CN107082628B - 一种基于分子筛膜合成残液的多孔陶瓷支撑体制备方法 - Google Patents
一种基于分子筛膜合成残液的多孔陶瓷支撑体制备方法 Download PDFInfo
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 46
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- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 3
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
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- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
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- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 2
- 229910021353 zirconium disilicide Inorganic materials 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
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- VWZIXVXBCBBRGP-UHFFFAOYSA-N boron;zirconium Chemical compound B#[Zr]#B VWZIXVXBCBBRGP-UHFFFAOYSA-N 0.000 description 1
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- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及一种以分子筛膜合成残液为烧结助剂的多孔陶瓷支撑体制备方法。采用陶瓷粉末作为骨料颗粒,NaA分子筛膜合成残液作为烧结助剂,活性炭粉作为造孔剂,充分混合均匀后;通过挤压成型法得到坯体,干燥后,按程序进行高温烧结,制备得到多孔陶瓷支撑体。本发明制备的陶瓷材料具有机械强度高、化学稳定性好、渗透性能高等优点,可用于废水处理、大气治理等环保领域。采用分子筛膜合成残液作为制备原料,不仅可实现废物资源化利用,而且可降低陶瓷材料原位反应烧结温度,节约能耗和资源,经济效益和环境效益显著。
Description
技术领域
本发明属于多孔陶瓷材料技术领域,具体涉及一种基于分子筛膜合成残液的多孔陶瓷支撑体制备方法。
背景技术
多孔陶瓷膜具有优异的力学性能、耐腐蚀性能以及渗透性能,在气体除尘或水处理领域独具优势。陶瓷支撑体是陶瓷膜制备的主要部件,通常需要在陶瓷浆料之间高温反应形成颈部连接,烧结温度一般高于1500 ℃,如纯质多孔SiC陶瓷的烧成温度一般大于1800 ℃,氧化铝多孔陶瓷的烧成温度在1650 ℃,高温烧结是导致陶瓷支撑体制备成本居高不下的主要原因。因此,在陶瓷支撑体制备过程中如何降低其烧结温度成为研究的热点。
常用的低温制备陶瓷支撑体的方法有添加烧结助剂法以及前驱体法。专利CN102674355A公开了一种多孔碳化硅陶瓷的制备方法,将间苯二酚、甲醛、3-氨丙基三乙氧基硅烷在一定条件下制备成碳化硅前驱体,再经过高温烧结等过程制备出多孔碳化硅材料,烧结过程温度仅为700 ℃左右。然而,前驱体法使用的原料多为聚合物等,且前驱体还原成SiC过程依然需要高温反应(1500 ℃),且工艺繁多复杂,不利于工业化生产多孔陶瓷。添加烧结助剂法仅需将烧结助剂直接混合于陶瓷浆料中,工艺简单,因此被广泛应用于工业化制备多孔陶瓷。专利CN103553627A公开了一种陶瓷基复合材料的制备方法,以二硼化锆粉末作为基体,以二硅化锆粉末作为烧结助剂,将陶瓷材料的烧结温度从2000 ℃降温至1600 ℃。专利CN102030515A公开了一种低温合成氧化铝陶瓷材料的方法,以氧化铝、氧化钇或氧化镧作为原料,二氧化硅和碳酸锂作为烧结助剂,将陶瓷材料烧结温度降低至约1400 ℃。文献报道[Lee et al, J Mater Sci, 2004, 39(11):3801-3803]添加Al2O3、Y2O3、CaO等烧结助剂将碳化硅陶瓷烧结温度由2000 ℃降低至1600 ℃。然而,二硅化锆、碳酸锂、Y2O3等材料本身价格较高,增加陶瓷材料的制备成本,并且1400 ℃以上的烧结温度仍会带来较高的能耗,因此,开发低成本且能达到更低烧结温度的助剂在陶瓷支撑体的规模化制备中具有很大优势。
分子筛常作为催化剂、膜材料使用的多孔材料,其中NaA分子筛膜利用其规则孔道可实现溶剂和水的分离,已被广泛应用于工业化有机物脱水领域。分子筛膜的制备方法主要为水热合成法,生产过程中残留大量的分子筛残液。这些分子筛合成残液中含有的丰富分子筛如何处理成为急需解决的问题。这些残液中富含硅、铝等,易于与氧化铝、碳化硅等材料在高温下发生化学反应生成具有化学稳定性好的化合物。因此本发明提出将分子筛膜合成残液作为多孔陶瓷的烧结助剂,实现烧结温度的降低和分子筛残液资源化利用的有益效应。
发明内容
本发明将分子筛膜合成残液废物利用,作为烧结助剂进行陶瓷支撑体的制备,既节约了陶瓷支撑体原材料的成本,又降低了烧结温度,制备的多孔材料又可用于环保治理中,真正起到了节约能源和资源,保护环境的作用。
为了达到发明目的,本发明的技术方案为:
一种基于分子筛膜合成残液的多孔陶瓷支撑体制备方法,制备步骤如下:
(1) 按一定比例配制陶瓷浆料a,陶瓷浆料a包括:陶瓷粉末、烧结助剂、造孔剂,并将其均匀混合;
(2) 使用挤压成型法将陶瓷浆料a制备成一定形状尺寸的坯体,烘干,得到干燥后的坯体b;
(3) 将坯体b放入高温电炉中,按照一定的升温程序并在一定的气氛中进行烧结,得到陶瓷支撑体。
其中:
步骤(1)所述陶瓷浆料a中烧结助剂为NaA分子筛膜合成残液,造孔剂为活性炭粉,陶瓷粉末为SiC、Al2O3中的一种。
步骤(1)所述的陶瓷浆料a按各成分的质量配比为:NaA分子筛膜合成残液为2 -10%,活性炭粉为0-20%,其余为陶瓷粉末。
所述陶瓷粉料的平均粒径为10 - 100 μm,活性炭粉的平均粒径为1- 20 μm。
步骤(2)所述的烘干温度为60-90 ℃,烘干时间为60-120 min。
步骤(3)所述的升温程序为0-100 ℃时,以1 ℃/min升温至100 ℃,保温1h,然后2-3 ℃/min升温至500 ℃,保温0.5- 3 h,再以2-3 ℃/min升温至900 ℃,最后以1 ℃/min的速率升温至1100-1200 ℃,保温4-6 h,之后空气气氛下自然降温。
步骤(3)所述的烧结气氛为,900 ℃之前为空气气氛,900 ℃之后为氩气或氮气气氛。
所述的坯体b为平板状或管状。
本发明制备的陶瓷支撑体应用气体除尘或水处理领域。其制备原理在于,利用添加烧结助剂法在陶瓷骨料颗粒中加入烧结助剂,使其发生反应形成颈部连接,从而增大陶瓷支撑体的强度。同时,颈部连接的生成有助于形成多孔结构,利于陶瓷支撑体的渗透性能。
测试分析:试样的渗透性能采用氮气渗透系数表示,抗弯强度采用三点抗弯强度仪表征,微观结构采用扫描电子显微镜表征。
本发明的有益效果:
(1)采用分子筛膜合成残液作为烧结助剂,达到了废物利用,节约成本,保护环境的作用;
(2)降低了支撑体的烧结温度,节约了其制备成本;
(3)制备的陶瓷支撑体具有高渗透性能、高强度、高稳定性,可满足气体除尘或水处理领域的应用需求。
附图说明
图1是本发明以一种基于分子筛膜合成残液的多孔陶瓷支撑体制备方法的工艺流程图。
图2是实施例6和对比例1制备所得的陶瓷支撑体的SEM图,(A)为未加分子筛膜合成残液的对比例1样品,(B)为加入10 % NaA分子筛膜合成残液的实施例6样品,(C)文献报道十二烷基苯磺酸钠(SDBS)为烧结助剂制备的多孔陶瓷支撑体(烧结温度1150 ℃),(D)文献报道莫来石纤维为烧结助剂制备的多孔陶瓷支撑体(烧结温度1450 ℃)。
具体实施方式
下面结合实施例对本发明做更进一步地解释,下列实施例仅用于说明本发明,但并不用来限定本发明的实施范围。
实施例1
按质量比计算,将4%的NaA分子筛膜合成残液、20%的粒径为1 μm 活性炭粉、76%的粒径为20 μm 氧化铝粉体均匀混合。混合好的浆料采用干压法制备出平板状的陶瓷支撑体坯体。将压好的陶瓷支撑体坯体放在60 ℃的烘箱中干燥60 min,然后将其放入高温电炉中以1 ℃/min升温到100 ℃,保温1 h,再以2 ℃/min升温到500 ℃并保温2 h,然后再以2℃/min升温到900 ℃,将烧结气氛转换为氮气,接着以1 ℃/min 升温到1100 ℃,并保温4h,之后空气气氛下自然降温。
测试结果是:制得的陶瓷支撑体氮气渗透系数为330 m3/(m2·h·kPa),抗弯强度为15.3 MPa,平均孔径3.2 μm。
实施例2
按质量比计算,将8%的NaA分子筛膜合成残液、10%的粒径为20 μm 活性炭粉、82%的粒径为10 μm 碳化硅粉体均匀混合。将混合好的浆料采用干压法制备出平板状的陶瓷支撑体坯体。将压好的陶瓷支撑体坯体放在60 ℃的烘箱中干燥60 min,然后将其放入高温电炉中以1 ℃/min升温到100 ℃,保温1 h,再以2 ℃/min升温到500 ℃并保温1 h,然后再以2 ℃/min升温到900 ℃,将烧结气氛转换为氩气,接着以1 ℃/min 升温到1200 ℃,并保温6 h,之后空气气氛下自然降温。
测试结果是:制得的陶瓷支撑体氮气渗透系数为120 m3/(m2·h·kPa),抗弯强度为39.5 MPa,平均孔径1.6 μm。
实施例3
按质量比计算,将10%的NaA分子筛膜合成残液、90 %的粒径为100 μm 碳化硅粉体均匀混合。将混合好的粉料采用干压法制备出平板状的陶瓷支撑体坯体。将压好的陶瓷支撑体坯体放在90 ℃的烘箱中干燥90 min,然后将其放入高温电炉中以1 ℃/min升温到100℃,保温1 h,再以3 ℃/min升温到500 ℃并保温0.5 h,然后再以2 ℃/min升温到900 ℃,将烧结气氛转换为氮气,接着以1 ℃/min 升温到1200 ℃,并保温5 h,之后空气气氛下自然降温。
测试结果是:制得的陶瓷支撑体氮气渗透系数为450 m3/(m2·h·kPa),抗弯强度为45.6 MPa,平均孔径15.3 μm。
实施例4
按质量比计算,将8%的NaA分子筛膜合成残液、20%的粒径为20 μm 活性炭粉、72 %的粒径为100 μm 碳化硅粉体均匀混合。将混合好的粉料采用干压法制备出管状的陶瓷支撑体坯体。将压好的陶瓷支撑体坯体放在90 ℃的烘箱中干燥90 min,然后将其放入高温电炉中以1 ℃/min升温到100 ℃,保温1 h,再以3 ℃/min升温到500 ℃并保温0.5 h,然后再以2 ℃/min升温到900 ℃,将烧结气氛转换为氮气,接着以1 ℃/min 升温到1200 ℃,并保温5 h,之后空气气氛下自然降温。
测试结果是:制得的陶瓷支撑体氮气渗透系数为120 m3/(m2·h·kPa),抗弯强度为33.5 MPa,平均孔径29.6 μm。
实施例5
按质量比计算,将2%的NaA分子筛膜合成残液、20%的粒径为10 μm 活性炭粉、78%的粒径为50 μm 碳化硅粉体均匀混合。将混合好的浆料采用干压法制备出平板状的陶瓷支撑体坯体。将压好的陶瓷支撑体坯体放在80 ℃的烘箱中干燥120 min,然后将其放入高温电炉中以1 ℃/min升温到100 ℃,保温1 h,再以2 ℃/min升温到500 ℃并保温3 h,然后再以3 ℃/min升温到900 ℃,接着以1 ℃/min 升温到1200 ℃,并保温6 h,之后空气气氛下自然降温。
测试结果是:制得的陶瓷支撑体氮气渗透系数为450 m3/(m2·h·kPa),抗弯强度为7.5 MPa,平均孔径16.5 μm。
实施例6
按质量比计算,将10%的NaA分子筛膜合成残液、20%的粒径为20 μm 活性炭粉、70%的粒径为100 μm 碳化硅粉体均匀混合。将混合好的粉料采用干压法制备出平板状的陶瓷支撑体坯体。将压好的陶瓷支撑体坯体放在80 ℃的烘箱中干燥90 min,然后将其放入高温电炉中以1 ℃/min升温到100 ℃,保温1 h,再以2 ℃/min升温到500 ℃并保温3 h,然后再以3 ℃/min升温到900 ℃,接着以1 ℃/min 升温到1200 ℃,并保温6 h,之后空气气氛下自然降温。
测试结果是:制得的多孔碳化硅支撑体氮气渗透系数为1300 m3/(m2·h·kPa),抗弯强度为27 MPa,平均孔径27 μm。
对比例1
不添加NaA分子筛的性能比较。按照实施例6的方法制备不含NaA分子筛膜合成残液的碳化硅陶瓷支撑体,制备的样品标记为对比例1。
对比例2
文献(Yang et al, Ceram Int, 2017, 43: 3377-3383)报道使用十二烷基苯磺酸钠(SDBS)作为烧结助剂低温制备的碳化硅支撑体。
对比例3
文献(Han et al, J European Ceram Soc, 2016, 36: 3909-3917)报道使用莫来石纤维制备的碳化硅支撑体。
实施例6、对比例1、对比例2、对比例3的样品表征结果如表1。
表1 实施例6与对比样品表征结果对比
表1结果表明,添加NaA分子筛膜合成残液制备的陶瓷支撑体气体渗透系数及抗弯强度均高于未添加NaA分子筛膜合成残液的样品,与文献报道的两种多孔碳化硅支撑体相比,其烧结温度以及性能均具有一定的优势。由此可见,在陶瓷支撑体制备过程中,NaA分子筛膜合成残液的加入能够提高陶瓷支撑体的渗透性能及强度。
由图2可知,(A)为未添加NaA分子筛膜合成残液的对比例1,(B)为添加NaA分子筛膜合成残液的实施例6,(C)为添加SDBS制备碳化硅支撑体的对比例2,(D)为添加莫来石纤维制备碳化硅支撑体的对比例3。不添加NaA分子筛膜合成残液时,制备的陶瓷支撑体骨料颗粒之间无连接生成,且堆积较密,导致其渗透性能及强度低;而添加NaA分子筛膜合成残液后,陶瓷支撑体骨料颗粒之间有牢固的颈部连接产生,且有明显的孔结构,因此给陶瓷支撑体带来优异的渗透性能与强度,且制备的样品孔结构与使用SDBS、莫来石纤维制备的样品基本相似,因此均具有优异的渗透性能与强度,有利于其在气体净化或水处理领域的应用。
Claims (8)
1.一种基于分子筛膜合成残液的多孔陶瓷支撑体制备方法,其特征在于,制备步骤如下:
(1)按一定比例配制陶瓷浆料a,陶瓷浆料a包括:陶瓷粉末、烧结助剂、造孔剂,并将其均匀混合,烧结助剂为NaA分子筛膜的合成残液;
(2)使用挤压成型法将陶瓷浆料a制备成一定形状尺寸的坯体,烘干,得到干燥后的坯体b;
(3)将坯体b放入高温电炉中,按照一定的升温程序在一定气氛下进行烧结,得到多孔陶瓷支撑体。
2.根据权利要求1所述的一种基于分子筛膜合成残液的多孔陶瓷支撑体制备方法,其特征在于,步骤(1)所述陶瓷浆料a中陶瓷粉末为SiC、Al2O3中的一种,造孔剂为活性炭粉。
3.根据权利要求1或2所述的一种基于分子筛膜合成残液的多孔陶瓷支撑体制备方法,其特征在于,步骤(1)所述的陶瓷浆料a按各成分的质量配比为:NaA分子筛膜合成残液为2-10%,造孔剂为0-20%,其余为陶瓷粉末。
4.根据权利要求2所述的一种基于分子筛膜合成残液的多孔陶瓷支撑体制备方法,其特征在于,所述陶瓷粉料的平均粒径为10-100μm,活性炭粉的平均粒径为1-20μm。
5.根据权利要求1所述的一种基于分子筛膜合成残液的多孔陶瓷支撑体制备方法,其特征在于,步骤(2)所述的烘干温度为60-90℃,烘干时间为60-120min。
6.根据权利要求1所述的一种基于分子筛膜合成残液的多孔陶瓷支撑体制备方法,其特征在于,步骤(3)所述的升温程序为0-100℃时,以1℃/min升温至100℃,保温1h,然后以2-3℃/min升温至500℃,保温0.5-3h,再以2-3℃/min升温至900℃,最后以1℃/min的速率升温至1100-1200℃,保温4-6h,之后空气气氛下自然降温。
7.根据权利要求1所述的一种基于分子筛膜合成残液的多孔陶瓷支撑体制备方法,其特征在于,步骤(3)所述的烧结气氛为在900℃之前为空气,900℃之后转换烧结氛围为氩气或氮气。
8.根据权利要求1所述的一种基于分子筛膜合成残液的多孔陶瓷支撑体制备方法,其特征在于,所述的坯体b为平板状或管状。
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