CN106220221A - 一种用于合成分子筛膜的支撑体制备方法及其应用 - Google Patents

一种用于合成分子筛膜的支撑体制备方法及其应用 Download PDF

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CN106220221A
CN106220221A CN201610617669.4A CN201610617669A CN106220221A CN 106220221 A CN106220221 A CN 106220221A CN 201610617669 A CN201610617669 A CN 201610617669A CN 106220221 A CN106220221 A CN 106220221A
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朱月馨
杨占照
纪祖焕
余从立
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JIANGSU NINE HEAVEN HIGH-TECH Co Ltd
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Abstract

本发明涉及一种高强度分子筛膜支撑体的制备方法,将氧化铝粉料与硅铝质粉料的混合物作为陶瓷骨料,利用两种粉料之间的粒径的大小进行调配,制得性能可控、颗粒堆积及孔道分布均匀并有利于分子筛膜生长的支撑体。本发明方法工艺简单经济,适用范围广。

Description

一种用于合成分子筛膜的支撑体制备方法及其应用
技术领域
本发明涉及一种多孔陶瓷支撑体的制备方法,特别涉及一种适合分子筛膜合成的支撑体的制备方法,以及其在应用于分子筛膜制备中的应用。
背景技术
分子筛膜是一类具有规则微孔道结构的无机膜材料,该类膜材料孔径在1nm以下,其孔道的吸附选择性及分子筛分特性使其在分子间分离领域有着非常广泛的应用。分子筛膜的合成需在适合分子筛晶体生长的多孔支撑体的基础上,因此对支撑体的结构、机械性能等具有很高的要求。一般来说通过在陶瓷骨料中添加纳米氧化铝、氧化钛等可使得支撑体的强度提高,但这种方法通常会降低支撑体的孔隙率及渗透性。
公开号CN101913873A的专利提供了一种能提高强度和孔隙连通度的多孔陶瓷过滤管支撑体的制法,通过使得骨料与各类添加剂的合理分布从而提高支撑体烧结后的强度,但主要是改善强度分布的均匀性。
发明内容
本发明的目的是:提供一种可制备出性能可控、颗粒堆积及孔道分布更加均匀的用于合成分子筛膜的支撑体制备方法,主要是通过氧化铝粉料与硅铝质粉料的互相作用,同时可通过两种粉料的粒径大小及配合比,制备出性能可控的分子筛膜支撑体。具体内容包括以下方面:
一种用于合成分子筛膜的支撑体制备方法,包括如下步骤:
1)、将氧化铝粉料和硅铝质粉料混合均匀,作为骨料;
2)、向骨料中加入造孔剂、粘结剂、增塑剂和润滑剂搅拌均匀,再经陈腐后制得泥料;
3)、再将泥料经真空练泥、挤出成型、烘干、烧结制得多孔分子筛膜支撑体。
所述氧化铝粉料为白刚玉、α-Al2O3、氢氧化铝中的一种或几种的混合物;所述硅铝质粉料为莫来石、高岭土、煤矸石、铝矾土中的一种或几种的混合物;氧化铝粉料和/或硅铝质粉料的平均粒径为1~15μm。
氧化铝粉料和硅铝质粉料的重量比范围是1:(0.1~10),优选1:(0.2~6),优选1:(0.4~4)。
所述造孔剂为活性碳粉、淀粉或纤维素类中的一种或两种以上的组合,所述造孔剂平均粒径小于骨料,加入量是骨料质量的1~15%。
所述粘结剂为石蜡、糊精或者纤维素类中的一种或两种以上的组合;增塑剂为聚醇类,润滑剂为甘油、桐油、大豆油等油脂类;粘结剂、增塑剂或者润滑剂的加入量分别为骨料的重量的0~15wt%,更优选是0.5~10wt%,更优选是1~10wt%。
所述烧结温度为1200~1600℃,烧结保温时间为1~12h。
所述的支撑体在制备分子筛膜中的应用,包括NaA型、T型、Y型分子筛膜等的制备。
有益效果
通过氧化铝粉料与硅铝质粉料的复合,通过两者粒径大小及配合比的调控,可制备出性能可控、颗粒堆积及孔道分布更加均匀的分子筛膜支撑体。本发明方法工艺简单经济,除适用于分子筛膜的制备外,也适用于其他陶瓷滤膜的制备,适用范围广。本发明制备的支撑体孔隙率≥38%,平均孔径0.2~5μm,三点抗折强度≥70MPa。
附图说明
图1为实施例1制备的支撑体的电子显微镜照片。
图2为对照例1制备的支撑体的电子显微镜照片。
图3a、b分别为实施例1制备的支撑体合成的分子筛膜的表面和断面电子显微镜照片。
具体实施方式
实施例1
1) 将5kg平均孔径为6μm的α-Al2O3粉、5kg平均孔径为6μm的莫来石精细粉以及500g粒径小于6μm的活性炭混合均匀;
2) 边搅拌边向步骤1)得到的混合粉体中加入500g羟丙基甲基纤维素、1kg聚乙二醇、1kg甘油,搅拌均匀,陈腐12小时制得泥料;
3) 将泥料经真空练泥、挤出成型制得单管型多孔分子筛膜支撑体湿坯;
4) 将湿坯烘干,在1480℃下烧成,保温时间为4小时,然后自然冷却,得分子筛膜支撑体。
获得的支撑体经表征,平均孔径为1.3μm,孔隙率40%,三点抗折强度85Mpa。
实施例2
1)将6kg平均粒径为5μm的白刚玉粉、4kg平均粒径为3μm的高岭土以及450g粒径小于3μm的淀粉混合均匀;
2) 边搅拌边向步骤1)得到的混合粉体中加入500g石蜡、1kg聚乙烯醇、1kg桐油,搅拌均匀,陈腐24小时制得泥料;
3) 将泥料经真空练泥、挤出成型制得四通道型多孔分子筛膜支撑体湿坯;
4) 将湿坯烘干,在1550℃下烧成,保温时间为6小时,然后自然冷却,得分子筛膜支撑体。
获得的支撑体经表征,平均孔径为1.5μm,孔隙率38%,三点抗折强度98MPa。
实施例3
1)将8kg平均粒径为2μm的α氧化铝粉作、2kg平均粒径为5μm的煤矸石以及600g粒径小于2μm的活性炭混合均匀;
2) 边搅拌边向步骤1)得到的混合粉体中加入400g含量为40%的纳米氧化钛、500g石蜡、800g聚乙二醇、1.2kg甘油,搅拌均匀,陈腐24小时制得泥料;
3) 将泥料经真空练泥、挤出成型制得单管式多孔分子筛膜支撑体湿坯;
4) 将湿坯烘干,在1200℃下烧成,保温时间为2小时,然后自然冷却,得分子筛膜支撑体。
对照例1
与实施例1的区别在于:骨料中完全采用α-Al2O3粉。
1) 将10kg平均孔径为6μm的α-Al2O3粉以及500g粒径小于6μm的活性炭混合均匀;
2) 边搅拌边向步骤1)得到的混合粉体中加入500g羟丙基甲基纤维素、1kg聚乙二醇、1kg甘油,搅拌均匀,陈腐12小时制得泥料;
3) 将泥料经真空练泥、挤出成型制得单管型多孔分子筛膜支撑体湿坯;
4) 将湿坯烘干,在1480℃下烧成,保温时间为4小时,然后自然冷却,得分子筛膜支撑体。
获得的支撑体经表征,平均孔径为1.1μm,孔隙率28%,三点抗折强度61Mpa。
对照例2
与实施例1的区别在于:骨料中完全采用莫来石精细粉。
1) 将10kg平均孔径为6μm的莫来石精细粉以及500g粒径小于6μm的活性炭混合均匀;
2) 边搅拌边向步骤1)得到的混合粉体中加入500g羟丙基甲基纤维素、1kg聚乙二醇、1kg甘油,搅拌均匀,陈腐12小时制得泥料;
3) 将泥料经真空练泥、挤出成型制得单管型多孔分子筛膜支撑体湿坯;
4) 将湿坯烘干,在1480℃下烧成,保温时间为4小时,然后自然冷却,得分子筛膜支撑体。
获得的支撑体经表征,平均孔径为1.5微米,孔隙率28%,三点抗折强度56MPa。
表1 实施例与对照例支撑体性能对比
从表1可以看出实施例制备的支撑体孔隙率较对照例提高35%以上,强度提高39%以上。
支撑体应用试验:
将上述的支撑体应用于NaA分子筛膜的制备,膜制备方法参照:一种NaA分子筛膜的制备方法及装置(CN105056769A)。分别由实施例和对照例中支撑体所得的NaA分子筛膜进行渗透汽化实施,试验条件是:操作温度70 ℃,分离体系是5 wt.%的乙醇/水溶液。所得结果如表2所示。
表2 各实施例所合成的分子筛膜的渗透汽化实验结果
从表中可以看出,采用上述的支撑体可以合成出表面完整无缺陷的NaA分子筛膜,其分离因子>5000,通量>2.5kg·h–1·m–2,兼具有高的选择性和渗透通量,优于对照例样品。

Claims (10)

1.一种用于合成分子筛膜的支撑体制备方法,其特征在于,包括如下步骤:1)、将氧化铝粉料和硅铝质粉料混合均匀,作为骨料;2)、向骨料中加入造孔剂、粘结剂、增塑剂和润滑剂搅拌均匀,再经陈腐后制得泥料;3)、再将泥料经真空练泥、挤出成型、烘干、烧结制得多孔分子筛膜支撑体。
2.根据权利要求1所述的用于合成分子筛膜的支撑体制备方法,其特征在于,所述氧化铝粉料为白刚玉、α-Al2O3、氢氧化铝中的一种或几种的混合物;所述硅铝质粉料为莫来石、高岭土、煤矸石、铝矾土中的一种或几种的混合物;氧化铝粉料和/或硅铝质粉料的平均粒径为1~15μm。
3.根据权利要求1所述的用于合成分子筛膜的支撑体制备方法,其特征在于,氧化铝粉料和硅铝质粉料的重量比范围是1:0.1~10,更优选1:0.2~6。
4.根据权利要求1所述的用于合成分子筛膜的支撑体制备方法,其特征在于,所述造孔剂为活性碳粉、淀粉或纤维素类中的一种或两种以上的组合,所述造孔剂平均粒径小于骨料,加入量是骨料质量的1~15%。
5.根据权利要求1所述的用于合成分子筛膜的支撑体制备方法,其特征在于,所述粘结剂为石蜡、糊精或者纤维素类中的一种或两种以上的组合;增塑剂为聚醇类,润滑剂为甘油、桐油、大豆油等油脂类;粘结剂、增塑剂或者润滑剂的加入量分别为骨料的重量的0~15wt%,更优选是0.5~10wt%。
6.根据权利要求1所述的用于合成分子筛膜的支撑体制备方法,其特征在于,所述烧结温度为1200~1600℃,烧结保温时间为1~12h。
7.根据权利要求1所述的用于合成分子筛膜的支撑体制备方法,其特征在于所制备的支撑体为管式、平板式、中空纤维式等。
8.权利要求1~7任一项所述的用于合成分子筛膜的支撑体制备方法得到的支撑体。
9.权利要求8所述的支撑体在制备分子筛膜中的应用。
10.根据权利要求9所述的应用,其特征在于,分子筛膜的膜层选自NaA型、T型、Y型分子筛膜等。
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CN108484149A (zh) * 2018-03-30 2018-09-04 滁州学院 一种NaA分子筛膜支撑体制备方法
CN108484149B (zh) * 2018-03-30 2020-12-01 滁州学院 一种NaA分子筛膜支撑体制备方法
CN109433020A (zh) * 2018-12-27 2019-03-08 延海港 一种用于工业溶剂脱水用管式膜材料的制备方法
CN111646785A (zh) * 2020-06-15 2020-09-11 吉林大学 多孔氧化铝膜、含银离子多孔氧化铝复合膜及其制备方法

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Application publication date: 20161214