CN117430443A - 高流道密度的大尺寸多孔陶瓷膜一体化制备方法 - Google Patents
高流道密度的大尺寸多孔陶瓷膜一体化制备方法 Download PDFInfo
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- CN117430443A CN117430443A CN202311763022.9A CN202311763022A CN117430443A CN 117430443 A CN117430443 A CN 117430443A CN 202311763022 A CN202311763022 A CN 202311763022A CN 117430443 A CN117430443 A CN 117430443A
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- ceramic membrane
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Abstract
本发明属于陶瓷膜材料的制备技术领域,具体涉及高流道密度的大尺寸多孔陶瓷膜一体化制备方法。本发明所述的高流道密度的大尺寸多孔陶瓷膜一体化制备方法,包括以下步骤:将原料A与球石、球磨助剂等混合预球磨,再加入原料B、无机添加剂,继续球磨脱水,向泥料中加入有机复合助剂,经捏合、练泥、陈腐后挤出生坯,将生坯冷、热风干燥定型;烧结,制得大尺寸蜂窝状支撑体;以大尺寸蜂窝状支撑体为载体,在通道内表面采用真空负压,多次浸渍、干燥烧结方式制得膜层,最终得到高流道密度的大尺寸多孔陶瓷膜。本发明提供的高流道密度的大尺寸多孔陶瓷膜一体化制备方法,条件温和,制备的泥料加工性能好,制备的大尺寸多孔陶瓷膜合格率高。
Description
技术领域
本发明属于陶瓷膜材料的制备技术领域,具体涉及高流道密度的大尺寸多孔陶瓷膜一体化制备方法。
背景技术
水资源是人类生存和经济社会发展不可或缺的资源要素。随着各行各业的废水处理的逐渐增大,传统的水处理工艺已无法满足新问题。膜技术作为一门新型的水处理技术在各个行业得到了广泛的应用。近年来,陶瓷膜因其强度高、亲水性好、耐腐蚀性强、结构稳定、不会被微生物腐蚀、孔径分布均匀等特点,在市政供水、高难度污水、中水回用和海水淡化等领域展示出了明显的优势。
目前,用于水处理行业的陶瓷膜多以平板和低孔道密度(19和37通道)为主,在成本、装填面积和应用过程中存在的问题限制了其大规模化的应用。高流道密度的大尺寸多孔陶瓷膜(孔道数>1000,管直径>150mm,长度>1200mm)具有较低能耗、通量高、其装填面积是传统陶瓷膜几十倍,膜污堵后清洗恢复性好,能与现有有机超滤系统兼容和替换,原水处理回收率高达98%,成为水处理陶瓷膜的理想构型。
目前高流道密度的大尺寸多孔陶瓷膜主流的制作方式是拼接而成,如CN102172477A公开了一种组合式蜂窝陶瓷膜过滤元件,包括蜂窝陶瓷支撑体以及设置在其内的过滤孔道,蜂窝陶瓷支撑体为平板状,过滤孔道其轴线与蜂窝陶瓷支撑体的板面平行。CN114311232A公开了一种大直径组合式蜂窝陶瓷过滤膜的制备方法。这些通过拼接组成的圆形结构陶瓷膜,虽然渗透路径短、价格较低、过滤效率高,但进水和反冲时、水流分布不均一,制作工艺复杂、封装不方便,装填密度较小。一体化挤出成型制备技术存在:泥料体系流动性差,大尺寸产品无开裂、变形干燥、烧结控制,孔道内涂膜均匀性,成本控制等需要克服的技术难点,比如高流道密度的大尺寸多孔陶瓷膜是制备侧积水流道陶瓷膜的基础材料,其孔密度高,孔壁薄,生坯自重大,其在成型过程中存在阻力大、易变形,且成品率低,制备成本高昂的难题。CN114307665A公开了一种大直径侧积水流道蜂窝陶瓷过滤膜的制备方法,采用粒径较大45-55μm的原材料氧化铝粉和氧化硅微粉,并加入氧化镁、桐油、明胶粉末、羟丙基甲基纤维素作为助剂,挤压成型后低温氮气降温,然后开槽侧机水道,冷冻-52至-48℃干燥,高温1735-1750℃烧结,然后普通浸渍膜层,得到直径为110-130mm且长度为1.2m的大直径侧积水流道蜂窝陶瓷过滤膜,虽然得到了尺寸较大的过滤膜,但是产品的孔道密度未提及,制备的工艺条件苛刻,烧结能耗较高。另外,侧面开口的蜂窝状陶瓷膜能加快渗透测水的流量,但加工非常复杂,且存在暗裂纹等缺陷,产品的使用稳定性存在隐患。
发明内容
本发明要解决的技术问题是克服现有技术存在的上述缺陷,提供一种高流道密度的大尺寸多孔陶瓷膜一体化制备方法,制备工艺简单,条件温和,制备的泥料流动性好,进一步提高加工性能,制备的大尺寸多孔陶瓷膜完整度高,通量高,完整产品的合格率高。
本发明所述的高流道密度的大尺寸多孔陶瓷膜一体化制备方法,包括以下步骤:
(1)将原料A与水、球石、球磨助剂混合,进行预球磨,再加入原料B、无机添加剂,继续球磨,脱水,制得含水量为10~15%的泥料;
所述的原料A为刚玉、莫来石、堇青石、氧化铝粉体的一种或多种,D50粒径为20~30μm;原料B为氧化铝粉体,D50粒径为1~3μm;
(2)向泥料中加入有机复合助剂,经捏合、练泥、陈腐后挤出生坯,将生坯转运至转动轴上冷、热风干燥定型,二次干燥脱水;将干燥后的坯体进行烧结,制得大尺寸多孔支撑体;
所述的冷、热风干燥定型方式为先用常温风沿支撑体的多孔通道进行吹气,进气温度10~30℃,进气速度为3~8m/s,进气时间为6~12h;热风沿支撑体的多孔通道进行吹气,进气温度30~60℃,速度为3~8m/s,进气时间为4~8h;
(3)以大尺寸多孔支撑体为载体,在多孔通道内表面采用真空负压,多次浸渍、干燥烧结方式制得膜层,最终得到高流道密度的大尺寸多孔陶瓷膜。
步骤(1)中球石为聚氨酯包覆的氧化锆、高铝球中的一种;球石是由直径分别为60~80mm、30~50mm、10~20mm按照质量比为10~30%、20~40%、30~70%组成的;球磨助剂为油酸、硬脂酸中的一种,加入量为原料A质量的1~3%。
步骤(1)中原料A与水、球石的质量比为:1:(1.5~2.5):(1~2)。
步骤(1)中预球磨速度为:30~60r/min,预球磨时间3~6h。
步骤(1)中原料A和原料B的质量比为:(8.5~9.5):(0.5~1.5)。
步骤(1)中无机添加剂为粘土、碳化硅晶须、硅酸锆晶须中的一种,加入量为原料A质量的0.5~2%。
步骤(1)中球磨时间为1~2h,球磨速度为30~50r/min。脱水方式为真空抽滤。
步骤(2)中有机复合助剂为羟丙基甲基纤维素、甲壳素、液蜡、异丙醇、卵磷脂按照质量比为(2~5):(1~2):(2~3):(0.05~0.1):(1~3)的复合物,优选的配比为2:1:2:0.05:1,有机复合助剂的加入量为泥料的3~5%。羟丙基甲基纤维素的粘度5000~10000mPa·s,甲壳素的粘度1000~3000mPa·s。
步骤(2)中二次干燥脱水是在烘箱深度干燥脱水,干燥温度100~120℃,干燥时间2~4h。
步骤(2)中转动轴为对辊式,对辊轮间距为坯体直径的2/5,辊筒直径为坯体直径的1~1.5倍,辊筒转动速度为10~30r/min。
步骤(2)中的烧结采用吊烧工艺,烧结温度为1400~1550℃,烧结时间为15~20h。所述的吊烧工艺中采用的窑具是以重结晶碳化硅的碳化硅窑具作为棚架,管胚上端80~150mm处开三个平行贯穿孔,孔直径为10~20mm,孔间隔50~100mm,用直径10~15mm的重结晶碳化硅小棒穿放在碳化硅方梁上,管胚下端采用无机材料托住下端底部或者用氧化铝空心球覆盖下端底部30~50mm。
步骤(3)中的真空负压,压力为0.02~0.05MPa,负压时间为3~6s。
步骤(3)中的多次浸渍、干燥烧结方式为第一次浸渍料浆为氧化铝,D50粒径为3~5μm,浸渍料浆质量为0.04~0.08kg/m2,干燥烧结温度为1250~1350℃,烧结时间为10~15h;第二次浸渍料浆为氧化锆和氧化钛按照质量比(6~8):(2~4)的复合物,D50粒径为0.2~0.5μm,浸渍料浆质量为0.02~0.05kg/m2。
浸渍料浆的粘度为60~100mPa·s,浸渍料浆的固含量为5~15%,浸渍料浆流动速度为0.3~1m/s。
具体的,所述的高流道密度的大尺寸多孔陶瓷膜一体化制备方法,包括以下步骤:
(1)将原料A与水、球石、球磨助剂混合,在30~60r/min下进行预球磨3~6h,再加入原料B、无机添加剂,继续30~50r/min球磨1~2h,真空抽滤脱水,制得含水量为10~15%的泥料;
原料A和原料B的质量比为:(8.5~9.5):(0.5~1.5);
球石为聚氨酯包覆的氧化锆、高铝球中的一种;球石是由直径分别为60~80mm、30~50mm、10~20mm按照质量比为10~30%、20~40%、30~70%组成的;
球磨助剂为油酸、硬脂酸中的一种,加入量为原料A质量的1~3%;
原料A与水、球石的质量比为:1:(1.5~2.5):(1~2);
所述的原料A为刚玉、莫来石、堇青石、氧化铝粉体的一种或多种,D50粒径为20~30μm;原料B为氧化铝粉体,D50粒径为1~3μm。
(2)向泥料中加入3~5%的有机复合助剂羟丙基甲基纤维素、甲壳素、液蜡、异丙醇、卵磷脂按照质量比为(2~5):(1~2):(2~3):(0.05~0.1):(1~3)的复合物,经捏合、练泥、陈腐后挤出生坯,将生坯转运至转动轴上冷、热风干燥定型,转动轴为对辊式,对辊轮间距为坯体直径的2/5,辊筒直径为坯体直径的1~1.5倍,辊筒转动速度为10~30r/min,管坯通道然后转入烘箱在100~120℃干燥2~4h;将干燥后的坯体在1400~1550℃吊烧烧结15~20h,制得大尺寸多孔支撑体(蜂窝状);
所述的冷、热风干燥定型方式为先用常温风沿支撑体的多孔通道进行吹气,进气温度10~30℃,进气速度为3~8m/s,进气时间为6~12h;热风沿支撑体的多孔通道进行吹气,进气温度30~60℃,速度为3~8m/s,进气时间为4~8h;
所述的吊烧工艺中采用的窑具是以重结晶碳化硅的碳化硅窑具作为棚架,管胚上端80~150mm处开三个平行贯穿孔,孔直径为10~20mm,孔间隔50~100mm,用直径10~15mm的重结晶碳化硅小棒穿放在碳化硅方梁上,管胚下端采用无机材料托住下端底部或者用氧化铝空心球覆盖下端底部30~50mm。
(3)以大尺寸多孔支撑体为载体,在多孔通道内表面采用在0.02~0.05MPa真空负压3~6s,多次浸渍、干燥烧结方式制得膜层,最终得到高流道密度的大尺寸多孔陶瓷膜;
所述多次浸渍、干燥烧结方式为第一次浸渍料浆为氧化铝,D50粒径为3~5μm,浸渍料浆质量为0.04~0.08kg/m2,干燥烧结温度为1250~1350℃,烧结时间为10~15h;第二次浸渍料浆为氧化锆和氧化钛按照质量比(6~8):(2~4)的复合物,D50粒径为0.2~0.5μm,浸渍料浆质量为0.02~0.05kg/m2。浸渍料浆的粘度为60~100mPa·s,浸渍料浆的固含量为5~15%,浸渍料浆流动速度为0.3~1m/s。
本发明所述的高流道密度的大尺寸多孔陶瓷膜一体化制备方法,采用球石颗粒级配、球磨速度等方式对原料颗粒进行球磨,使原料棱角圆润化,降低颗粒间流动摩擦力。加入羟丙基甲基纤维素、甲壳素、液蜡、异丙醇、卵磷脂复合的有机助剂,可在粉体表面形成一层有机包覆层,减少颗粒间的硬接触的同时增加润滑性。对产品采用冷风、热风干燥定型,使产品内部的水分温和的充分扩散至坯体表面,产品表面的水分被室温空气带走,减少直接热风造成的脱水过快而开裂、变形、收缩不一致等问题。对大尺寸、大重量产品采用吊烧工艺,规避了卧烧带来的翘曲和椭圆变型问题。采用真空负压制膜工艺,能够保证高密度流道内部面对浆料形成均匀吸附性能,制备的膜层完整、连续。
与现有技术相比,本发明具有的有益效果是:
(1)本发明所述的高流道密度的大尺寸多孔陶瓷膜一体化制备方法,科学合理、简单易行,制备过程添加有机复合助剂的泥料流动性好,对模具磨损小,提高干燥速度,降低干燥和烧结过程开裂率。
(2)采用本发明的方法制备的高流道密度的大尺寸多孔陶瓷膜,通量高,垂直度好,孔径分布均匀,具有低的收缩率。
附图说明
图1为本发明的步骤(2)将生坯转运至转动轴上冷、热风干燥定型的结构示意图。
图2为实施例1的步骤(2)制得的大尺寸多孔蜂窝状支撑体的SEM图。
图3为实施例1制得的高流道密度的大尺寸多孔陶瓷膜的膜表面SEM图。
图4为实施例1制得的高流道密度的大尺寸多孔陶瓷膜的断面SEM图。
图5为实施例1制得的高流道密度的大尺寸多孔陶瓷膜在100nm下的修正差分流量孔径分布图。
图6为实施例2制得的高流道密度的大尺寸多孔陶瓷膜在50nm下的修正差分流量孔径分布图。
图1中:1、坯体;2、对辊轮;3、多孔。
具体实施方式
下面结合具体实施例对本发明作进一步说明。
以下实施例和对比例所采用的原料均为市售产品,所述的含量均为质量含量。
以下实施例所采用的生坯转运至转动轴上冷、热风干燥定型的结构如图1所示,转动轴为对辊式,对辊轮2圆心之间的间距为坯体1直径的2/5,每个辊轮直径为坯体1直径的1.5倍,坯体1上设置有多孔3,冷热风的方向是顺着多孔3的方向的。
所述的吊烧工艺中采用的窑具是以重结晶碳化硅的碳化硅窑具作为棚架,管胚上端100mm处开三个平行贯穿孔,孔直径为15mm,孔间隔50mm,用直径15mm的重结晶碳化硅小棒穿放在碳化硅方梁上,管胚下端采用无机材料托住下端底部或者用氧化铝空心球覆盖下端底部30~50mm。
以下原料B为氧化铝粉体,D50粒径为1~3μm。羟丙基甲基纤维素的粘度5000~10000mPa·s,甲壳素的粘度1000~3000mPa·s。以下实施例所述的吊烧烧结为采用吊装装窑烧结,对比例4的卧烧烧结为采用紧密叠卧装装窑烧结。
实施例1
所述的高流道密度的大尺寸多孔陶瓷膜一体化制备方法,包括以下步骤:
(1)将原料A与水、球石、球磨助剂混合,在50r/min下进行预球磨5h,再加入原料B、无机添加剂,继续40r/min球磨1.5h,真空抽滤脱水,制得含水量为12%的泥料;
原料A和原料B的质量比为:9:1;
球石为聚氨酯包覆的氧化锆;球石是由直径分别为60~80mm、30~50mm、10~20mm按照质量比为20%、30%、50%组成的;
球磨助剂为油酸,加入量为原料A质量的2%;
原料A与水、球石的质量比为:1:2.0:1.5;
无机添加剂为碳化硅晶须,加入量为原料A质量的1%;
所述的原料A为刚玉和氧化铝粉体质量比1:1,D50粒径为20~30μm。
(2)向泥料中加入4%的有机复合助剂羟丙基甲基纤维素、甲壳素、液蜡、异丙醇、卵磷脂按照质量比为2:1:2:0.05:1的复合物,经捏合、练泥、陈腐后挤出生坯,将生坯转运至转动轴上冷、热风干燥定型,先用常温风沿支撑体的多孔通道进行吹气,进气温度20℃,进气速度为5m/s,进气时间为8h;热风沿支撑体的多孔通道进行吹气,进气温度40℃,速度为5m/s,进气时间为6h;辊筒转动速度为20r/min,管坯通道然后转入烘箱在110℃干燥3h;将干燥后的坯体在1500℃吊烧烧结17h,制得大尺寸多孔蜂窝状支撑体,其SEM图如图2所示。
(3)以大尺寸多孔支撑体为载体,在多孔通道内表面采用在0.04MPa真空负压4s,多次浸渍、干燥烧结方式制得膜层,最终得到高流道密度的大尺寸多孔陶瓷膜;尺寸为管直径150mm,长度1400mm;大尺寸多孔陶瓷膜的膜表面SEM图,如图3所示;大尺寸多孔陶瓷膜的断面SEM图,如图4所示;
所述多次浸渍、干燥烧结方式为第一次浸渍料浆为氧化铝,D50粒径为3~5μm,浸渍料浆质量为0.05kg/m2,干燥烧结温度为1300℃,烧结时间为12h;第二次浸渍料浆为氧化锆和氧化钛按照质量比7:3的复合物,D50粒径为0.2~0.5μm,浸渍料浆质量为0.03kg/m2。浸渍料浆的粘度为80mPa·s,浸渍料浆的固含量为10%,浸渍料浆流动速度为0.5m/s。
本实施例制备的大尺寸多孔陶瓷膜在100nm下的修正差分流量孔径分布图,如图5所示,孔径主要分布在0.08-0.12μm范围内。
实施例2
所述的高流道密度的大尺寸多孔陶瓷膜一体化制备方法,包括以下步骤:
(1)将原料A与水、球石、球磨助剂混合,在60r/min下进行预球磨3h,再加入原料B、无机添加剂,继续30r/min球磨2h,真空抽滤脱水,制得含水量为10%的泥料;
原料A和原料B的质量比为:8.5:1.5;
球石为高铝球;球石是由直径分别为60~80mm、30~50mm、10~20mm按照质量比为30%、40%、30%组成的;
球磨助剂为油酸,加入量为原料A质量的1%;
原料A与水、球石的质量比为:1:2.5:2;
无机添加剂为粘土,加入量为原料A质量的0.5%;
所述的原料A为氧化铝粉体,D50粒径为20~30μm。
(2)向泥料中加入3%的有机复合助剂羟丙基甲基纤维素、甲壳素、液蜡、异丙醇、卵磷脂按照质量比为3:2:3:0.1:2的复合物,经捏合、练泥、陈腐后挤出生坯,将生坯转运至转动轴上冷、热风干燥定型,先用常温风沿支撑体的多孔通道进行吹气,进气温度30℃,进气速度为8m/s,进气时间为6h;热风沿支撑体的多孔通道进行吹气,进气温度60℃,速度为3m/s,进气时间为4h;辊筒转动速度为30r/min,管坯通道然后转入烘箱在120℃干燥2h;将干燥后的坯体在1400℃吊烧烧结20h,制得大尺寸多孔蜂窝状支撑体;
(3)以大尺寸多孔支撑体为载体,在多孔通道内表面采用在0.05MPa真空负压3s,多次浸渍、干燥烧结方式制得膜层,最终得到高流道密度的大尺寸多孔陶瓷膜,尺寸为管直径160mm,长度1300mm;
所述多次浸渍、干燥烧结方式为第一次浸渍料浆为氧化铝,D50粒径为3~5μm,浸渍料浆质量为0.08kg/m2,干燥烧结温度为1350℃,烧结时间为10h;第二次浸渍料浆为氧化锆和氧化钛按照质量比6:4的复合物,D50粒径为0.2~0.5μm,浸渍料浆质量为0.05kg/m2。浸渍料浆的粘度为100mPa·s,浸渍料浆的固含量为8%,浸渍料浆流动速度为1m/s。
本实施例制备的大尺寸多孔陶瓷膜在50nm下的修正差分流量孔径分布图,如图6所示,孔径主要分布在0.034-0.068μm范围内。
实施例3
所述的高流道密度的大尺寸多孔陶瓷膜一体化制备方法,包括以下步骤:
(1)将原料A与水、球石、球磨助剂混合,在30r/min下进行预球磨6h,再加入原料B、无机添加剂,继续50r/min球磨1h,真空抽滤脱水,制得含水量为15%的泥料;
原料A和原料B的质量比为:9.5:0.5;
球石为聚氨酯包覆的氧化锆;球石是由直径分别为60~80mm、30~50mm、10~20mm按照质量比为10%、40%、50%组成的;
球磨助剂为硬脂酸,加入量为原料A质量的3%;
原料A与水、球石的质量比为:1:1.5:1;
无机添加剂为硅酸锆晶须,加入量为原料A质量的2%;
所述的原料A为刚玉、堇青石、氧化铝粉体,D50粒径为20~30μm。
(2)向泥料中加入5%的有机复合助剂羟丙基甲基纤维素、甲壳素、液蜡、异丙醇、卵磷脂按照质量比为5:1:3:0.1:3的复合物,经捏合、练泥、陈腐后挤出生坯,将生坯转运至转动轴上冷、热风干燥定型,先用常温风沿支撑体的多孔通道进行吹气,进气温度10℃,进气速度为3m/s,进气时间为12h;热风沿支撑体的多孔通道进行吹气,进气温度30℃,速度为8m/s,进气时间为8h;辊筒转动速度为10r/min,管坯通道然后转入烘箱在100℃干燥4h;将干燥后的坯体在1550℃吊烧烧结15h,制得大尺寸多孔蜂窝状支撑体。
(3)以大尺寸多孔支撑体为载体,在多孔通道内表面采用在0.02MPa真空负压6s,多次浸渍、干燥烧结方式制得膜层,最终得到高流道密度的大尺寸多孔陶瓷膜。尺寸为管直径180mm,长度1500mm;所述多次浸渍、干燥烧结方式为第一次浸渍料浆为氧化铝,D50粒径为3~5μm,浸渍料浆质量为0.04kg/m2,干燥烧结温度为1250℃,烧结时间为15h;第二次浸渍料浆为氧化锆和氧化钛按照质量比8:2的复合物,D50粒径为0.2~0.5μm,浸渍料浆质量为0.02kg/m2。浸渍料浆的粘度为60mPa·s,浸渍料浆的固含量为15%,浸渍料浆流动速度为0.3m/s。
实施例4
所述的高流道密度的大尺寸多孔陶瓷膜一体化制备方法,包括以下步骤:
(1)将原料A与水、球石、球磨助剂混合,在45r/min下进行预球磨4h,再加入原料B、无机添加剂,继续40r/min球磨2h,真空抽滤脱水,制得含水量为14%的泥料;
原料A和原料B的质量比为:9:1;
球石为聚氨酯包覆的氧化锆;球石是由直径分别为60~80mm、30~50mm、10~20mm按照质量比为10%、20%、70%组成的;
球磨助剂为油酸,加入量为原料A质量的1%;
无机添加剂为碳化硅晶须,加入量为原料A质量的0.5%;
原料A与水、球石的质量比为:1:2:1;
所述的原料A为刚玉、莫来石,D50粒径为20~30μm。
(2)向泥料中加入5%的有机复合助剂羟丙基甲基纤维素、甲壳素、液蜡、异丙醇、卵磷脂按照质量比为4:2:3:0.08:2的复合物,经捏合、练泥、陈腐后挤出生坯,将生坯转运至转动轴上冷、热风干燥定型,先用常温风沿支撑体的多孔通道进行吹气,进气温度20℃,进气速度为6m/s,进气时间为7h;热风沿支撑体的多孔通道进行吹气,进气温度40℃,速度为5m/s,进气时间为5h;辊筒转动速度为25r/min,管坯通道然后转入烘箱在100℃干燥3h;将干燥后的坯体在1450℃吊烧烧结18h,制得大尺寸多孔蜂窝状支撑体。
(3)以大尺寸多孔支撑体为载体,在多孔通道内表面采用在0.03MPa真空负压4s,多次浸渍、干燥烧结方式制得膜层,最终得到高流道密度的大尺寸多孔陶瓷膜;尺寸为管直径170mm,长度1500mm;
所述多次浸渍、干燥烧结方式为第一次浸渍料浆为氧化铝,D50粒径为3~5μm,浸渍料浆质量为0.06kg/m2,干燥烧结温度为1300℃,烧结时间为12h;第二次浸渍料浆为氧化锆和氧化钛按照质量比6:4的复合物,D50粒径为0.2~0.5μm,浸渍料浆质量为0.03kg/m2。浸渍料浆的粘度为70mPa·s,浸渍料浆的固含量为5%,浸渍料浆流动速度为0.5m/s。
对比例1
本对比例与实施例1相同,但是将步骤(1)的预球磨工艺去掉。
对比例2
本对比例与实施例1相同,但是将步骤(1)无机添加剂中的碳化硅晶须去掉。
对比例3
本对比例与实施例1相同,但是将步骤(2)有机复合助剂中的液蜡和卵磷脂去掉。
对比例4
本对比例与实施例1相同,但是将步骤(2)的吊烧烧结替换为卧烧烧结。
将以上实施例和对比例制备的陶瓷膜,根据GB/T1965-1996检测抗弯强度。根据HY/T 063-2002检测耐酸/碱腐蚀性能(质量损失率%)。通量测试条件:水的浊度为200~300,操作温度为25℃,操作压力0.1MPa。其检测结果如表1所示。表1中的挤出速度为每个实施例和对比例的步骤(2)的经捏合、练泥、陈腐后挤出生坯的挤出速度,收缩率则是指步骤(2)的支撑体在烧结前后的长度的变化率%:(L1-L0)/L0×100%,其中L0为烧结前的长度尺寸,L1为烧结后的长度尺寸。所述的弯曲度为陶瓷膜坯体受重力影响在制备过程中会弯曲变形,将陶瓷膜放置于平面上,其呈变形量最大的拱形位置与平面的距离即为弯曲度;所述的椭圆度是在烧结前后陶瓷膜的圆形横截面上存在着外径不等的现象,即存在着不一定互相垂直的最大外径和最小外径,则最大外径与最小外径之差即为椭圆度。
表1检测结果
本发明所制备的高流道密度的大尺寸多孔陶瓷膜在泥料润滑性能、收缩率、产品外观度、强度及通量等方面性能较优,实施例1~4,产品的挤出速度在5~10mm/s,收缩率在4.6~5.1%,证明泥料具有较好的高润滑和低收缩性能;采用的大尺寸产品吊烧技术使产品的弯曲度和椭圆度尺寸控制在<1mm范围内;烧结后的强度也大于54.3MPa,通量在195~236L/m2·h,耐酸腐蚀质量损失小于0.35%,耐碱腐蚀质量损失小于0.17%。产品的SEM电镜显示,支撑体孔径分布规整、膜表面连续、平整,孔径测试显示制备的膜孔径分布窄。对比例1去掉了预球磨工艺后,产品的挤出速度变慢;调整烧结助剂后的对比例2产品收缩较小,强度也下降,这说明烧结程度低,耐酸碱腐蚀质量损失增加;对比例3减少了复配有机助剂,产品的挤出速度变慢,产品的内在强度也受到影响而降低,耐酸碱腐蚀质量损失随强度降低而增加;改变烧结工艺的对比例4,产品的弯曲度和椭圆度尺寸变大,产品外观不规则。
Claims (10)
1.一种高流道密度的大尺寸多孔陶瓷膜一体化制备方法,其特征在于:包括以下步骤:
(1)将原料A与水、球石、球磨助剂混合,进行预球磨,再加入原料B、无机添加剂,继续球磨,脱水,制得含水量为10~15wt%的泥料;
所述的原料A为刚玉、莫来石、堇青石、氧化铝粉体的一种或多种,D50粒径为20~30μm;原料B为氧化铝粉体,D50粒径为1~3μm;
(2)向泥料中加入有机复合助剂,经捏合、练泥、陈腐后挤出生坯,将生坯转运至转动轴上冷、热风干燥定型,二次干燥脱水;将干燥后的坯体进行烧结,制得大尺寸多孔支撑体;
所述的冷、热风干燥定型方式为先用常温风沿支撑体的多孔通道进行吹气,进气温度10~30℃,进气速度为3~8m/s,进气时间为6~12h;热风沿支撑体的多孔通道进行吹气,进气温度30~60℃,速度为3~8m/s,进气时间为4~8h;
(3)以大尺寸多孔支撑体为载体,在多孔通道内表面采用真空负压,多次浸渍、干燥烧结方式制得膜层,最终得到高流道密度的大尺寸多孔陶瓷膜。
2.根据权利要求1所述的高流道密度的大尺寸多孔陶瓷膜一体化制备方法,其特征在于:步骤(1)中球石为聚氨酯包覆的氧化锆、高铝球中的一种;球石是由直径分别为60~80mm、30~50mm、10~20mm按照质量比为10~30%、20~40%、30~70%组成的;球磨助剂为油酸、硬脂酸中的一种,加入量为原料A质量的1~3%。
3.根据权利要求1所述的高流道密度的大尺寸多孔陶瓷膜一体化制备方法,其特征在于:步骤(1)中原料A和原料B的质量比为:(8.5~9.5):(0.5~1.5)。
4.根据权利要求3所述的高流道密度的大尺寸多孔陶瓷膜一体化制备方法,其特征在于:步骤(1)中无机添加剂为粘土、碳化硅晶须、硅酸锆晶须中的一种,加入量为原料A质量的0.5~2%。
5.根据权利要求1所述的高流道密度的大尺寸多孔陶瓷膜一体化制备方法,其特征在于:步骤(2)中有机复合助剂为羟丙基甲基纤维素、甲壳素、液蜡、异丙醇、卵磷脂按照质量比为(2~5):(1~2):(2~3):(0.05~0.1):(1~3)的复合物,有机复合助剂的加入量为泥料的3~5%。
6.根据权利要求1所述的高流道密度的大尺寸多孔陶瓷膜一体化制备方法,其特征在于:步骤(2)中转动轴为对辊式,对辊轮间距为坯体直径的2/5,辊筒直径为坯体直径的1~1.5倍,辊筒转动速度为10~30r/min。
7.根据权利要求1所述的高流道密度的大尺寸多孔陶瓷膜一体化制备方法,其特征在于:步骤(2)中的烧结采用吊烧工艺,烧结温度为1400~1550℃,烧结时间为15~20h。
8.根据权利要求1所述的高流道密度的大尺寸多孔陶瓷膜一体化制备方法,其特征在于:步骤(3)中的真空负压,压力为0.02~0.05MPa,负压时间为3~6s。
9.根据权利要求8所述的高流道密度的大尺寸多孔陶瓷膜一体化制备方法,其特征在于:步骤(3)中的多次浸渍、干燥烧结方式为第一次浸渍料浆为氧化铝,D50粒径为3~5μm,浸渍料浆质量为0.04~0.08kg/m2,干燥烧结温度为1250~1350℃,烧结时间为10~15h;第二次浸渍料浆为氧化锆和氧化钛按照质量比(6~8):(2~4)的复合物,D50粒径为0.2~0.5μm,浸渍料浆质量为0.02~0.05kg/m2。
10.根据权利要求9所述的高流道密度的大尺寸多孔陶瓷膜一体化制备方法,其特征在于:浸渍料浆的粘度为60~100mPa·s,浸渍料浆的固含量为5~15%,浸渍料浆流动速度为0.3~1m/s。
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