机成分，最后经过吸附塔吸附净化后从烟囱排出；
2）将经过喷淋塔的含碱废水和含硫废水先经过第一过滤区进行除杂处理，而后在第一反应区加入絮凝剂和pH调节剂，搅拌反应一定时间之后进入第一沉淀池进行沉淀处理；
3）将鞣制和/或复鞣废水经过膜分离器，将渗余物回用于鞣制和/或复鞣工序，渗透物流入水解酸化池与染色等工序的废水汇合进行水解和酸化处理，沉淀物送入污泥搅拌器，上层液体送入紫外搅拌池，在紫外灯的照射下加入Fenton试剂以及双氧水以降解染料以及COD等成分，之后加入絮凝剂并送至第一沉淀池；
4）将第一沉淀池处理后的沉积物送至污泥搅拌器，投入一定量的EM菌，搅拌一定时间通过风机通入空气，在40℃下继续反应10小时，然后采用压滤机对污泥进行脱水处理并对其进行干燥，将处理后的污泥用作土地改良剂和烧坯原料等。
进一步的，所述低温等离子体发生器为介质阻挡放电方式或高频放电等离子体；
进一步的，所述絮凝剂为无机高分子絮凝剂或有机高分子絮凝剂；
进一步的，所述絮凝剂为阳离子絮凝剂或阴离子絮凝剂；
进一步的，所述膜分离器为平板式膜分离器或中空纤维膜分离器，膜材质为聚偏氟乙烯、聚醚砜或聚砜中的一种；
进一步的，所述渗余物回收的鞣制剂为条状形貌微胶囊复鞣剂，所述条状形貌微胶囊复鞣剂的制备方法为：
A 将质量比50%的丙烯酸类单体、25%的羧甲基纤维素、2%的交联剂、1%的2，2’-偶氮二异丁腈、22%异丁烷混合均匀，制得悬浮聚合的油相；丙烯酸类单体为丙烯酸乙酯、丙烯酸甲酯、甲基丙烯酸甲酯中的一种，交联剂为甲基丙烯酸烯丙酯、聚乙二醇二甲基丙烯酸酯、三羟甲基丙烷三甲基丙烯酸酯中的一种。
B 将质量比为20%的硫酸铁、15%的硫酸锆、15%硫酸铝以及5%的吐温-80加入到45%的水中，搅拌均匀得到水相；
C 将在高速剪切条件下将水相加入到油相中，继续加入油相和水相总质量5%-20%的非离子表面活性剂P123作为模板剂，继续高速剪切形成油包水分散溶液，然后在高压均质机中搅拌反应15～24小时，喷雾干燥，即得条状形貌微胶囊复鞣剂。其中，油相和水相的质量比为1.2-2.0，步骤B水相中还可以加入抗菌剂以及防霉剂等。
进一步的，所述EM菌的投料量为污泥重量的2%-5%，优选的为3%；
进一步的，所述风机为罗茨风机。
本发明的有益效果：本发明提供一种环保型皮革污水减排处理的方法，通过将鞣制剂进行膜分离回收再利用，不仅减轻了后续污染物的处理压力，还节省了皮革制备工艺的用料，降低了生产成本；将废气废水进行一体化协同处理，并将不同工序的废水首先进行预处理然后在汇总共同处理，更佳针对性的并且全面消除各方面存在的污染物，实现资源的有效配置，符合循环经济的理念极大提高了污染治理效率；对污泥实现资源化利用，减少了资源浪费和环境污染，符合可持续发展和清洁生产的要求。
附图说明
图1是实施例1环保型废水处理工艺的示意图；
图2是实施例1鞣制剂的扫描电镜SEM图。
具体实施方式
以下通过具体实施例详细说明本发明技术方案的实施和所具有的有益效果，但不能认定为对本发明的可实施范围的任何限定。
实施例1
一种环保型皮革污水减排处理的方法，工艺流程如图1，具体步骤如下：
1）将收集的车间废气和/或污水处理工序产生的废气送入喷淋塔，来自皮革制备工序的含碱废水对其喷淋，除去废气中的水溶性酸性气体以及固体颗粒，然后将废气经过介质阻挡放电低温等离子体发生器，降解废气中的挥发性有机成分，最后经过吸附塔吸附净化后从烟囱排出，经检测，排出烟气中的污染物成分清除率达99%，满足国家环保要求；
2）将经过喷淋塔的含碱废水和含硫废水先经过第一过滤区进行除杂处理，而后在第一反应区加入聚丙烯酰胺并调节pH呈弱碱性，搅拌反应8h进入第一沉淀池进行沉淀处理；
3）将鞣制和/或复鞣废水经过膜分离器，将渗余物回收的鞣制剂为条状形貌微胶囊复鞣剂回用于鞣制和/或复鞣工序，渗透物流入水解酸化池与染色等工序的废水汇合进行水解和酸化处理，沉淀物送入污泥搅拌器，上层液体送入紫外搅拌池，在紫外灯的照射下加入Fenton试剂以及双氧水以降解染料以及COD等成分，之后加入聚合氯化铝并送至第一沉淀池；
4）将第一沉淀池处理后的沉积物送至污泥搅拌器，上清液出水经检测，处理后的废水COD含量为32mg/L，氨氮含量为4mg/L，硫化物含量为0.3mg/L，脱色率在97%以上，满足污水治理排放标准，投入污泥重量3%的EM菌，搅拌6小时然后通过罗茨风机通入空气，在40℃下继续反应10小时，然后采用压滤机对污泥进行脱水处理并对其进行干燥，将处理后的污泥用作土地改良剂和烧坯原料等。
Claims (8)
1.一种皮革污水减排处理方法，其特征在于：具体步骤如下：
1）将收集的车间废气和/或污水处理工序产生的废气送入喷淋塔，来自皮革制备工序的含碱废水对其喷淋，除去废气中的水溶性酸性气体以及固体颗粒，然后将废气经过低温等离子体发生器，降解废气中的挥发性有机成分，最后经过吸附塔吸附净化后从烟囱排出；
2）将经过喷淋塔的含碱废水和含硫废水先经过第一过滤区进行除杂处理，而后在第一反应区加入絮凝剂和pH调节剂，搅拌反应一定时间之后进入第一沉淀池进行沉淀处理；
3）将鞣制和/或复鞣废水经过膜分离器，将渗余物回用于鞣制和/或复鞣工序，渗透物流入水解酸化池与染色等工序的废水汇合进行水解和酸化处理，沉淀物送入污泥搅拌器，上层液体送入紫外搅拌池，在紫外灯的照射下加入Fenton试剂以及双氧水以降解染料以及COD等成分，之后加入絮凝剂并送至第一沉淀池；
4）将第一沉淀池处理后的沉积物送至污泥搅拌器，投入一定量的EM菌，搅拌一定时间通过风机通入空气，在40℃下继续反应10小时，然后采用压滤机对污泥进行脱水处理并对其进行干燥，将处理后的污泥用作土地改良剂和烧坯原料；
所述渗余物回收的鞣制剂为条状形貌微胶囊复鞣剂，所述条状形貌微胶囊复鞣剂的制备方法为：
A 将质量比50%的丙烯酸类单体、25%的羧甲基纤维素、2%的交联剂、1%的2，2’-偶氮二异丁腈、22%异丁烷混合均匀，制得悬浮聚合的油相；丙烯酸类单体为丙烯酸乙酯、丙烯酸甲酯、甲基丙烯酸甲酯中的一种，交联剂为甲基丙烯酸烯丙酯、聚乙二醇二甲基丙烯酸酯、三羟甲基丙烷三甲基丙烯酸酯中的一种；
B 将质量比为20%的硫酸铁、15%的硫酸锆、15%硫酸铝以及5%的吐温-80加入到45%的水中，搅拌均匀得到水相；
C 在高速剪切条件下将水相加入到油相中，继续加入油相和水相总质量5%-20%的非离子表面活性剂P123作为模板剂，继续高速剪切形成油包水分散溶液，然后在高压均质机中搅拌反应15～24小时，喷雾干燥，即得条状形貌微胶囊复鞣剂。
2.根据权利要求1所述的皮革污水减排处理方法，其特征在于：所述低温等离子体发生器为介质阻挡放电方式或高频放电等离子体。
3.根据权利要求1所述的皮革污水减排处理方法，其特征在于：所述絮凝剂为无机高分子絮凝剂或有机高分子絮凝剂。
4.根据权利要求1所述的皮革污水减排处理方法，其特征在于：所述絮凝剂为阳离子絮凝剂或阴离子絮凝剂。
5.根据权利要求1所述的皮革污水减排处理方法，其特征在于：所述膜分离器为平板式膜分离器或中空纤维膜分离器，膜材质为聚偏氟乙烯、聚醚砜或聚砜中的一种。
6.根据权利要求1所述的皮革污水减排处理方法，其特征在于：油相和水相的质量比为1.2-2.0，其特征在于：步骤B水相中加入抗菌剂以及防霉剂。
7.根据权利要求1所述的皮革污水减排处理方法，其特征在于：所述EM菌的投料量为污泥重量的2%-5%。
8.根据权利要求1所述的皮革污水减排处理方法，其特征在于：所述风机为罗茨风机。
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