CN104671497A - 实现秸秆制浆造纸与废旧铅酸电池再生两产业共生互赢的节能环保新工艺 - Google Patents
实现秸秆制浆造纸与废旧铅酸电池再生两产业共生互赢的节能环保新工艺 Download PDFInfo
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Abstract
一种实现秸秆制浆造纸与废旧铅酸电池再生两产业共生互赢的节能环保新工艺，针对秸秆制浆污水碱性特征、废旧铅酸蓄电池再生的污水酸性特征和余热存在耦合利用空间的情况，提供一种酸碱废水综合耦合处理和热能互补利用的节能环保工艺，该工艺可以大大降低两个产业污染治理成本和难度，实现能量互补利用，获得产业共生互赢。该发明实现了两远缘产业能源互补利用，使秸秆制浆产业碱性黑液和再生铅产业含铅酸性废水全部循环利用，解决了两大产业污水处理成本高的难题，有效地增加了两大产业经济效益。
Description
技术领域
本发明涉及资源综合利用节能环保技术领域，具体涉及一种实现秸秆制浆造纸与废旧铅酸电池再生两产业共生互赢的节能环保新工艺。
背景技术
随着农村生活水平提高，秸秆作为燃柴的时代已经过去，由此造成大量秸秆堆积田间地头，影响耕种，农民被迫一把火焚之。据调查我国每年的秸秆产量约为10亿吨，巨量的秸秆直接焚烧不仅浪费了可以变废为宝的秸秆资源，而且危害严重，会造成严重的大气污染、引发交通事故，影响道路交通和航空安全，还会破坏土壤结构，造成农田质量下降。如何综合利用秸秆、杜绝秸秆焚烧成为一个迫在眉睫的课题。
农作物秸秆资源丰富、纤维含量高，最适于制浆造纸，但因制浆污染问题始终没有很好解决而一直被严令禁止。秸秆制浆造纸污染之所以根治难度大，主要是由于治污成本高。所以能否解决秸秆焚烧的问题很大程度上就在于能否解决秸秆造纸的污染问题。
现有的秸秆制浆造纸方法主要是通过秸秆破碎、筛选、除尘、蒸煮、强碱洗涤、净化、漂白以及打浆等步骤来实现秸秆制浆。制浆产生的废水俗称黑液，含有大量碱和难溶的木质素等物质，直接排放会对环境造成较大污染。造纸黑液从源头治理是秸秆制浆造纸必须攻克的课题。目前最为行之有效的方法是碱回收技术。但由于秸秆制浆产生的黑液存在滤水性能差、黑液黏度大、含硅量高等不利因素，其中木质素很难分离处理，使碱回收的成本非常高，加之秸秆制浆蒸煮工序能耗高，这些在很大程度上都限制了秸秆制浆造纸产业的发展。
目前另外一个废旧铅酸蓄电池再生产业，在废旧电池拆解、再生铅冶炼脱硫和电池极板加工过程中，也会产生大量的废水，这些废水酸性高而且含有重金属铅，未经处理严禁直接排放，但要按照规范要求达标处理好这些污 水，成本高、难度大。而且再生铅冶炼存在能耗高余热利用率低的问题。
国家严格禁止秸秆焚烧，鼓励秸秆综合利用，采用环保工艺发展秸秆制浆造纸是一个非常有前景的产业。废旧铅酸蓄电池再生利用也是国家大力鼓励的循环经济产业。目前这两个产业都存在耗能高、污染重的问题，都有节能环保的共性需求。
发明内容
针对秸秆制浆造纸需要大量高温高压蒸汽蒸煮且产生的黑液污水碱性特征、废旧铅酸蓄电池再生过程中产生的污水酸性特征且冶炼尾气余热可回收产生大量的高温高压蒸汽的情况，本发明提供一种酸碱废水综合耦合处理和热能互补利用的节能环保工艺，该工艺可以大大降低两个产业污染治理成本和难度，实现能量互补利用，获得两个产业共生互赢。
一种实现秸秆制浆造纸与废旧铅酸电池再生两产业共生互赢的节能环保新工艺，其特征在于，该方法步骤如下：
1)对秸秆制浆造纸过程中产生的废水先内部过滤絮凝反复循环使用，将不能再循环利用的含碱黑液废水集中放入碱性废水收集池中，投入絮凝剂进行沉淀，用污泥泵将沉淀泥输送到压滤设备，进行一级压滤，滤液回收到碱性废水收集池中；再将压滤后的沉淀泥加入清水和适量硫酸搅拌混合进行中和反应，使沉淀泥pH值接近中性，然后进行二次压滤，滤液回收到碱性废水收集池；二次压滤所得的中性沉淀泥多数是木质素，其余是糖类、有机酸和少量的无机成分，均可以用于配置生产有机肥料；
2)将废旧铅酸电池拆解和电池极板加工过程中产生的含酸含铅废水集中到酸性废水收集池，然后投入絮凝剂进行沉淀处理，含铅沉淀泥压滤干燥后投入冶炼炉熔炼，铅得到回收，滤液收集到酸性废水收集池；
3)将步骤1)中碱性废水收集池和步骤2)中酸性废水收集池中收集的两种废水，分别用抽水泵输送到中和池进行中和处理，基于再生铅冶炼脱硫需要弱碱性循环水，通过控制两种废水比例，尽可能使中和后废水调配呈弱碱性，再投入絮凝剂进行沉淀处理；沉淀泥富含木质素、糖类、硫酸钠、氢氧化钠和铅尘等成分，压滤干燥后投入冶炼炉，有机成分被燃烧，铅尘被熔 炼回收，无机成分成为熔渣排出，滤液回收到中和池；中和絮凝沉淀后的废水视水质情况确定是否需要净化处理：若水质比较澄清，可直接作为脱硫中水进行循环利用，若水质比较差、有机成分含量高，难以直接循环利用，则要泵入曝气池进行曝气氧化处理，然后投入絮凝剂再次沉淀，沉淀泥压滤干燥后投入冶炼炉进行铅回收，曝气净化处理后的中水再用于脱硫循环利用；若中和絮凝沉淀后的澄清中水呈酸性，则在用于脱硫时添加适量生石灰或烧碱，使中水变为弱碱性。
4)利用再生铅冶炼过程中的高温尾气进行余热回收生产高温高压蒸汽，用管道把这些高温高压蒸汽输送给秸秆制浆造纸的蒸煮车间用于软化疏松秸秆纤维，也可用于环保工序沉淀物、脱硫产物的干燥，实现再生铅冶炼余热用于秸秆制浆造纸，达到能源互补利用。
5)再生铅冶炼尾气余热回收利用后，尾气中富含铅尘和二氧化硫、二氧化碳、水蒸气等成分。先进行一级重力除尘，二级袋式除尘，使尾气中95％以上的铅尘得到回收，然后进行三级循环喷淋水洗，回收尾气中剩余的铅尘，将回收的铅尘投入冶炼炉进行再冶炼。脱尘后的尾气用步骤3)得到的弱碱性中水进行喷淋脱硫、脱碳处理，中水中的碱与尾气中的二氧化硫、二氧化碳发生反应，生成亚硫酸钠、碳酸钠，使二氧化硫、二氧化碳得到捕获，达到脱除的目的。亚硫酸钠、碳酸钠浓度达到一定程度时结晶析出成为脱硫产物。在脱硫循环中弱碱性中水的碱性逐渐下降，最后会失去脱硫功能，需不断地从步骤3)得到弱碱性中水给予补充，恢复脱硫功能。
6)将步骤5)得到的脱硫产物亚硫酸钠、碳酸钠加水溶解后，投入生石灰，碳酸钠与石灰反应生成碳酸钙沉淀，使亚硫酸钠与碳酸钠分离，当碳酸钠脱除后溶液接近中性、石灰消耗殆尽时，将亚硫酸钠溶液用步骤4)获得的高温蒸汽进行蒸发干燥，所得的亚硫酸钠可以用作秸秆制浆造纸过程中木质素脱除剂和纤维漂白剂。
本发明的有益效果：
(1)使秸秆能够用于制浆造纸，可以节约大量木材，减少树木砍伐；
(2)避免秸秆焚烧，防止大气污染，有益于保护环境；
(3)再生铅冶炼余热得到有效利用，节省了秸秆制浆造纸的能源消耗；
(4)黑液回收的木质素等高有机废物可加工有机肥料，实现资源利用最大化；
(5)实现秸秆制浆造纸和再生铅产业废水综合互补耦合式治理，使造纸黑液和含铅废水全部循环利用，没有任何外排，解决了污水处理成本高的世界性难题，有效地增加了两大产业经济效益。
具体实施方式
为了使本发明实现的技术手段、创作特征、达成目的与功效易于明白了解，下面结合具体实施例，进一步阐述本发明。
实施例1
1)对秸秆制浆造纸过程中产生的废水先内部过滤絮凝反复循环使用，将不能再循环利用的含碱黑液废水集中放入碱性废水收集池中，投入絮凝剂进行沉淀，用污泥泵将沉淀泥输送到压滤设备，进行一级压滤，滤液回收到碱性废水收集池中；再将压滤后的沉淀泥加入清水和适量硫酸搅拌混合进行中和反应，使沉淀泥pH值接近中性，然后进行二次压滤，滤液回收到碱性废水收集池；二次压滤所得的中性沉淀泥多数是木质素，其余是糖类、有机酸和少量的无机成分，均可以用于配置生产有机肥料；
2)将废旧铅酸电池拆解和电池极板加工过程中产生的含酸含铅废水集中到酸性废水收集池，然后投入絮凝剂进行沉淀处理，含铅沉淀泥压滤干燥后投入冶炼炉熔炼，铅得到回收，滤液收集到酸性废水收集池；
3)将步骤1)中碱性废水收集池和步骤2)中酸性废水收集池中收集的两种废水，分别用抽水泵输送到中和池进行中和处理，基于再生铅冶炼脱硫需要弱碱性循环水，通过控制两种废水比例，尽可能使中和后废水调配呈弱碱性，再投入絮凝剂进行沉淀处理；沉淀泥富含木质素、糖类、硫酸钠、氢氧化钠和铅尘等成分，压滤干燥后投入冶炼炉，有机成分被燃烧，铅尘被熔炼回收，无机成分成为熔渣排出，滤液回收到中和池；中和絮凝沉淀后的废水视水质情况确定是否需要净化处理：若水质比较澄清，可直接作为脱硫中水进行循环利用，若水质比较差、有机成分含量高，难以直接循环利用，则要泵入曝气池进行曝气氧化处理，然后投入絮凝剂再次沉淀，沉淀泥压滤干 燥后投入冶炼炉进行铅回收，曝气净化处理后的中水再用于脱硫循环利用；若中和絮凝沉淀后的澄清中水呈酸性，则在用于脱硫时添加适量生石灰或烧碱，使中水变为弱碱性。
4)利用再生铅冶炼过程中的高温尾气进行余热回收生产高温高压蒸汽，用管道把这些高温高压蒸汽输送给秸秆制浆造纸的蒸煮车间用于软化疏松秸秆纤维，也可用于环保工序沉淀物、脱硫产物的干燥，实现再生铅冶炼余热用于秸秆制浆造纸，达到能源互补利用。
5)再生铅冶炼尾气余热回收利用后，尾气中富含铅尘和二氧化硫、二氧化碳、水蒸气等成分。先进行一级重力除尘，二级袋式除尘，使尾气中95％以上的铅尘得到回收，然后进行三级循环喷淋水洗，回收尾气中剩余的铅尘，将回收的铅尘投入冶炼炉进行再冶炼。脱尘后的尾气用步骤3)得到的弱碱性中水进行喷淋脱硫、脱碳处理，中水中的碱与尾气中的二氧化硫、二氧化碳发生反应，生成亚硫酸钠、碳酸钠，使二氧化硫、二氧化碳得到捕获，达到脱除的目的。亚硫酸钠、碳酸钠浓度达到一定程度时结晶析出成为脱硫产物。在脱硫循环中弱碱性中水的碱性逐渐下降，最后会失去脱硫功能，需不断地从步骤3)得到弱碱性中水给予补充，恢复脱硫功能。
6)将步骤5)得到的脱硫产物亚硫酸钠、碳酸钠加水溶解后，投入生石灰，碳酸钠与石灰反应生成碳酸钙沉淀，使亚硫酸钠与碳酸钠分离，当碳酸钠脱除后溶液接近中性、石灰消耗殆尽时，将亚硫酸钠溶液用步骤4)获得的高温蒸汽进行蒸发干燥，所得的亚硫酸钠可以用作秸秆制浆造纸过程中木质素脱除剂和纤维漂白剂。
以上显示和描述了本发明 的基本原理和主要特征和本发明的优点。本行业的技术人员应该了解，本发明不受上述实施例的限制，上述实施例和说明书中描述的只是说明本发明的原理，在不脱离本发明精神和范围的前提下，本发明还会有各种变化和改进，这些变化和改进都落入要求保护的本发明范围内。本发明要求保护范围由所附的权利要求书及其等效物界定。
Claims (2)
1.一种实现秸秆制浆造纸与废旧铅酸电池再生两产业共生互赢的节能环保新工艺，其特征在于，该方法步骤如下：
1)对秸秆制浆造纸过程中产生的废水先内部过滤絮凝反复循环使用，将不能再循环利用的含碱黑液废水集中放入碱性废水收集池中，投入絮凝剂进行沉淀，用污泥泵将沉淀泥输送到压滤设备，进行一级压滤，滤液回收到碱性废水收集池中；再将压滤后的沉淀泥加入清水和适量硫酸搅拌混合进行中和反应，使沉淀泥pH值接近中性，然后进行二次压滤，滤液回收到碱性废水收集池；
2)将废旧铅酸电池拆解和电池极板加工过程中产生的含酸含铅废水集中到酸性废水收集池，然后投入絮凝剂进行沉淀处理，含铅沉淀泥压滤干燥后投入冶炼炉熔炼，铅得到回收，滤液收集到酸性废水收集池；
3)将步骤1)中碱性废水收集池和步骤2)中酸性废水收集池中收集的两种废水，分别用抽水泵输送到中和池进行中和处理，基于再生铅冶炼脱硫需要弱碱性循环水，通过控制两种废水比例，尽可能使中和后废水调配呈弱碱性，再投入絮凝剂进行沉淀处理；沉淀泥富含木质素、糖类、硫酸钠、氢氧化钠和铅尘等成分，压滤干燥后投入冶炼炉，有机成分被燃烧，铅尘被熔炼回收，无机成分成为熔渣排出，滤液回收到中和池；中和絮凝沉淀后的废水视水质情况确定是否需要净化处理：若水质比较澄清，可直接作为脱硫中水进行循环利用，若水质比较差、有机成分含量高，难以直接循环利用，则要泵入曝气池进行曝气氧化处理，然后投入絮凝剂再次沉淀，沉淀泥压滤干燥后投入冶炼炉进行铅回收，曝气净化处理后的中水再用于脱硫循环利用；若中和絮凝沉淀后的澄清中水呈酸性，则在用于脱硫时添加适量生石灰或烧碱，使中水变为弱碱性；
4)利用再生铅冶炼过程中的高温尾气进行余热回收生产高温高压蒸汽，用管道把这些高温高压蒸汽输送给秸秆制浆造纸的蒸煮车间用于软化疏松秸秆纤维，也可用于环保工序沉淀物、脱硫产物的干燥，实现再生铅冶炼余热用于秸秆制浆造纸，达到能源互补利用；
5)再生铅冶炼尾气余热回收利用后，尾气中富含铅尘和二氧化硫、二氧 化碳、水蒸气成分；先进行一级重力除尘，二级袋式除尘，使尾气中95％以上的铅尘得到回收，然后进行三级循环喷淋水洗，回收尾气中剩余的铅尘，将回收的铅尘投入冶炼炉进行再冶炼；
6)脱尘后的尾气用步骤3)得到的弱碱性中水进行喷淋脱硫、脱碳处理，中水中的碱与尾气中的二氧化硫、二氧化碳发生反应，生成亚硫酸钠、碳酸钠，使二氧化硫、二氧化碳得到捕获，达到脱除的目的；
7)将步骤5)得到的脱硫产物亚硫酸钠、碳酸钠加水溶解后，投入生石灰，碳酸钠与石灰反应生成碳酸钙沉淀，使亚硫酸钠与碳酸钠分离，当碳酸钠脱除后溶液接近中性、石灰消耗殆尽时，将亚硫酸钠溶液用步骤4)获得的高温蒸汽进行蒸发干燥，所得的亚硫酸钠可以用作秸秆制浆造纸过程中木质素脱除剂和纤维漂白剂。
2.根据权利要求1所述的实现秸秆制浆造纸与废旧铅酸电池再生两产业共生互赢的节能环保新工艺，其特征在于：上述步骤1)中二次压滤所得的中性沉淀泥多数是木质素，其余是糖类、有机酸和少量的无机成分，均可以用于生产有机肥料。
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| CN111167273A (zh) * | 2018-11-13 | 2020-05-19 | 湖南省金翼有色金属综合回收有限公司 | 一种烟道尾气脱硫装置及其工艺 |
| CN111167273B (zh) * | 2018-11-13 | 2023-12-12 | 湖南省金翼有色金属综合回收有限公司 | 一种烟道尾气脱硫装置及其工艺 |
| CN111411232A (zh) * | 2020-03-11 | 2020-07-14 | 中南大学 | 一种废旧动力锂电池正极极片中有价金属元素的全量回收方法 |
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