CN115432813A - 一种高比表面积,耐老化的mbbr填料及其制备方法 - Google Patents
一种高比表面积,耐老化的mbbr填料及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种高比表面积,耐老化的MBBR填料,所述有效表面积为5000‑6500m2/m3,厚度为0.5‑2μm。本发明采用聚乙烯,聚丙烯和乙烯醋酸乙烯酯聚合物作为树脂基体,使制备的MBBR填料具有良好的亲水性和生物亲和性,提高了MBBR填料表面的挂膜率,有利于微生物在填料表面附着。并且采用钙粉和硬脂酸钙搭配,可以提高聚集在MBBR填料表面微生物的新陈代谢,加快微生物对污染物的吸收和降解。同时泡孔的每一个面为微生物提供0.5mm最佳生活及提取营养空间,不堵塞,流化快,由于产品带有保护环,能更好的保护微孔体,耐冲击性能佳,更耐老化,投入使用以后,终身免维护,无需冲洗及补充。
Description
技术领域
本发明涉及一种高比表面积,耐老化的MBBR填料及其制备方法,涉及C02F,具体涉及水、废水、污水或污泥的处理领域。
背景技术
MBBR工艺是运用生物膜法的原理,在污水处理器中投入悬浮填料载体,为微生物分解提供生活温床,微生物依靠吸收周围富营养,形成密集代谢分解污水中有害杂质,加快水质沉淀清澈。MBBR填料是应用在MBBR工艺中的微生物载体,主要是为微生物提供适合生长的环境。前的MBBR传统填料依靠几何形状增加有效表面积,为微生物提供更多的负载空间,但是几何形状的变化对有效表面积增加有一定瓶颈无法突破,通过进一步探索采用海绵体结构可以进一步增加表面积,但是海绵体在处理污水的过程中容易堵塞,处理污水效率不稳定,需要定期维护,并且长时间使用容易磨损老化掉渣,二次污染环境。
中国发明专利CN201910829291.8公开了一种MBBR污水处理用填料及其使用方法,通过在填料原料中增加活性炭、淀粉和明胶材料作为生物活性添加剂,使得制备的填料能够促进微生物的生长和繁殖,但是引入的聚氨酯泡沫使得填料的阻力增大,长时间使用容易堵塞。中国发明专利CN202010429113.9公开了一种MBBR悬浮生物填料及其制备方法,引入缓释碳源和生物酶增活材料,易于微生物生长;表面粗糙有效表面积大、亲水性好,易于微生物生长附着,但是形成的MBBR填料为平面填料,有效面积不够大。
发明内容
为了提高MBBR填料的有效比表面积,增加微生物负载率,延长MBBR填料的使用寿命,本发明的第一个方面提供了一种高比表面积,耐老化的MBBR填料,所述有效表面积为5000-6500m2/m3,厚度为0.5-2μm。
作为一种优选的实施方式,制备原料以重量份计包括树脂基体300-400份,交联剂1-5份,发泡剂10-30份,矿物质粉30-45份,润滑剂2-8份,金属氧化物5-15份。
作为一种优选的实施方式,所述树脂基体选自聚乙烯、聚丙烯、聚氨酯、聚乙烯醇、乙烯-丙烯聚合物、聚乳酸、乙烯-醋酸乙烯酯聚合物中的一种或几种的组合。
作为一种优选的实施方式,所述乙烯-醋酸乙烯聚合物中醋酸乙烯酯的质量分数为5-40%。
作为一种优选的实施方式,所述树脂基体为聚乙烯、聚丙烯和乙烯-醋酸乙烯聚合物的组合。
作为一种优选的实施方式,所述聚乙烯、聚丙烯和乙烯-醋酸乙烯聚合物的重量比为(190-210):(12-18):(115-125)。
作为一种优选的实施方式,所述聚乙烯、聚丙烯和乙烯-醋酸乙烯聚合物的重量比为(180-210):(11-15):(110-120)。
作为一种优选的实施方式,所述聚乙烯、聚丙烯和乙烯-醋酸乙烯聚合物的重量比为200:15:120。
申请人在实验过程中发现,采用PE,PP的组合作为树脂基体可以使制备的MBBR填料具有一定的力学性能,可以承受水力的剪切,气流的冲击和载体之间的摩擦碰撞,但是形成的树脂基体亲水性不佳,微生物在填料表面不易附着,申请人发现通过引入EVA树脂,可以增加树脂基体的亲水性和生物亲和性,提高微生物在MBBR填料表面的附着,为微生物生长提供相对稳定的环境。猜测可能的原因是:采用VA含量为28%的EVA对PE和PP进行改性,EVA中含有的羰基通过乙烯基之间的反应接枝到聚合物表面,增加MBBR填料的表面润湿性能和亲水性能,使微生物容易在填料载体表面附着。申请人进一步发现,当PE,PP,EVA的重量比为(180-210):(11-15):(110-120)时,制得的MBBR填料具有良好的机械性能,超出优选的重量比范围,形成的MBBR填料质地较软,泡孔之间承载力不够,不利于微生物的长期稳定生存。
作为一种优选的实施方式,所述交联剂起到架桥剂的作用,分子内含有多个不饱和双键,选自二乙烯基苯、二异氰酸酯,N,N-亚甲基双丙烯酰胺(MBA)中的一种或几种的组合。采用交联剂使线型的大分子转变成三维网状结构,提高基体树脂发泡后的力学性能。
作为一种优选的实施方式,所述发泡剂选自有机发泡剂或无机发泡剂中的一种,所述有机发泡剂选自偶氮类发泡剂、磺酰肼类发泡剂、亚硝基类发泡剂中的一种或几种的组合。
作为一种优选的实施方式,所述矿物质粉选自钙类化合物、淀粉、磷灰石、活性炭中的一种或几种的组合。
作为一种优选的实施方式,所述钙类化合物包括钙粉和硬脂酸钙,所述钙粉为大结晶方解石构型,粒径为600-800目。
作为一种优选的实施方式,所述钙粉和硬脂酸钙的质量比为(3-4):(1-3)。
作为一种优选的实施方式,所述钙粉和硬脂酸钙的质量比为4:3。
申请人在实验过程中发现在MBBR填料的制备原料中引入钙粉和硬脂酸钙可以提高表面聚集微生物的新陈代谢,加快微生物对污染物的吸收和降解,提高污染物的净化率,猜测可能的原因是:将大结晶方解石构型,粒径为600-800目的钙粉引入基体树脂中,可以为聚集微生物提供外加碳源,促进微生物的反硝化作用,提高微生物降解有毒污染物的速率,但是申请人进一步发现,钙粉在基体树脂中容易析出,长时间使用后使用效果会显著下降,通过引入钙粉和硬脂酸钙的组合,可以延长MBBR填料的使用效果,原因可能是:硬脂酸钙的引入为基体树脂表面引入了负离子,增加了对钙离子的吸附作用,提高了钙粉对基体树脂的附着,使钙粉在MBBR填料中缓慢释放,从而延长了MBBR填料的使用时效。
作为一种优选的实施方式,所述润滑剂为PE蜡。
通过引入PE蜡,可以改善MBBR填料在挤出发泡过程中的加工性能,减少挤出发泡过程中由于泡孔壁较薄造成的泡孔破碎,降低次品率。
作为一种优选的实施方式,所述金属氧化物为钛白粉。
本发明的第二个方面提供了一种高比表面积,耐老化的MBBR填料的制备方法,包括以下步骤:
(1)将树脂基体,交联剂,矿物质粉,润滑剂,金属氧化物通过混合搅拌机加热恒温50-70℃,混合搅拌20-30min;
(2)统一导入密炼机内进行密炼,加入发泡剂后经螺杆挤出机挤出发泡,发泡时形成的泡孔均匀稳定。
作为一种优选的实施方式,所述螺杆挤出机的温度区间为170-180℃,160-170℃,135-145℃,125-135℃。
作为一种优选的实施方式,所述螺杆挤出机的温度区间为175℃,165℃,140℃,130℃。
申请人在实验过程中发现,采用偶氮二甲酰胺作为发泡剂,并搭配175℃,165℃,140℃,130℃温度下的发泡温度,可以提高MBBR填料的发泡均匀度,形成泡孔均匀的三维立体结构,增加MBBR填料的微生物承载率,猜测可能的原因是,在发泡剂偶氮二甲酰胺的作用下均匀搅拌,形成泡核分布均匀的体系,在不同的发泡温度中,泡孔不断生长,立体叠加的泡核在不同的温度区间下缓慢生长,形成了三维立体微孔填料,并且本发明形成的是开放式泡孔,在厚度仅为1.1mm的MBBR填料中实现了3D泡孔,有效增加了MBBR填料的有效比表面积,并且MBBR填料不易堵塞,流化快。
作为一种优选的实施方式,所述步骤2的发泡时间为25-35s,螺杆挤出机的挤出速度为3-8m/min。
申请人在实验过程中发现,现有的高微生物承载量的MBBR填料在长时间使用后由于水流、气流或载体之间的冲刷,会导致填料壁变薄,在不断的冲击力下会出现MBBR填料磨损掉渣的情况,对环境造成二次污染,并且对微生物的营养补充性能急剧下降需要定期维护,本申请中树脂基体与矿物质粉和金属氧化物采用(30-35):(3-5):1的重量比,可以延长MBBR填料的使用寿命,减少或避免传统填料出现的掉渣问题。原因可能是:在优选的重量比下,MBBR填料具有良好的机械性能,可以维持泡孔壁一定的硬度,避免泡孔冲刷变薄,减少外界冲击对MBBR填料的损害,超出优选的重量比范围,可能会导致树脂基体发泡不足,降低泡孔的发泡率,减少对微生物的承载。
申请人进一步发现,树脂基体与矿物质粉和钛白粉采用(30-35):(3-5):1的重量比可以提高泡孔的表面粗糙度,进一步增加微生物在填料表面的附着率,提高微生物承载量。
与现有技术相比,本发明具有以下有益效果:
(1)本发明所述高比表面积,耐老化的MBBR填料,采用聚乙烯,聚丙烯和乙烯醋酸乙烯酯聚合物作为树脂基体,使制备的MBBR填料具有良好的亲水性和生物亲和性,提高了MBBR填料表面的挂膜率,有利于微生物在填料表面附着。
(2)本发明所述高比表面积,耐老化的MBBR填料,采用大结晶方解石构型的钙粉,搭配硬脂酸钙,可以提高聚集在MBBR填料表面微生物的新陈代谢,加快微生物对污染物的吸收和降解,提高MBBR工艺的净化率。
(3)本发明所述高比表面积,耐老化的MBBR填料,采用偶氮二甲酰胺作为发泡剂,搭配175℃,165℃,140℃,130℃的区间发泡温度,可以形成三维立体微孔填料,增加了MBBR填料的有效比表面积,降低了MBBR填料的厚度,增加了相同体积下的微生物承载率。
(4)本发明所述高比表面积,耐老化的MBBR填料,树脂基体,矿物质粉和金属氧化物采用(30-35):(3-5):1的质量比,可以延长MBBR填料的使用寿命,减少对MBBR填料的短期维护,避免MBBR填料可能带来的环境污染。
(5)本发明所述高比表面积,耐老化的MBBR填料,有效比表面积达到5500㎡/m3,厚度仅为1.1mm呈双面表面粗糙微孔,每一个面为微生物提供0.5mm最佳生活及提取营养空间,不堵塞,流化快,由于产品带有保护环,能更好的保护微孔体,耐冲击性能佳,更耐老化,投入使用以后,终身免维护,无需冲洗及补充。
(6)本发明所述高比表面积,耐老化的MBBR填料,还可以应用在循环水养殖业的污水处理上面,该产品因为比表面积大而挂微生物稳定,大大的节省了循环水养殖的生化池占地面积,促进循环水养殖业,提高鱼苗虾苗的养殖效率,加快了养殖业量产的推进,一立方填料可以服务800-1000公斤成品鱼类。
(7)本发明所述高比表面积,耐老化的MBBR填料,应用具有广谱性,可广泛应用在工业污水处理,生活污水处理,循环水养殖污水处理,屠宰业血水污水处理等领域中。
附图说明
图1为本发明高比表面积,耐老化的MBBR填料的结构示意图。
图中:1.保护环;2.微孔体。
具体实施方式
实施例1
如图1所示:一种高比表面积,耐老化的MBBR填料,制备原料以重量份计包括树脂基体335份,交联剂3份,发泡剂20份,矿物质粉35份,润滑剂5份,金属氧化物10份。
所述树脂基体为聚乙烯、聚丙烯和乙烯-醋酸乙烯聚合物的组合,重量比为200:15:120。所述乙烯-醋酸乙烯聚合物中醋酸乙烯酯的质量分数为28%,购自韩国乐天,型号为VS430。所述聚乙烯购自茂名石化,型号为7042,聚丙烯购自巨正源,型号为T03。
所述交联剂为N,N-亚甲基双丙烯酰胺。
所述发泡剂为偶氮二甲酰胺。
所述矿物质粉为钙粉和硬脂酸钙的组合,重量比为4:3,所述钙粉为大结晶方解石构型,粒径为800目,购自郑州利兴化工产品有限公司。
所述润滑剂为PE蜡,购自宁海博尔化工有限公司;所述金属氧化物为钛白粉。
一种高比表面积,耐老化的MBBR填料的制备方法,包括以下步骤:
(1)将树脂基体,交联剂,矿物质粉,润滑剂,金属氧化物通过混合搅拌机加热恒温60℃,混合搅拌25min;
(2)统一导入密炼机内进行密炼,加入发泡剂后经螺杆挤出机挤出发泡,发泡时形成的泡孔均匀稳定。
所述螺杆挤出机的温度区间为175℃,165℃,140℃,130℃。
所述步骤2的发泡时间为30s,螺杆挤出机的挤出速度为5m/min。
实施例2
一种高比表面积,耐老化的MBBR填料,具体步骤同实施例1,不同点在于所述树脂基体为聚乙烯、聚丙烯的组合。
实施例3
一种高比表面积,耐老化的MBBR填料,具体步骤同实施例1,不同点在于所述矿物质粉为碳粉和硬脂酸钙。
实施例4
一种高比表面积,耐老化的MBBR填料,具体步骤同实施例1,不同点在于所述螺杆挤出机的温度区间为175℃,130℃。
实施例5
一种高比表面积,耐老化的MBBR填料,具体步骤同实施例1,不同点在于所述制备原料以重量份计包括树脂基体340份,交联剂3份,发泡剂20份,矿物质粉3份,润滑剂5份,金属氧化物0.8份。
性能测试
1.有效比表面积:参考CJ/T 461―2014标准测试制备的MBBR填料的有效比表面积。
2.厚度:使用游标卡尺测量制备的MBBR填料的厚度。
3.使用寿命:将制备的MBBR填料置于pH为2的水中,使用800rpm/min的搅拌速率,测试3个月后,观察实施例1-5制备的MBBR填料的外观表现。
测试结果见表1。
表1
Claims (10)
1.一种高比表面积,耐老化的MBBR填料,其特征在于,所述有效表面积为5000-6500m2/m3,厚度为0.5-2μm。
2.根据权利要求1所述高比表面积,耐老化的MBBR填料,其特征在于,制备原料以重量份计包括树脂基体300-400份,交联剂1-5份,发泡剂10-30份,矿物质粉30-45份,润滑剂2-8份,金属氧化物5-15份。
3.根据权利要求2所述高比表面积,耐老化的MBBR填料,其特征在于,所述树脂基体选自聚乙烯、聚丙烯、聚氨酯、聚乙烯醇、乙烯-丙烯聚合物、聚乳酸、乙烯-醋酸乙烯酯聚合物中的一种或几种的组合。
4.根据权利要求3所述高比表面积,耐老化的MBBR填料,其特征在于,所述乙烯-醋酸乙烯聚合物中醋酸乙烯酯的质量分数为5-40%。
5.根据权利要求2所述高比表面积,耐老化的MBBR填料,其特征在于,所述发泡剂选自有机发泡剂或无机发泡剂中的一种,所述有机发泡剂选自偶氮类发泡剂、磺酰肼类发泡剂、亚硝基类发泡剂中的一种或几种的组合。
6.根据权利要求2所述高比表面积,耐老化的MBBR填料,其特征在于,所述矿物质粉选自钙类化合物、淀粉、磷灰石、活性炭中的一种或几种的组合。
7.根据权利要求6所述高比表面积,耐老化的MBBR填料,其特征在于,所述钙类化合物包括钙粉和硬脂酸钙,所述钙粉为大结晶方解石构型,粒径为600-800目。
8.一种根据权利要求1-7任一项所述高比表面积,耐老化的MBBR填料的制备方法,其特征在于,包括以下步骤:
(1)将树脂基体,交联剂,矿物质粉,润滑剂,金属氧化物通过混合搅拌机加热恒温50-70℃,混合搅拌20-30min;
(2)统一导入密炼机内进行密炼,加入发泡剂后经螺杆挤出机挤出发泡,发泡时形成的泡孔均匀稳定。
9.根据权利要求8所述高比表面积,耐老化的MBBR填料的制备方法,其特征在于,所述螺杆挤出机的温度区间为170-180℃,160-170℃,135-145℃,125-135℃。
10.根据权利要求8所述高比表面积,耐老化的MBBR填料的制备方法,其特征在于,所述步骤2的发泡时间为25-35s,螺杆挤出机的挤出速度为3-8m/min。
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