CN107216126A - 以城市污泥为原料的陶粒的制备方法 - Google Patents

以城市污泥为原料的陶粒的制备方法 Download PDF

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Publication number
CN107216126A
CN107216126A CN201710255007.1A CN201710255007A CN107216126A CN 107216126 A CN107216126 A CN 107216126A CN 201710255007 A CN201710255007 A CN 201710255007A CN 107216126 A CN107216126 A CN 107216126A
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haydite
sludge
raw material
municipal sludge
preparation
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CN201710255007.1A
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CN107216126B (zh
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林荣亮
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Qingdao Easy Ecological Environmental Protection Technology Co Ltd
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Qingdao Easy Ecological Environmental Protection Technology Co Ltd
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Priority to CN201710255007.1A priority Critical patent/CN107216126B/zh
Publication of CN107216126A publication Critical patent/CN107216126A/zh
Priority to PCT/CN2018/083283 priority patent/WO2018192467A1/zh
Priority to US16/656,600 priority patent/US10894741B2/en
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Abstract

本发明提供了以城市污泥为原料的陶粒的制备方法，由以下具体步骤制成：干燥；配料包括污泥、粉煤灰、高岭土、炼钢炉渣、沸石、赤铁矿、钙质页岩、垃圾焚烧飞灰、Fe2O3、废玻璃、碳酸钙、十二烷基硫酸钠、苯甲酸钠；将各原料搅拌均匀后投入造粒机中造粒；造粒后的料球颗粒干燥、预热，然后迅速转移至烧结设备中先进行低温烧结、后进行高温烧结；对大块的烧成物破碎；对破碎后的物料分筛。按照本发明的方法制备得到的陶粒减少了大块烧成物的产生，从而也相应的减少了后续的破碎工作，节省了能耗；制备得到的陶粒的筒压强度大，堆积密度低，明显改善了陶粒的品质和性能；将废弃物进行转化、循环利用方式，有利于保护环境。

Description

以城市污泥为原料的陶粒的制备方法
技术领域
本发明属于陶粒制备领域，具体涉及到一种以城市污泥为原料的陶粒的制备方法。
背景技术
近年来，随着我国城市的飞速发展，人口的增多，城市污泥量明显增加，对于城市污泥传统的处理方法是堆肥、焚化、填海，其中的大量有害微生物及重金属及其沥出物所造成的污染已经引起了人们的关注。近年来的环保法规对城市污泥处理已经作出了严格的规定，如几年前城市污泥可以直接作农业肥料，由于污泥中的重金属含量较高，现在已经禁止污泥作为肥料使用。
利用城市污泥生产陶粒是最有效的城市污泥处理方法之一，不仅有效的解决了城市污泥的堆放问题，避免排放不当对环境造成的二次污染，而且陶粒作为轻骨料可以用于基础建筑，也缓解了砂、石等建材紧张的资源危机，符合当前国家固体废弃物资源化利用的政策。
但是目前污水处理厂的城市污泥中有机质含量过高，其绝干比重占70％以上，单纯使用这种污泥焙烧陶粒在通常情况下是不可行的。如果生料球处于高温之下，首先失去的是占总体积90％以上的可燃物，可燃物变成灰烬体积急剧变小，料球失去支撑而瓦解，粉末状的无机物质在高温下会形成一些微小颗粒或崩散为粉末，也有少量小颗粒会破壁相互粘连形成较大颗粒，但为数不多，可被称为渣滓，这些渣滓具有一定的活性，理论上可作为生产水泥的填充料，但因为原料污泥本身的不稳定，这些渣滓的活性也极不稳定，所以很难被采用。
将城市污泥制备成陶粒，焙烧工艺是重要的因素，不仅决定了焙烧的烧胀过程，而且对于陶粒的微观结构及晶相组成有重要的影响。除此之外，陶粒原料成分、配比结构也对陶粒的品质影响显著。中国专利申请号2011101491242(申请日为2011.06.03)的《城市污水处理厂污泥处置及资源化利用的方法》公开了一种城市污水处理厂污泥处置及资源化利用的方法，以城市污水处理厂的居民生活污泥为原料，经过干燥、搅拌、造粒、烧结、破碎、除尘、粉筛的步骤，将污泥烧制为能为人们所利用的陶粒，由于该方法以单一的城市污泥为原料，污泥成分比较单一，得到的陶粒在性能及其应用方面有一定的局限性。中国专利申请号021149380(申请日为2002.03.07)的《一种利用污水处理厂生物污泥烧制粘土陶粒的方法》公开了一种利用污水处理厂生物污泥烧制粘土陶粒的方法，具体的原料组分包括粘土、污水处理厂干生物污泥、石灰石、铁粉，该方法使用了较多的粘土，造成资源的浪费。因此，需要探索一种将城市污泥和各种辅料相结合，辅以特定的生产工艺的制备陶粒的方法，以得到性能和品质有所改善的适应不同需求的陶粒，进而扩大陶粒的应用范围。
发明内容
为了解决现有技术的问题，本发明提供了一种以城市污泥为原料的陶粒的制备方法。该制备方法制得的陶粒强度较高、堆积密度小，不仅有利于保护环境，节约资源，而且符合国家标准要求，满足市场需求，使该陶粒更好的向市场推广。
为了达到上述目的，本发明提供以下技术方案：
以城市污泥为原料的陶粒的制备方法，由以下具体步骤制成：
(1)干燥：对城市污泥浓缩、消化、机械脱水、烘干，得到含水率为22～24％的原料污泥；
以上的消化步骤为，采用普通厌氧工艺法去除污泥中的易生化的有机物，具体为，将城市污泥投入消化池中，加入兼性菌和厌氧菌，将城市污泥中的可生物降解的有机物分解成二氧化碳、甲烷和水等物质；
(2)配料：按以下的重量份数配比取各原料：原料污泥80～120、粉煤灰10～20、高岭土1～5、炼钢炉渣5～20、沸石5～15、赤铁矿1～5、钙质页岩5～15、垃圾焚烧飞灰5～20、Fe2O3 0.5～2、废玻璃1～4、碳酸钙0.1～2、十二烷基硫酸钠0.1～2、苯甲酸钠0.1～1.5；
(3)取步骤(2)中的各原料，混合、搅拌均匀，将搅拌后的物料投入造粒机中造粒，粒径控制在15～20mm之间；
(4)将造粒后的料球颗粒置于90-110℃下干燥1～2小时，再在220～280℃预热10～20分钟，然后迅速转移至烧结设备中烧结；
烧结设备中进行两段式烧结，先低温烧结，后高温烧结；
烧结设备有两个炉膛，炉膛A中提供的温度为600～800℃，炉膛B提供的温度为900～1100℃；预热后的物料在炉膛A中烧制3～5分钟，再迅速转移到炉膛B中烧制4～6分钟，冷却至室温；
(5)将冷却后的物料卸下，并且对大块的烧成物破碎，使破碎物料的最大粒径控制在20～26mm之间；
(6)对破碎后的物料分筛，分筛出粒径为5～15mm的陶粒，15～26mm的陶粒，0.5～5mm的陶砂，粒径小于0.5mm的细末。
优选地，垃圾焚烧飞灰来自于城市固体废物处理厂。
采用上述技术方案，本发明的有益效果是：
(1)按照本发明的方法制备得到的陶粒减少了大块烧成物的产生，从而也相应的减少了后续的破碎工作，节省了能耗；
(2)制备得到的陶粒的筒压强度大，堆积密度低，明显改善了陶粒的品质和性能，扩大了应用范围，可更好的向市场推广；
(3)利用城市污泥、炼钢炉渣、垃圾焚烧飞灰、废玻璃等进行陶粒的制备，是废弃物的转化的一种循环利用方式，有利于保护环境。
具体实施方式
下面结合实施例进一步说明本发明。
实施例1
以取自青岛市某污水处理厂的城市污泥为原料的陶粒的制备方法，由以下具体步骤制成：
(1)干燥：对城市污泥进行浓缩、消化、机械脱水、烘干，得到的原料污泥含水率为23％左右；
消化的具体步骤为：将城市污泥投入至消化池中，在消化池中加入甲烷菌菌剂、产乙酸菌菌剂，调节城市污泥的pH为6.5左右，于37℃左右厌氧处理30小时左右；其中每吨城市污泥中投入甲烷菌剂2升，投入产乙酸菌菌剂2升，每升菌剂中，活菌数量为109-1012cfu/g；
(2)配料：按以下重量份数取各原料原料污泥100、粉煤灰15、高岭土4、炼钢炉渣8、沸石12、赤铁矿4、钙质页岩12、垃圾焚烧飞灰15、Fe2O3 1、废玻璃2、碳酸钙1.5、十二烷基硫酸钠1.5、苯甲酸钠1.2；
(3)取步骤(2)中的各原料，混合、搅拌均匀，将搅拌后的物料投入造粒机中造粒，粒径控制在15～20mm之间；
(4)将造粒后的料球颗粒置于100℃下干燥1.5小时，再在260℃预热15分钟，然后迅速转移至烧结设备中烧结；
烧结设备有两个炉膛，炉膛A中提供的温度为700℃，炉膛B提供的温度为1040℃；预热后的物料在炉膛A中烧制4分钟，再迅速转移到炉膛B中烧制5分钟，冷却至室温；
(5)将冷却后的物料卸下，并且对大块的烧成物破碎，使破碎物料的最大粒径控制在20～26mm之间；
(6)对破碎后的物料分筛，分筛出粒径为5～15mm的陶粒，15～26mm的陶粒，0.5～5mm的陶砂，粒径小于0.5mm的细末。
垃圾焚烧飞灰来自于城市固体废物处理厂。
设置4组对照例，分别制备陶粒，并对陶粒的性质进行比较。
对照例1：陶粒的各原料的重量份数配比为：原料污泥250、粉煤灰15、高岭土4、炼钢炉渣8、沸石12、赤铁矿4、钙质页岩12、垃圾焚烧飞灰15、Fe2O3 1、废玻璃2、碳酸钙1.5、十二烷基硫酸钠1.5、苯甲酸钠1.2。
对照例1将城市污泥的量调整为较高的比例，城市污泥的重量百分比约为82％，其他步骤与实施例1相同。
对照例2：陶粒的各原料的重量份数配比为：原料污泥20、粉煤灰15、高岭土4、炼钢炉渣8、沸石12、赤铁矿4、钙质页岩12、垃圾焚烧飞灰15、Fe2O3 1、废玻璃2、碳酸钙1.5、十二烷基硫酸钠1.5、苯甲酸钠1.2。
对照例1、对照例2中原料污泥的处理均同实施例1；
对照例2将城市污泥的量调整为较低的比例，原料污泥的重量百分比约为27％，其他步骤与实施例1相同。
对照例3：将步骤(4)调整为：将造粒后的料球颗粒置于100℃下干燥1.5小时，再在260℃预热15分钟，然后迅速转移至烧结设备中烧结；
该烧结设备有两个炉膛，炉膛A中提供的温度为900℃，炉膛B提供的温度为1250℃；预热后的物料在炉膛A中烧制4分钟，再迅速转移到炉膛B中烧制5分钟；冷却至室温。
对照例3的其他步骤与实施例1相同。
对照例4：将造粒后的料球颗粒置于100℃下干燥1.5小时，再在260℃预热15分钟，然后迅速转移至烧结设备中烧结；
该烧结设备有两个炉膛，炉膛A中提供的温度为500℃，炉膛B提供的温度为850℃；预热后的物料在炉膛A中烧制4分钟，再迅速转移到炉膛B中烧制5分钟；冷却至室温。
对照例4的其他步骤与实施例1相同。
实施例1与4组对照例制备得到的陶粒的性能具体如表1所示：
表1实施例1与4组对照例制备得到的陶粒的性能
实施例1 对照例1 对照例2 对照例3 对照例4
颗粒级配 2.8 2.9 3.1 2.9 3.0
堆积密度(kg/m3) 184 164 254 284 295
表观密度(kg/m3) 846 812 905 916 943
筒压强度(MPa) 2.5 1.4 2.3 1.6 1.3
吸水率％ 17.6 10.5 11.6 10.4 10.8
软化系数 0.95 0.69 0.81 0.54 0.62
粒型系数 1.36 1.45 1.52 1.69 1.73
含泥量％ 1.8 2.5 2.1 2.8 3.1
泥块含量％ 0.54 1.09 1.04 1.54 2.13
煮沸质量损失％ 4.17 5.63 5.48 6.35 6.11
烧失量％ 3.8 3.9 4.1 5.2 5.6
硫化物和硫酸盐含量％ 0.73 0.64 0.58 0.87 0.91
从上表内容可以看出，污泥量、烧结温度均对陶粒的性能、品质产生重要影响：
(1)污泥量的增加或减少，都会对陶粒的品质产生影响。
当污泥的重量含量过多时，对照例1与实施例1相比，陶粒的筒压强度较低，陶粒烧制后易碎，这主要是由于污泥含量较大时，陶粒烧制的过程中会有较多的表面裂纹和较大的内部空隙导致陶粒强度降低；
当污泥的量减少到一定程度时，则会影响陶粒的堆积密度和筒压强度，对照例2与实施例1相比，陶粒堆积密度增大、筒压强度略微降低，在本发明所限定的污泥数值范围内，陶粒的强度和堆积密度是较理想的。
(2)烧结温度对陶粒的品质的影响较显著。
对照例3与实施例1相比，当温度过高时，越来越多的原料成分熔化为液相并成为玻璃态的物质，增加了陶粒体积收缩率，使得陶粒表面和内部的密度增大，吸水率降低，当温度超过1050℃时，由于后期产气反应的发生，陶粒内部气压增大，造成体积膨胀和密度降低；
对照例4与实施例1相比，当温度过低时，料球中部分组分未完全熔化，其内部结构疏松，仅有少部分形成玻璃态，而陶粒要烧胀必须满足2个条件：原料被加热到高温时，必须生成黏性的玻璃相，能密封住由原料内部释放的气体；高温下生成黏性的玻璃相后必须有气体物质释放。过低的温度会导致部分原料无法达到玻璃相，从而影响陶粒的烧胀。
只有当温度保持在一定范围时，陶粒内部形成玻璃体为主体，并能形成致密结构和均匀封闭的孔结构，该结构使得陶粒获得较高的强度；
本发明通过两段式烧结，低温烧结中使原料为烧胀形成的玻璃态作准备，使烧过程中的液相黏度大小适中，对陶粒膨胀性能有较有利的影响，再经过迅速高温烧结，有利于烧胀的进行。随着炉膛B中焙烧温度的升高，越来越多的原料成分熔化成液相并成为玻璃态物质，增加了陶粒体积收缩率，使得陶粒表面和内部的密度增大，吸水率降低，当温度过高时，反而会导致陶粒的性能下降。
采用本发明的技术方案，制备得到的陶粒具有明显的有益效果：
(1)减少了大块烧成物的产生，从而也相应的减少了后续的破碎工作。
以城市污泥为原料加入了辅料之后，制备陶粒，大块的烧成物较少，经过实验发现，大块烧成物的重量占所得的物料重量的8％左右，大大的减少了后续的破碎工作，节省了能耗，分析原因如下：
污泥料球在炉膛中自燃温度不易散失，自身温度迅速提高，而周边压力和有机物的减少，本身体积迅速减小，此时料球中的无机物处于半熔化状态，彼此之间发生粘连，而由于本发明中添加了部分辅料，使得料球在燃烧过程中产生了一些气体，这就使包裹在外层的半熔体发生膨胀形成空气泡，由于大量的空气泡的存在又互相粘连使失去了大量物质的污泥料球不会崩溃，只是比原来缩小了体积，而又由于辅料的加入，使料球之间的粘连度相应的减小，从而减少了大块烧成物的产生。因此，对于后续的破碎工作相应的也减少。
(2)筒压强度大，堆积密度低。
本发明的工艺采用分段式焙烧，在第一阶段焙烧时，陶粒内部孔隙分布相对均匀，孔隙小而多，主要是由于随着烧制温度的增加，陶粒表面的液相增多，陶粒料球表面粘度适合，内部有机物在高温下分解为气体，从而从陶粒料球的表面不断逸出，形成陶粒内部中空多孔的结构。第一阶段的升温过程中，陶粒表面的液相渗入陶粒的孔隙内部，减少了孔隙的大小，陶粒内部开始致密化，从而使得陶粒颗粒密度增加，当陶粒的烧制温度进一步升高并保持一定时间时，料球内部就会形成致密小孔结构，同时，这些小孔会互相连通或串通，进而形成大的孔隙，也会导致陶粒颗粒的堆积密度减小。
通过表1中关于陶粒性能的数据可以得出结论：实施例1的陶粒强度较高，堆积密度小，不仅符合国家标准要求，而且满足市场需求，得到了具有较低堆积密度性能的陶粒，可以使该陶粒更好的向市场推广。
实施例2
以取自青岛市某污水处理厂的城市污泥为原料的陶粒的制备方法，由以下具体步骤制成：
(1)干燥：对城市污泥进行浓缩、消化、机械脱水、烘干，得到原料污泥的含水率为22％左右；其消化步骤同实施例1；
(2)配料：按以下的重量份数配比取各原料：原料污泥80、粉煤灰10、高岭土1、炼钢炉渣5、沸石5、赤铁矿1、钙质页岩5、垃圾焚烧飞灰5、Fe2O3 0.5、废玻璃1、碳酸钙0.1、十二烷基硫酸钠0.1、苯甲酸钠0.1；
(3)将步骤(2)中的各原料混合、搅拌均匀，将搅拌后的物料投入造粒机中造粒，粒径控制在15～20mm之间；
(4)将造粒后的料球颗粒置于90℃下干燥2小时，再在220℃预热20分钟，然后迅速转移至烧结设备中烧结；
烧结设备有两个炉膛，炉膛A中提供的温度为600℃，炉膛B提供的温度为900℃；预热后的物料在炉膛A中烧制5分钟，再迅速转移到炉膛B中烧制6分钟，冷却至室温；
(5)将冷却后的物料卸下，并且对大块的烧成物破碎，使破碎物料的最大粒径控制在20～26mm之间；
(6)对破碎后的物料分筛，分筛出粒径为5～15mm的陶粒，15～26mm的陶粒，0.5～5mm的陶砂，粒径小于0.5mm的细末。
垃圾焚烧飞灰来自于城市固体废物处理厂。
实施例2制备得到的陶粒强度较高，堆积密度小，品质好，有利于陶粒的市场推广。
实施例3
以取自青岛市某污水处理厂的城市污泥为原料的陶粒的制备方法，由以下具体步骤制成：
(1)干燥：对城市污泥进行浓缩、消化、机械脱水烘干，得到的原料污泥的含水率为24％左右；其消化步骤同实施例1；
(2)配料：按以下重量份数配比取各原料：城市污泥120、粉煤灰20、高岭土5、炼钢炉渣20、沸石15、赤铁矿5、钙质页岩15、垃圾焚烧飞灰20、Fe2O3 2、废玻璃4、碳酸钙2、十二烷基硫酸钠2、苯甲酸钠1.5；
(3)取步骤(2)中的各原料，混合、搅拌均匀，将搅拌后的物料投入造粒机中造粒，粒径控制在15～20mm之间；
(4)将造粒后的料球颗粒置于110℃下干燥1小时，再在280℃预热10分钟，然后迅速转移至烧结设备中烧结；
烧结设备有两个炉膛，炉膛A中提供的温度为800℃，炉膛B提供的温度为1100℃；预热后的物料在炉膛A中烧制3分钟，再迅速转移到炉膛B中烧制4分钟，冷却至室温；
(5)将冷却后的物料卸下，并且对大块的烧成物破碎，使破碎物料的最大粒径控制在20～26mm之间；
(6)对破碎后的物料分筛，分筛出粒径为5～15mm的陶粒，15～26mm的陶粒，0.5～5mm的陶砂，粒径小于0.5mm的细末。
垃圾焚烧飞灰来自于城市固体废物处理厂。
实施例3制备得到的陶粒强度较高，堆积密度小，品质好，有利于陶粒的市场推广。
上述虽然结合实施例对本发明的具体实施方式进行了描述，但并非对本发明保护范围的限制，所属领域技术人员应该明白，在本发明的技术方案的基础上，本领域技术人员不需要付出创造性劳动即可做出的各种修改或变形仍在本发明的保护范围以内。

Claims (6)

1.以城市污泥为原料的陶粒的制备方法，其特征是，由以下具体步骤制成：
(1)干燥：对城市污泥浓缩、消化、机械脱水、烘干，得到原料污泥；
消化步骤为，采用普通厌氧工艺法去除污泥中的易生化的有机物；
(2)配料：按以下重量份数配比取各原料：原料污泥80～120、粉煤灰10～20、高岭土1～5、炼钢炉渣10～20、沸石5～15、赤铁矿1～5、钙质页岩5～15、垃圾焚烧飞灰5～20、Fe2O30.5～2、废玻璃1～4、碳酸钙0.1～2、十二烷基硫酸钠0.1～2、苯甲酸钠0.1～1.5；
(3)取步骤(2)中的各原料，混合、搅拌均匀，将搅拌后的物料投入造粒机中造粒，粒径控制在15～20mm；
(4)将造粒后的料球颗粒置于90-110℃下干燥1～2小时，再在220～280℃预热10～20分钟，然后迅速转移至烧结设备中烧结；
(5)将冷却后的物料卸下，并且对大块的烧成物破碎，使破碎物料的最大粒径控制在20～26mm之间；
(6)对破碎后的物料分筛，分筛出粒径为5～15mm的陶粒，15～26mm的陶粒，0.5～5mm的陶砂，粒径小于0.5mm的细末。
2.根据权利要求1所述的以城市污泥为原料的陶粒的制备方法，其特征是，所述步骤(1)的干燥后的原料污泥的含水率为22～24％。
3.根据权利要求1所述的以城市污泥为原料的陶粒的制备方法，其特征是，所述步骤(4)的烧结设备中进行两段式烧结，先低温烧结，后高温烧结。
4.根据权利要求1或3所述的以城市污泥为原料的陶粒的制备方法，其特征是，所述步骤(4)的烧结设备有两个炉膛，炉膛A中提供的温度为600～800℃，炉膛B提供的温度为900～1100℃；预热后的物料在炉膛A中烧制3～5分钟，再迅速转移到炉膛B中烧制4～6分钟，冷却至室温。
5.根据权利要求1所述的以城市污泥为原料的陶粒的制备方法，其特征是，所述步骤(2)的垃圾焚烧飞灰来自于城市固体废物处理厂。
6.根据权利要求1所述的以城市污泥为原料的陶粒的制备方法，其特征是，所述步骤(1)的消化步骤为，将城市污泥投入消化池中，加入兼性菌和厌氧菌，将城市污泥中的可生物降解的有机物分解成二氧化碳、甲烷和水。
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