CN111410547B - 一种固废基陶瓷催化膜及其制备方法和应用 - Google Patents
一种固废基陶瓷催化膜及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种固废基陶瓷催化膜及其制备方法和应用。该方法利用硅酸盐尾矿和冶金渣作为主要原料,通过颗粒堆积法制备固废基陶瓷催化膜,固废基陶瓷催化膜具有力学性能好、催化活性高等特点,可以高效催化过一硫酸盐氧化降解水体中有机污染物,且可多次回收并重复利用。
Description
技术领域
本发明涉及一种固废基陶瓷催化膜,具体涉及一种利用硅酸盐尾矿、铝土矿和冶金渣制备的陶瓷催化膜,还涉及一种固废基陶瓷催化膜的制备方法以及固废基陶瓷催化膜在催化过一硫酸盐氧化降解水体中有机污染物方面的应用,属于催化材料制备技术领域。
背景技术
膜催化技术是将膜技术应用于催化反应领域,结合了催化剂的膜分离和自由基对有机污染物的催化分解,利用表面催化剂的高催化活性和高亲水性去除污染物,有效地避免催化剂难以回收而引起的水体二次污染情况,是一种很有前景的用于处理水体中难降解有机物的方法。目前针对水中难降解有机物催化膜的构建研究主要集中在光催化膜技术上,但是光催化技术完全依赖于光源,在实际废水处理中很难实现应用。高级氧化技术与光催化技术相比,不需要光源的刺激,在催化剂和氧化剂存在的条件下,就能实现对有机污染物有效地去除。
目前,对于高级氧化陶瓷催化膜制备研究还较少,专利(CN 108640227A)用Al2O3、TiO2、SiO2、ZrO2、SiC中的一种或几种作为陶瓷膜基体材料,以CuO、Fe2O3、Co3O4、MnO2、Fe3O4、RuO2金属氧化物纳米颗粒中的一种或几种为陶瓷膜中催化剂,制备出膜孔径大小为0.01μm~1μm的高级氧化催化陶瓷膜。Wu等人将MnO2,Al2O3,聚乙烯醇和甘油按一定比例配成原料,采用一步球磨法制备陶瓷催化膜(Hong Wu,Xinyuan Xu,Lei Shi,Yu Yin,Lai-ChangZhang,Zhentao Wu,Xiaoguang Duan,Shaobin Wang,Hongqi Sun.Manganese oxideintegrated catalytic ceramic membrane for degradation of organic pollutantsusing sulfate radicals.Water Research.167(2019)115110)。MnO2能在催化膜孔内提供大量的活性位点,促进PMS的活化,对4-羟基苯甲酸的去除率达到98.6%。这种催化膜催化效率较高,但是所用的原料成本和烧结成本高,导致催化膜制备成本偏高,难以实现工业应用。李2等人通过真空抽滤法,将制备所得的MnOOH负载于商业有机膜上,成功制备纳米MnOOH催化膜,构建了MnOOH催化膜/PMS体系(李易丞.MnOOH催化膜活化过一硫酸盐去除水中2,4-二氯酚的机理研究[M],吉林大学)。该陶瓷膜在120min内,对2,4-二氯苯酚去除率超过99%,但是有机膜与无机膜相比,化学稳定性弱、机械强度低、不耐高温、抗微生物能力差,冲洗和反冲洗能力差,循环利用效果不理想。
近年来,我国尾矿和冶金渣等固体废弃物堆存的问题愈发明显,给环境带来了的压力日益增大,如何妥善的处置和利用这些固体废弃物是当前的一大难题。国内外利用固体废弃物的资源属性,制备了各种建筑材料,但是冶金渣中含有丰富的过渡金属元素或催化成分,其作为建筑材料的原料不能得到最大价值的利用。
发明内容
针对现有技术中高级氧化陶瓷催化膜的制备方法存在原料成本高,能耗高等技术问题,本发明的第一个目的是在于提供一种对过一硫酸盐分解产生自由基具有较高催化活性的固废基陶瓷催化膜,该固废基陶瓷催化膜利用硅酸盐尾矿、铝土矿与冶金渣等原料来制备,实现二次资源的高值化利用,解决了现有催化膜原料成本高的问题。
本发明的第二个目的是在于提供一种制备固废基陶瓷催化膜的方法,该方法利用硅酸盐尾矿与冶金渣两种固体废弃物为主要原料,不但降低了固废基陶瓷催化膜原料成本,且大量消纳了固体废弃物,减少环境污染,且固废基陶瓷催化膜制备过程简单,能耗低,有利于工业化生产应用。
本发明的第三个目的是在于提供一种利用固废基陶瓷催化膜催化过一硫酸盐高效氧化去除水体中有机污染物的应用方法,固废基陶瓷催化膜的催化活性高,且使用成本低,可以回收利用,解决现有粉末催化剂在去除水体有机污染物时难以回收利用的问题。
为了实现上述技术目的,本发明提供了一种固废基陶瓷催化膜的制备方法,该方法是将硅酸盐尾矿、铝土矿、冶金渣通过湿法球磨后,干燥,得到混合原料;所述混合原料与粘合剂搅拌均匀后,经过干燥、研磨和过筛,得到粉体;所得粉体通过压制成型得到坯体;所述坯体经过烧结,即得。
优选的方案,所述冶金渣为锰渣、钢渣、赤泥中至少一种。
优选的方案,硅酸盐尾矿、铝土矿和冶金渣的质量百分比组成:硅酸盐尾矿60~65%,铝土矿10~15%,冶金渣20~25%。其中,硅酸盐尾矿和铝土矿为陶瓷膜提供必要的硅源和铝源作为陶瓷膜的骨架结构和基底材料,而冶金渣含有丰富的过渡金属元素,能为陶瓷膜提供活性组分,在催化膜上或膜孔内提供大量的活性位点,促进PMS的活化。
优选的方案,所述湿法球磨的条件为:球磨转速为300~380rpm,时间为10~12h。湿法球磨采用的球磨介质如水等常规的介质。
优选的方案,所述粘合剂为质量百分比浓度为5%~8%的聚乙烯醇溶液;聚乙烯醇溶液与混合原料的质量比为0.5~1:8~10。采用聚乙烯醇溶液作为粘合剂,其除了起到粘合作用,还具有保湿作用,有利于后续的压制成型过程。
优选的方案,所述搅拌过程中加热温度至85~90℃。在适当的加热条件下有利于粘合剂溶液充分润湿混合原料。
优选的方案,所述烧结采用两段烧结方式:第一段烧结在500~600℃(优选为550℃)烧结90min~120min,第二段烧结在1130~1150℃烧结20~30min。第一段烧结主要是进行脱胶过程,同时形成孔隙结构,孔隙结构有利于暴露固废基陶瓷催化膜内部具有催化活性的过渡金属,提高催化活性,如果脱胶不干净会影响材料的催化性能。第二段烧结是在高温下进行复杂的固相反应形成具有高强度陶瓷相,从而得到具有一定力学强度和具有多孔孔隙的固废基陶瓷催化膜。
优选的方案,所述过筛为通过300~350目筛网。
优选的方案,所述压制成型采用的成型压力为5~8MPa。
本发明的技术方案中湿法球磨得到的浆料进行干燥的温度为60~65℃,干燥时间为7~8h。
本发明的技术方案中混合原料与聚乙烯醇溶液在加热条件下搅拌混合均匀后,经过85~90℃干燥7~8h。
本发明还提供了一种固废基陶瓷催化膜,其由所述制备方法得到。
本发明还提供了一种固废基陶瓷催化膜的应用,将其应用于催化过一硫酸盐氧化降解水体中有机污染物。
优选的方案,所述有机污染物为染料和/或抗生素。所述染料为甲基橙、亚甲基蓝或罗丹明B等;所述抗生素为磺胺甲基嘧啶或四环素等。
优选的方案,水体中过一硫酸盐的添加浓度为1~3g/L;水体中有机污染物的浓度:包含染料100~200mg/L和/或抗生素10~20mg/L。在优选的条件下,固废基陶瓷催化膜对染料的去除率达到90~92%,对抗生素的去除率达到85~88%。
本发明的固废基陶瓷催化膜在处理有机物污染水体时,将固废基陶瓷催化膜固定后,使含有机物的废水和过一硫酸盐混合水体从固废基陶瓷催化膜上表面流下,在催化膜层进行降解反应,经过催化降解后的废水从固废基陶瓷催化膜下表面流出。固废基陶瓷催化膜的一般尺寸为:直径大小为d=30mm,厚度为5mm,控制废水通过固废基陶瓷催化膜的流速为1~2mL/min。固废基陶瓷催化膜的尺寸大小可以根据需要来进行相应设计。
本发明的固废基高强度泡沫陶瓷的制备方法,包括以下步骤:
步骤1)称取一定量的硅酸盐尾矿、铝土矿和冶金渣(原料质量百分比组成为硅酸盐尾矿60~65%,铝土矿10~15%,冶金渣20~25%)加入到球磨罐中,以300~380rpm球磨10~12h,得到混合均匀的浆料;
步骤2)将步骤1)所得的浆料在60~65℃烘干7~8h,按照m(聚乙烯醇溶液):m(粉体)为1:10加入5%的聚乙烯醇溶液,在85~90℃高温下搅拌均匀;
步骤3)将步骤2)所得搅拌均匀浆料继续于60~65℃干燥7~8h,然后将所得粉体过300~350目筛网后,于5~8MPa下成型。
步骤4)将步骤3)所得成型后胚体置于马弗炉内烧结,烧结温度为:第一段550℃烧结2h,第二段1130~1150℃烧结20~30min。
本发明的固废基陶瓷催化膜抗压强度为5.4MPa左右,气孔率为53%左右。
本发明的固废基陶瓷催化膜应用于去除水体中有机污染物的过程:将催化膜固定好后,使含有机物废水与1~3g/L过一硫酸盐混合后水体,以1~2mL/min从催化膜表上面流至下表面,其中含染料的有机废水浓度为100~200mg/L,含抗生素的有机废水浓度为10~20mg/L。采用催化膜层对有机废水进行降解后,对染料的去除率为90~92%,对抗生素的去除率为85~88%。
本发明技术方案主要利用硅酸盐尾矿和铝土矿作为硅源和铝源,利用冶金渣提供催化活性组分,硅酸盐尾矿中硅铝等与冶金渣中的钙、铁等经过高温固相反应形成强度较高的陶瓷相,同时利用冶金渣中的过渡金属组分提供催化活性中心,制备成一体式高级氧化陶瓷催化膜。
与现有技术相比,本发明具有以下优点:
1)本发明充分利用了尾矿和冶金渣两种固体废弃物中的成分,利用硅酸盐尾矿作为硅源,配入适量的铝土矿作为铝源,同时充分发挥冶金渣中过渡元素的催化作用,通过高温固相反应,形成了具有力学性能好,孔隙率高,催化活性高的固废基陶瓷催化膜。
2)本发明的固废基陶瓷催化膜的制备充分利用固体废弃资源,原料价格低廉,有利于缓解固体废弃物对环境带来的压力。
3)本发明的固废基陶瓷催化膜的制备工艺简单,无需对尾矿和冶金渣等原料进行特殊处理,且烧结温度低,能耗低,有利于工业化生产。
4)本发明的固废基陶瓷催化膜克服传统粉末催化剂难以回收利用的弊端,同时,固废基陶瓷催化膜将膜技术和高级氧化技术充分结合,在去除水体中有机污染物的同时,提高了催化膜的抗污染能力。
附图说明
图1a、1b和1c分别为以锰渣、钢渣和赤泥为添加原料制备所得的固废基陶瓷催化膜。
图2a为制备所得的固废基催化陶瓷膜对染料去除的效果图;图2b为制备所得的固废基催化陶瓷膜对抗生素去除的效果图。
具体实施方式
以下实施例旨在进一步说明本发明内容,而不是限制权利要求保护范围。
实施例1
表1为几类原料的主要元素组成(%)
表2为湖南宁乡某染料厂的废水,该染料厂废水含有大量罗丹明B,其水质情况如表2所示为(mg/L,pH除外)
固废基陶瓷催化膜的制备:称取硅酸盐尾矿65g,铝土矿15g和锰渣20g放入球磨罐中以350rpm湿磨10h,得到的浆料在60℃下干燥7h,干燥后的粉体过300目筛,称取将2g筛下粉体装入圆形模具中,5MPa下成型;550℃下烧结2h后,再在1130℃下烧结30min,随炉冷却后取出样品。对制备所得陶瓷膜进行表征,抗压强度为11.6MPa,气孔率为51.4%,平均孔径大小为550nm。
固废基陶瓷催化膜的应用:将制备所得的催化膜固定好,将500mL表2中所述废水与1g过一硫酸盐混合均匀后,按1~2mL/min的水流速度从催化膜上表面流至下表面,收集催化膜下表面流出的处理后水体,紫外-可见分光广度法检测得罗丹明B含量为6.4mg/L,COD检测仪测得水样的最终COD含量为80.9mg/L。
实施例2
表3为几类原料的主要元素组成(%)
表4为湖南株洲某制药厂的废水,其水质情况如表4所示为(mg/L,pH除外)
固废基陶瓷催化膜的制备:称取硅酸盐尾矿65g、铝土矿15g和赤泥20g放入球磨罐中以300rpm湿磨12h,得到的浆料在65℃下干燥8h,干燥后的粉体过320目筛,称取将2g筛下粉体装入圆形模具中8MPa下成型;550℃下烧结2h后,再在1140℃下烧结20min,随炉冷却后取出样品。对制备所得陶瓷膜进行表征,抗压强度为13.1MPa,气孔率为48.5%,平均孔径大小为517nm。固废基陶瓷催化膜的应用:将制备所得的催化膜固定好,将200mL表4中所述废水与0.4g过一硫酸盐混合均匀后,按2mL/min的水流速度从催化膜上表面流至下表面,收集催化膜下表面流出的处理后水体,检测得紫外-可见分光光度法四环素含量为2.24mg/L,COD检测仪测得剩余COD含量为20.8mg/L。
实施例3
表5为几类原料的主要元素组成(%)
表6为不同配方中各原料的百分比含量(%):
表7为湖南湘潭某印染厂的废水,其水质情况如表7所示为(mg/L,pH除外)
固废基陶瓷催化膜的制备:按照4种配方称取各原料,分别放入球磨罐中以320rpm湿磨10h,得到的浆料在65℃下干燥8h,干燥后的粉体过320目筛,分别称取将2g筛下粉体装入圆形模具中7MPa下成型;550℃下烧结100min后,再在1130℃下烧结30min,随炉冷却后取出样品,分别记为样品1,样品2,样品3和样品4。对制备所得陶瓷膜进行表征,样品1,样品2,样品3和样品4抗压强度分别为11.7MPa,8.86MPa,13.43MPa和4.65MPa;气孔率分别为42.3%,47.5%,20.6%和59.4%;平均孔径大小分别为487nm,506nm,235nm和761nm。
固废基陶瓷催化膜的应用:将制备所得的催化膜固定好,分别将500mL表7中所述废水与0.55g过一硫酸盐混合均匀后,按1mL/min的水流速度从样品1,样品2,样品3和样品4催化膜上表面流至下表面,收集催化膜下表面流出的处理后水体,COD检测仪测得COD含量分别为4.06mg/L,6.78mg/L,36.24mg/L和8.84mg/L。
Claims (7)
1.一种固废基陶瓷催化膜的制备方法,其特征在于:将硅酸盐尾矿、铝土矿、冶金渣通过湿法球磨后,干燥,得到混合原料;所述混合原料与粘合剂搅拌均匀后,经过干燥、研磨和过筛,得到粉体;所得粉体通过压制成型得到坯体;所述坯体经过烧结,即得;
所述冶金渣为锰渣、钢渣、赤泥中至少一种;
硅酸盐尾矿、铝土矿和冶金渣的质量百分比组成:硅酸盐尾矿60~65%,铝土矿10~15%,冶金渣20~25%;
所述烧结采用两段烧结方式:第一段烧结在500~600℃烧结90~120min,第二段烧结在1130~1150℃烧结20~30min。
2.根据权利要求1所述的一种固废基陶瓷催化膜的制备方法,其特征在于:所述湿法球磨的条件为:球磨转速为300~380rpm,时间为10~12h。
3.根据权利要求1所述的一种固废基陶瓷催化膜的制备方法,其特征在于:所述粘合剂为质量百分比浓度为5%~8%的聚乙烯醇溶液;所述聚乙烯醇溶液与混合原料的质量比为0.5~1:8~10。
4.根据权利要求1所述的一种固废基陶瓷催化膜的制备方法,其特征在于:所述搅拌过程中加热温度至85~90℃。
5.一种固废基陶瓷催化膜,其特征在于:由权利要求1~4任一项所述制备方法得到。
6.权利要求5所述的一种固废基陶瓷催化膜的应用,其特征在于:应用于催化过一硫酸盐氧化降解水体中有机污染物。
7.根据权利要求6所述的一种固废基陶瓷催化膜的应用,其特征在于:所述有机污染物为染料和/或抗生素;
水体中过一硫酸盐的添加浓度为1~3g/L;
水体中有机污染物的浓度:包含染料100~200mg/L和/或抗生素10~20mg/L。
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