CN107297220A - 一种蠕虫状介孔Al2O3/分子筛复合材料及其制备方法 - Google Patents
一种蠕虫状介孔Al2O3/分子筛复合材料及其制备方法 Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 21
- -1 molecular sieves compound Chemical class 0.000 title claims abstract description 20
- 229910052593 corundum Inorganic materials 0.000 title claims abstract description 18
- 229910001845 yogo sapphire Inorganic materials 0.000 title claims abstract description 18
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 38
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000010703 silicon Substances 0.000 claims abstract description 18
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- 239000004411 aluminium Substances 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
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- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 5
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- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical group CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- 229910052681 coesite Inorganic materials 0.000 claims description 3
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- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
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- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
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- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 2
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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
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
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- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
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- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
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Abstract
本发明提供了一种蠕虫状介孔Al2O3/分子筛复合材料的制备方法,整个发明大致分为两步法:1)纳米级别分子筛的制备;2)分子筛与介孔氧化铝材料的原位复合。本发明通过调节铝源的水解,使铝源能缓慢水解形成蠕虫状的介孔氧化铝材料,并很好地与分子筛复合,形成同时具备介孔(氧化铝提供)和微孔(分子筛提供)结构的多级孔体系。本发明涉及的制备方法简单可行,条件易于调控,易于大量生产,有望应用应用于分子吸附、催化等工业领域。
Description
技术领域
本发明属于无机合成技术领域,具体涉及一种蠕虫状介孔Al2O3/分子筛复合材料及其制备方法。
背景技术
沸石分子筛属于一类具备结晶态的固体催化剂,广泛的应用在催化,吸附分离,离子交换等领域,是石油化工,精细化学领域不可或缺的一类固体催化剂材料。同时由于该材料通常只有单一的微孔孔道,其用作催化剂时,易造成反应传输路径过长、反应物分子或产物分子的运输受限等问题,从而造成转换率低下,催化剂产生积碳,造成催化剂失活中毒等一系列现象。
为解决以上问题,将具备其他孔隙(大孔,介孔)的材料引入到只具备单一微孔孔隙的分子筛上,合成一种多级孔复合材料是一种简易的策略去解决以上问题。许多研究者也进行了许多类似的研究:中国专利CN103962171A将分子筛直接生长在成型的氧化铝表面,从而得到较高机械强度的微米级别硅铝分子筛-氧化铝复合材料;中国专利CN105983438A将微孔分子筛浆料与中孔氧化铝分子筛水混合,通过调节pH、陈化时间温度以及焙烧温度等条件,合成出了一种具有和-壳结构的分子筛复合材料;中国专利CN104512907A将膨润土、高岭土等与沸石结构导向剂、水、硅源、模板剂、碱金属氢氧化物等混合晶化等一系列方法得到一种高硅铝比NaY沸石的多孔材料等等。
尽管以上发明专利均得到了一些多级孔复合材料,能在一定程度上解决常规微孔分子筛流通扩散性低等问题,但是制备方法仍旧过于复杂,在一定程度上增加了合成的成本。因此,如何发明一种简单的方和合成出具备多级孔道的分子筛复合材料一直是人们迫切希望的。
发明内容
本发明的目的在于提供一种新型蠕虫状介孔Al2O3/分子筛复合材料的制备方法,所制备出来的Al2O3/分子筛复合材料同时具备多级孔道结构(介孔和微孔),所述方法简单可行,无需额外引入其他表面活性剂或介孔模板剂,条件易于控制,易于工业化生产;在分子吸附,催化等领域均具有广阔的应用前景。
为实现上述目的,本发明采用的技术方案为:
一种蠕虫状介孔Al2O3/分子筛复合材料的制备方法,它包括以下步骤:
1)微孔纳米分子筛的合成:将微孔结构导向剂、硅源和水均匀混合均匀得澄清溶液,然后进行晶化反应,将所得产物进行洗涤、干燥、焙烧,得微孔纳米分子筛;
2)将微孔纳米分子筛加入醇类溶剂中,进搅拌超声,得均匀的混合液I;
3)将铝源加入与步骤2)对应的醇类溶剂中,搅拌混合均匀,得混合液II;
4)将所得混合液II滴加到混合液I中,搅拌混合均匀;
5)将步骤4)所得溶液体系进行烘干,然后将所得干燥粉末进行焙烧处理,即得所述蠕虫状介孔Al2O3/分子筛复合材料。
上述方案中,所述分子筛的微孔结构导向剂为四甲基氢氧化铵、四乙基氢氧化铵、四丙基氢氧化铵、四乙烯五铵、乙二胺等分子筛常用的微孔结构导向剂中的一种;所述、硅源为正硅酸四乙酯、硅溶胶、白炭黑等硅源中的一种;所述铝源为仲丁醇铝。
上述方案中,所述醇类溶剂为乙醇、甲醇、异丙醇或正丁醇。
上述方案中,步骤1)中所述硅源的添加量以其实际引入的SiO2的含量为准,所述微孔结构导向剂、SiO2和水(原料中引入的总水量)的质量比为(0.8-1.2):(0.8-1.2):(8-10);步骤1)中所述搅拌时间为2-5h。
上述方案中,所述晶化温度为100-110℃,时间为20-40h。
上述方案中,步骤1)中所述焙烧温度为500-600℃,时间为5-8h。
上述方案中,所述的步骤2)中微孔纳米分子筛与醇类溶液的质量比为1:(200-500),所述的搅拌时间为5-30min,所述的超声时间为2-20h。
上述方案中,步骤3)中所述铝源与醇类溶剂的质量比为1:(30-50);步骤3)中所述搅拌时间为1-10min。
上述方案中,步骤步骤2)中微孔纳米分子筛与步骤3)中所述铝源的质量比为1:(7~10)。
上述方案中,步骤4)中的滴加时间为1-2h,搅拌时间为3-5h。
上述方案中,步骤5)中所述干燥温度为40-100℃时间为10-24h;所述焙烧温度为400-600℃,时间为2-4h。
本发明的原理为:首先将纳米分子筛分散在含水量极少的醇类溶液中,超声分散均匀;然后将铝源仲丁醇铝分散在对应的醇类溶液中;将包含仲丁醇铝的混合溶液滴加到含有单分散分子筛粒子的混合溶液中,搅拌使仲丁醇铝能与分子筛充分混合;由于整个反应体系中含水量极少,仲丁醇铝缓慢水解成氧化铝分子并附着在分子筛纳米粒子上,仲丁醇铝水解缩合生成相应的醇分子向外扩散形成蠕虫状介孔,最后进行烘干焙烧,即得蠕虫状介孔Al2O3/分子筛复合材料。
本发明的有益效果为:以含水量极少的醇类溶液为反应体系,无需额外添加介孔模板剂,通过控制反应速率和反应体系条件,成功合成出具备极大介孔孔隙的蠕虫状介孔Al2O3材料,并成功实现了该蠕虫状介孔Al2O3材料与微孔分子筛材料的复合,最终合成出了同时具备介孔和微孔的多级孔介孔-微孔Al2O3复合材料,该方法简单可行,易于调控,有望大规模工业生产,合成出的复合材料具有两种孔隙,在分子吸附、催化等工业领域均有广阔的应用前景。
附图说明
图1为本发明实施例1所得产物的扫描电镜图。
图2为本发明实施例1所得产物的XRD图。
图3为本发明实施例2所得产物的透射电镜图。
图4为本发明实施例2所得产物的氩气吸脱附曲线图。
图5为本发明实施例3所得产物的介孔孔径分布图。
图6为本发明实施例3所得产物的微孔孔径分布图。
具体实施方式
为了更好的理解本发明,下面结合具体实施例和附图进一步阐明本发明的内容,但本发明的内容不仅仅局限于下面的实施例。
以下实施例中,如无具体说明,采用的试剂均为市售化学试剂。
实施例1
一种蠕虫状介孔Al2O3/分子筛复合材料,其制备方法包括如下步骤:
1)微孔纳米分子筛的合成:依次将11.4g TPAOH(40wt%)溶液、20g TEOS加到30g去离子水,搅拌3h,使其均匀混合,得到澄清溶液,将所得溶液倒入反应釜中,加热至100℃晶化24h,将晶化后的产物洗涤干净、烘干,置于550℃马弗炉中焙烧6h,即得到微孔纳米分子筛;
2)将0.2g所得微孔纳米分子筛加入到100mL乙醇中,超声5h得到单分散的均匀的混合液I;
3)将2g仲丁醇铝加到100mL乙醇中,搅拌5min使其充分混合,得混合液II;
4)将所得混合液II缓慢滴加到混合液I中,保持溶液I不停地搅拌,2h滴加完,之后再搅拌3h,混合均匀;
5)将步骤4)所得溶液体系置于100℃烘箱中干燥10h,得到干燥粉末,最后将得到的样品置于500℃马弗炉中焙烧3h,即得最终产物。
图1为本实施例所得最终产物的扫描电镜图,如图可见,所得产物为粒径在100-200nm的颗粒状物质,由微孔纳米分子筛表面包覆褶皱状(蠕虫状)Al2O3材料而成。图2为本实施例所得最终产物的XRD图,图中基本表现出MFI型分子筛的衍射峰,表明所得Al2O3以无定形形式存在。
实施例2
一种蠕虫状介孔Al2O3/分子筛复合材料,其制备方法包括如下步骤:
1)微孔纳米分子筛的合成:依次将11g TPAOH(40wt%)溶液、20g硅溶胶(30wt%)加到16g去离子水,搅拌4h,使其均匀混合,得到澄清溶液,将所得溶液倒入反应釜中,加热至110℃晶化20h,将晶化后的产物洗涤干净、烘干,置于550℃马弗炉中焙烧7h,即得到微孔纳米分子筛;
2)将0.2g所得微孔纳米分子筛加入到100mL乙醇中,超声6h得到单分散的均匀的混合液I;
3)将2g仲丁醇铝加到100mL乙醇中,搅拌2min使其充分混合,得混合液II;
4)将所得混合液II缓慢滴加到混合液I中,保持溶液I不停地搅拌,1h滴加完,之后再搅拌4h,混合均匀;
5)将步骤4)所得溶液体系置于60℃烘箱中干燥24h,得到干燥粉末,最后将得到的样品置于500℃马弗炉中焙烧2h,即得蠕虫状介孔Al2O3/分子筛复合材料。
图3为本实施例所得最终产物的透射电镜图,图中可以看出100-200nm的颗粒物即为纳米分子筛粒子,同时可以清晰看到有大片的蠕虫状介孔存在,即为介孔Al2O3材料,在高倍透射电镜图下可以清晰看到Al2O3和分子筛很好地复合在一起。图4为本发明实例所制得样品的氩气吸脱附曲线图,在相对压力P/P0小于0.02时,吸附量的陡增表明材料中存在大量微孔,由纳米分子筛提供,在相对压力P/P0为0.6-1时,出现迟滞环,表现材料中存在介孔结构,由蠕虫状介孔Al2O3提供;经检测,本实施例所得最终产物的总的比表面积为344m2/g,其中微孔比表面积为34m2/g,总的孔容为0.93cm3/g。
实施例3
一种蠕虫状介孔Al2O3/分子筛复合材料,其制备方法包括如下步骤:
1)微孔纳米分子筛的合成:依次将11.4g TPAOH(40wt%)溶液、5.9g白炭黑(即5.9g纳米SiO2粒子)加到50g去离子水,搅拌5h,使其均匀混合,得到澄清溶液,将所得溶液倒入反应釜中,加热至100℃晶化24h,将晶化后的产物洗涤干净、烘干,置于550℃马弗炉中焙烧6h,即得到微孔纳米分子筛;
2)将0.2g所得微孔纳米分子筛加入到100mL乙醇中,超声5h得到单分散的均匀的混合液I;
3)将1.5g仲丁醇铝加到80mL乙醇中,搅拌3min使其充分混合,得混合液II;
4)将所得混合液II缓慢滴加到混合液I中,保持溶液I不停地搅拌,2h滴加完,之后再搅拌3h,混合均匀;
5)将步骤4)所得溶液体系置于60℃烘箱中干燥20h,得到干燥粉末,最后将得到的样品置于500℃马弗炉中焙烧2h,即得蠕虫状介孔Al2O3/分子筛复合材料。
图5为本实施例所最终产物的介孔孔径分布图,其介孔孔径大致分布在7-25nm,分布比较广泛。图6为本实施例所最终产物的微孔孔径分布图,分布在0.45nm,孔径相对均一,为标准的分子筛微孔孔径分布图。
以上显示和描述了本发明的基本原理和主要特征和本发明的优点。本行业的技术人员应该了解,本发明不受上述实施例的限制,上述实施例和说明书中描述的只是说明本发明的原理,不脱离本发明精神和范围的前提下,本发明还会有各种变化和改进,这些变化和改进都落入要求保护的本发明的范围内。本发明要求保护范围由所附属的权利要求书及其等效物界定。
Claims (10)
1.一种蠕虫状介孔Al2O3/分子筛复合材料的制备方法,其特征在于,它包括以下步骤:
1)微孔纳米分子筛的合成:将微孔结构导向剂、硅源和水均匀混合均匀得澄清溶液,然后进行晶化反应,将所得产物进行洗涤、干燥、焙烧,得微孔纳米分子筛;
2)将微孔纳米分子筛加入醇类溶剂中,进搅拌超声,得均匀的混合液I;
3)将铝源加入与步骤2)对应的醇类溶剂中,搅拌混合均匀,得混合液II;
4)将所得混合液II滴加到混合液I中,搅拌混合均匀;
5)将步骤4)所得溶液体系进行烘干,然后将所得干燥粉末进行焙烧处理,即得所述蠕虫状介孔Al2O3/分子筛复合材料。
2.根据权利要求1所述的制备方法,其特征在于,所述微孔结构导向剂为四甲基氢氧化铵、四乙基氢氧化铵、四丙基氢氧化铵、四乙烯五铵或乙二胺;所述硅源为正硅酸四乙酯、硅溶胶或白炭黑;所述的铝源为仲丁醇铝。
3.根据权利要求1所述的制备方法,其特征在于,所述醇类溶剂为乙醇、甲醇、异丙醇或正丁醇。
4.根据权利要求1所述的制备方法,其特征在于,步骤1)中所述硅源的添加量以其引入的SiO2为准,所述微孔结构导向剂、SiO2和水的质量比为(0.8-1.2):(0.8-1.2):(8-10)。
5.根据权利要求1所述的制备方法,其特征在于,所述晶化反应温度为100-110℃,时间为20-40h。
6.根据权利要求1所述的制备方法,其特征在于,步骤2)中所述微孔纳米分子筛与醇类溶剂的质量比为1:(200-500)。
7.根据权利要求1所述的制备方法,其特征在于,步骤3)中所述铝源与醇类溶剂的质量比为1:(30-50)。
8.根据权利要求1所述的制备方法,其特征在于,步骤4)中所述滴加时间为1-2h。
9.根据权利要求1所述的制备方法,其特征在于,步骤1)中所述焙烧温度为500-600℃,时间为5-8h;步骤5)中所述焙烧温度为400-600℃,时间为2-4h。
10.权利要求1~9任一项所述的制备方法制备的蠕虫状介孔Al2O3/分子筛复合材料。
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