CN116375453B - 自洁型无掺混高铝粉煤灰陶瓷膜支撑体的制备方法 - Google Patents
自洁型无掺混高铝粉煤灰陶瓷膜支撑体的制备方法 Download PDFInfo
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Abstract
本发明为一种自洁型无掺混高铝粉煤灰陶瓷膜支撑体的制备方法。该方法包括如下步骤:将高铝粉煤灰、淀粉、甲基纤维素混合,进行干混1h~2h,得到混合物料;然后再向其中加入蒸馏水,在80~100℃下恒温搅拌1h~2h,得到泥料,将泥料放置到模具中,在6MPa~14MPa压力下挤压成型,得到生胚;再将得到的生胚升温到1200℃~1400℃下,烧结0.5h~1h,得到自洁型无掺混高铝粉煤灰陶瓷膜支撑体。本发明不额外添加氧化铝或其他含铝氧化物,支撑体中固溶了铁氧化物和钛氧化物具有降解有机污阻的自洁能力,受污染的支撑体经氧化剂处理后通量恢复率高。
Description
技术领域
本发明涉及陶瓷膜技术领域,具体为一种适用于焦化废水的自洁型无掺混高铝粉煤灰陶瓷膜支撑体的制备方法。
背景技术
我国蕴藏着近1000亿吨高铝煤资源,每年产生高铝粉煤灰约5000万吨,属于大宗工业固废,由于无法有效资源化利用,使环境承载巨大压力,生态安全受到严重影响。近年来,对高铝粉煤灰的高值利用集中于提取氧化铝副产硅酸钙、铝硅氧化物,铝硅合金及陶瓷材料。其中,无机多孔陶瓷膜是污水处理过程的一种重要产品,当前制备陶瓷膜支撑体多以纯Al2O3为骨料,但因其需求量大、原料价格昂贵且烧结能耗高等缺点,制约了生产产能。高铝粉煤灰中含有大量的Al2O3和SiO2,含有的CaO、Fe2O3、TiO2等又是良好的烧结助剂,可以有效降低烧结温度;粉煤灰中的残碳还可起到造孔的作用,因此利用高铝粉煤灰制备陶瓷膜支撑体,既可降低陶瓷膜支撑体的制备成本,又能提高固体废弃物的利用率。例如万泽林(万泽林,张学斌,丁辉,等.高铝粉煤灰制备陶瓷膜支撑体的性能研究[J].中国陶瓷,2017,53(04):69-74.)等以粉煤灰为骨料烧结制备性能较优的支撑体,但造孔剂碱式碳酸镁的添加量为20%,不仅增加了制备成本,还引入杂质元素。章志斌(章志斌,李旺,谢玮玮,等.粉煤灰-氧化铝多孔陶瓷的制备[J].中国陶瓷,2008,237(08):27-30.)等按照粉煤灰∶Al2O3=1∶0.9比例混合制备了性能较优的支撑体,但氧化铝添加量较高,原料成本较高。
在膜分离污水处理技术应用过程中,过滤的料液体系中的溶质分子、有机物等在膜表面或孔内部会产生吸附与沉积,造成膜孔阻塞,进而导致膜通量下降的现象称为膜污染。膜污染一般通过反冲洗、化学清洗和甚至更换膜组件来解决,但是的运行维护成本较高,这也是需要不断改进的方向。例如专利CN111195484B给出一种板式陶瓷膜的清洁方法,为提高膜组件的使用寿命,需要对膜组件进行表面活性剂清洗和酸碱清洗,虽然陶瓷膜通量恢复率达到97.5%以上,但是酸碱液清洗对膜材料和膜分离性能带来损伤,后期维护成本高,易造成二次污染。专利CN115245751A提供一种催化自清洁型陶瓷膜的制备方法,该陶瓷膜通过表面负载纳米氧化铁体现催化自洁性能,膜通量恢复率达到93.37%,但负载的纳米氧化铁在使用过程中存在易流失的风险。
本发明提供一种无掺混高铝粉煤灰陶瓷膜支撑体的低成本制备方法,同时具有稳定的自洁能力。
发明内容
本发明的目的为针对当前技术中存在的不足,提供一种无掺混高铝粉煤灰陶瓷膜支撑体的低成本制备方法。该方法采用高铝粉煤灰、淀粉、甲基纤维素为原料,先干混,再加入水后混合、压制,得到陶瓷膜支撑体。本发明不额外添加氧化铝或其他含铝氧化物,支撑体中固溶了铁氧化物和钛氧化物具有降解有机污阻的自洁能力,受污染的支撑体经氧化剂处理后通量恢复率高。
为实现以上发明目的,本发明通过以下技术方案:
一种自洁型无掺混高铝粉煤灰陶瓷膜支撑体的制备方法,该方法包括如下步骤:
(1)将高铝粉煤灰、淀粉、甲基纤维素混合,进行干混1h~2h,得到混合物料;然后再向其中加入蒸馏水,在80~100℃下恒温搅拌1h~2h,得到泥料,将泥料放置到模具中,在6MPa~14MPa压力下挤压成型,得到生胚;
所述的泥料的质量百分含水量为5%~10%;所述的生坯的厚度为2.5mm~3mm;
(2)将得到的生胚升温到1200℃~1400℃下,烧结0.5h~1h,得到自洁型无掺混高铝粉煤灰陶瓷膜支撑体;
烧结方式优选为:室温至300℃,速率5~10℃/min,保温0.5h~1h;300℃至650℃,速率5~10℃/min,保温0.5h~1h;650℃至1200℃~1400℃,速率3~5℃/min,保温0.5h~1h。
其中,质量比为,粉煤灰:淀粉:甲基纤维素=87%~97%:2~10%:1~3%;蒸馏水的加入量为总泥料质量的20%~30%;
所述的对原料高铝粉煤灰进行预处理,经球磨机研磨后得到粒度分布范围为500nm~1000nm的高铝粉煤灰。
所述的高铝粉煤灰组成及质量分数包括:
Al2O3:60%~65%,SiO2:20%~25%,CaO:3%~5%,Fe2O3:2%~5%,TiO2:2%~5%。
所述的方法制备的自洁型无掺混高铝粉煤灰陶瓷膜支撑体的应用,包括以下步骤:
在支撑体覆盖上分离膜,组成陶瓷膜,然后通入焦化废水,0.1MPa~0.2MPa下过滤;
所述的焦化废水组成及浓度如下:
悬浮物:1000mg/L~1200mg/L,COD:5000mg/L~8000mg/L,氨氮:2000mg/L~3000mg/L,挥发酚:500mg/L~700mg/L,硫化物:20mg/L~50mg/L,氰化物:5mg/L~10mg/L,SCN:400mg/L~600mg/L,油:50mg/L~80mg/L,pH为6~7,其余为水。
所述的自洁步骤:
调节去离子水流量对截留有机物受污染的支撑体进行反冲洗清洁1min~2min,过滤压力为0.1MPa~0.2MPa;然后再将受污染的支撑体浸没入0.1mol/L~0.3mol/L的过硫酸钾溶液中,控制反应温度20℃~25℃,搅拌30min~60min后取出,完成自清洁。
本发明的实质性特点:
(1)用无掺混高铝粉煤灰作为骨料,添加少量造孔剂和粘结剂,挤压成型后烧结制备陶瓷膜支撑体,不额外添加氧化铝或其他含铝氧化物,降低了制备成本。
(2)支撑体中的铁氧化物和钛氧化物催化氧化剂产生自由基参与氧化反应,提高有机膜污染物的氧化效率,因此支撑体具有较高的通量恢复率,可减少反冲洗频次和化学清洗剂的加入量,体现自洁能力,从而提高膜组件的使用寿命。
(3)铁氧化物和钛氧化物固熔进支撑体中,具有较高的稳定性,在催化氧化过程中不易流失。
本发明的有益效果:
(1)本发明制得性能良好的低成本无掺混高铝粉煤灰陶瓷膜支撑体,孔隙率为31.5%~45.2%,抗弯强度为7MPa~28MPa,水通量为1800L/h·m2·MPa~4100L/h·m2·MPa。
(2)支撑体具备降解有机污阻的自洁能力,经1min去离子水反冲洗和60min过硫酸钾处理后通量恢复率达到95%以上。
(3)根据《多孔陶瓷耐酸、碱腐蚀性能试验方法(GB/T1970-1996)》测试支撑体耐酸、碱腐蚀性能,支撑体在酸性和碱性介质下质量损失率都低于2%,满足性能要求。支撑体中固熔的铁氧化物和钛氧化物具有较高的稳定性,在催化氧化过程中不易流失,适用于处理酸性或碱性溶液。
附图说明
图1为实施例1-5中得到的支撑体的烧结温度对支撑体孔隙率和抗弯强度的影响;
图2为实施例1-5中得到的支撑体的烧结温度对支撑体水通量的影响;
图3为实施例1、6-9中得到的支撑体的造孔剂添加量对支撑体孔隙率和抗弯强度的影响;
图4为实施例1、6-9中得到的支撑体的造孔剂添加量对支撑体水通量的影响;
图5为实施例1、10、11中得到的支撑体的粘结剂添加量对支撑体孔隙率和抗弯强度的影响;
图6为实施例1中得到的支撑体的主晶相莫来石的低倍形貌图和原子像;其中,图6a为莫来石晶体的低倍形貌图,图6b为莫来石晶体的原子像;
图7为实施例1中得到的支撑体的主晶相莫来石中的元素分布图;其中,图7a、图7b、图7c、图7d分别为莫来石中Al、Si、Fe、Ti的元素分布;
图8水通量测试装置示意图。
具体实施方式
本发明涉及的高铝粉煤灰为公知材料,组成及质量分数如下:Al2O3:63.7%,SiO2:24.9%,CaO:3.54%,Fe2O3:2.60%,TiO2:2.49%。但不局限与此。
实施例1
原料高铝粉煤灰采用球磨机研磨后得到粒径为500nm~1000nm的高铝粉煤灰。按照粉煤灰:淀粉:甲基纤维素=95%:4%:1%比例进行原料混合,将混合物料在室温下搅拌1h。向混合均匀的物料中加入占总泥料质量20%的蒸馏水,在90℃下恒温搅拌1h,使泥料进一步混匀并控制泥料含水量(质量百分比)为5%,将泥料放入自制模具中,在10MPa下挤压成型。将支撑体胚体放入马弗炉中按照烧结制度煅烧至1300℃。烧结制度设定为:室温至300℃,速率10℃/min,保温1h;300℃至650℃,速率10℃/min,保温1h;650℃至1200℃,速率5℃/min,保温1h。制得支撑体的孔隙率为37%,抗弯强度为22MPa,水通量为2800L/h·m2·MPa。支撑体尺寸为:直径15mm,厚度3mm。
根据《多孔陶瓷显气孔率试验方法(GB/T1966-1996)》测试支撑体的孔隙率,根据《多孔陶瓷弯曲强度试验方法(GB/T1965-1996)》测试支撑体的抗弯强度,水通量由实验室自制装置测得,如图8所示。《多孔陶瓷产品通用技术条件(GB/T16533-1996)》规定产品尺寸:圆板状多孔陶瓷产品直径为200mm、500mm、800mm,厚度为15mm、20mm、30mm。管状产品直径为15mm~200mm,厚度为3mm~30mm,长度30mm~100mm。
本发明所述的陶瓷膜分为分离膜和支撑体两部分。支撑体主要为分离膜提供机械强度和支撑作用,厚度一般为3mm~5mm;分离膜主要起到分离过滤作用,厚度一般为0.09mm~0.15mm。在处理焦化废水的过程中,过滤压力为0.1MPa~0.2MPa,流量为2000L/h·m2,一般运行1-2天进行清洗,比分离膜孔径小的物质(如水、无机盐和小分子等)可透过分离膜和支撑体。在支撑体表面或孔道内累积的悬浮物、油、有机大分子等物质会阻塞孔道,导致膜污阻,一般需要通过反冲洗、化学清洗、甚至更换膜组件来恢复水通量。
具体测试条件为:
采用实施例1制备的支撑体处理焦化废水,孔隙率为37%,抗弯强度为22MPa,水通量为2800L/h·m2·MPa,支撑体的直径为14.5mm,厚度2.5mm,孔径大小为665nm,属于微滤陶瓷膜支撑体。过滤压力为0.1MPa,流量为2000L/h·m2,运行4天后取出进行自清洁性能测试。所用焦化废水的具体组成如下:
悬浮物:1200mg/L,COD:7000mg/L,氨氮:2500mg/L,挥发酚:600mg/L,硫化物:30mg/L,氰化物:8mg/L,SCN:500mg/L,油:60mg/,pH为7,其余为水。
实施例2-11
其他步骤同实施例1,不同之处见下表:
从图1可以看到,随着烧结温度的升高,支撑体的孔隙率由45.2%逐渐降低至31.5%,抗弯强度由7MPa逐渐升高至28MPa。支撑体孔隙率与抗弯强度呈反向变化,即孔隙率越小抗弯强度越高。分析原因是随着烧结温度的升高,SiO2和Al2O3逐渐熔融转化为莫来石相,莫来石含量不断增加,使得支撑体的致密化程度越来越高,从而导致陶瓷膜支撑体的孔隙率逐渐降低、抗弯强度逐渐升高。
从图2可以看到,随着烧结温度的升高,支撑体的水通量由2100L/h·m2·MPa先增大至2800L/h·m2·MPa后降低到1800L/h·m2·MPa。分析原因是烧结温度低于1300℃时,随着烧结温度增加,支撑体的孔径增大,单位时间、面积和压强下的水通量增加,1300℃达到最大值;当烧结温度高于1300℃时,随烧结温度升高基体致密化程度增加,孔径减小,水通量逐渐降低。
从图3可以看到,随着造孔剂含量的增加,支撑体的孔隙率由33%逐渐升高至42%,抗弯强度由26MPa逐渐降低至14MPa。分析原因是造孔剂参与粉煤灰颗粒的堆积,在烧结过程中,造孔剂完全燃烧留下孔洞,随着造孔剂含量的增加,燃烧后生成孔洞的总体积也逐渐增加,所以支撑体的孔隙率升高;然而孔洞越多,越容易引起孔与孔相连形成大孔,使得支撑体的结构变得松散,导致抗弯强度降低。
从图4可以看到,随着造孔剂含量的增加,支撑体的水通量由2200L/h·m2·MPa逐渐增大至4100L/h·m2·MPa。分析原因是随着造孔剂含量的增加,支撑体的孔隙率和孔径增加,使得支撑体在单位时间、压强下,单位面积的水通量增加。为保证支撑体的抗弯强度,降低制备成本,造孔剂的添加量不宜过高。
从图5可以看到,随着粘结剂含量的增加,支撑体的孔隙率由37%升高至39%,抗弯强度由22MPa降低至20.2MPa,均变化不大。原因是当粘结剂含量较低时,粘结剂占据的是泥料颗粒之间的间隙,因此当粘结剂烧失后,对支撑体孔隙率和抗弯强度的影响并不明显。为保证支撑体生胚的可塑性,降低制备成本,粘结剂的添加量不宜过高。
原料按照高铝粉煤灰:淀粉:甲基纤维素=87%~97%:2~10%:1~3%比例混合,在1200℃~1400℃下烧结制备陶瓷膜支撑体,支撑体的孔隙率为31.5%~45.2%,抗弯强度为7MPa~28MPa,水通量为1800L/h·m2·MPa~4100L/h·m2·MPa。较优的制备条件为高铝粉煤灰:淀粉:甲基纤维素=95%:4%:1%,烧结温度为1300℃,制得支撑体的孔隙率为37%,抗弯强度为22MPa,水通量为2800L/h·m2·MPa。
下面是相关实施例制备的支撑体的自洁性能测试。
自洁性能测试
由图6、7可知,支撑体的主晶相为莫来石,铁、钛元素固溶进莫来石晶体中且均匀分布,在催化氧化过程中不易流失,为自洁性能提供理论支撑。
利用实施例1中制备的支撑体处理焦化废水,运行了2天后进行自清洁测试,调节去离子水流量对截留有机物受污染的支撑体进行反冲洗清洁1min,过滤压力为0.1MPa,测试支撑体的水通量(JF1),计算支撑体通量恢复率(FRR1);控制实验温度为25℃,将受污染的支撑体放入0.1mol/L的过硫酸钾溶液中,液面盖过支撑体上表面,搅拌清洁60min后取出,测试支撑体的水通量(JF2),通过计算通量恢复率(FRR2)来表征支撑体的自清洁性能。具体计算公式如下:
FRR=JF/Jo×100%
其中FRR表示通量恢复率(%);Jo为支撑体的初始水通量;JF为清洁后支撑体的水通量(LMH)。
由实施例1可知支撑体的初始水通量Jo为2800L/h·m2·MPa,反冲洗后测得支撑体的水通量JF1为1456L/h·m2·MPa,计算支撑体水通量恢复率FRR1为52%。经过硫酸钾溶液处理后测试支撑体的水通量JF2为2670L/h·m2·MPa,计算支撑体水通量恢复率FRR2为95.4%。
上述仅为本发明的几个具体实施方式,本发明并不局限于以上几个实施例限制,本领域的普通技术人员在不偏离本发明的范围情况下做出的任何修改、替换、改进等都应在本发明的保护范围之内。
本发明未尽事宜为公知技术。
Claims (4)
1.一种自洁型无掺混高铝粉煤灰陶瓷膜支撑体的制备方法,其特征为所述方法包括如下步骤:
(1)将高铝粉煤灰、淀粉、甲基纤维素混合,进行干混1h~2h,得到混合物料;然后再向其中加入蒸馏水,在80~100℃下恒温搅拌1h~2h,得到泥料,将泥料放置到模具中,在6MPa~14MPa压力下挤压成型,得到生坯;
其中,质量比为,粉煤灰:淀粉:甲基纤维素=87%~97%:2~10%:1~3%;蒸馏水的加入量为总泥料质量的20%~30%;
(2)将得到的生坯升温到1200℃~1400℃下,烧结0.5h~1h小时,得到自洁型无掺混高铝粉煤灰陶瓷膜支撑体;
所述的泥料的质量百分含水量为5%~10%;
烧结方式为:室温至300℃,速率5~10℃/min,保温0.5h~1h;300℃至650℃,速率5~10℃/min,保温0.5h~1h;650℃至1200℃~1400℃,速率3~5℃/min,保温0.5h~1h;
所述的高铝粉煤灰的粒度为500nm~1000nm;
所述的高铝粉煤灰组成及质量分数包括:Al2O3:60%~65%,SiO2:20%~25%,CaO:3%~5%,Fe2O3:2%~5%,TiO2:2%~5%。
2.如权利要求1所述的自洁型无掺混高铝粉煤灰陶瓷膜支撑体的制备方法,其特征为所述的生坯的厚度为2.5mm~3mm。
3.如权利要求1所述的方法制备的自洁型无掺混高铝粉煤灰陶瓷膜支撑体的应用,其特征为包括以下步骤:
在支撑体覆盖上分离膜,组成陶瓷膜,然后通入焦化废水,0.1MPa~0.2MPa下过滤;
所述的焦化废水组成及浓度如下:
悬浮物:1000mg/L~1200mg/L,COD:5000mg/L~8000mg/L,氨氮:2000mg/L~3000mg/L,挥发酚:500mg/L~700mg/L,硫化物:20mg/L~50mg/L,氰化物:5mg/L~10mg/L,SCN:400mg/L ~600mg/L,油:50mg/L~80mg/L,pH为6~7,其余为水。
4.如权利要求3所述的应用,其特征为自洁步骤包括:
调节去离子水流量对截留有机物受污染的支撑体进行反冲洗清洁1min~2min,过滤压力为0.1MPa~0.2MPa;然后再将受污染的支撑体浸没入0.1mol/L~0.3mol/L的过硫酸钾溶液中,控制反应温度为20℃~25℃,搅拌30min~60min后取出,完成自清洁。
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