CN108147424B - 一种多级孔花瓣状sapo-34分子筛及其制备与应用 - Google Patents
一种多级孔花瓣状sapo-34分子筛及其制备与应用 Download PDFInfo
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Abstract
本发明涉及一种多级孔花瓣状SAPO‑34分子筛及制备与应用,制备方法主要包括:(1)Mor‑PEG结构导向剂的制备:将PEG溶于去离子水中,然后加热搅拌滴加Mor溶液,得到溶液A;(2)前驱体溶液的制备:将铝源、硅源、磷源和去离子水混合,加热搅拌2‑4h,得溶液B;(3)将溶液A加入到溶液B中,加热搅拌4‑8h,得溶胶C;(4)将溶胶C装入反应釜中,在160~180℃温度下晶化24~48h,反应结束后,将所得产品过滤、洗涤、干燥、焙烧。本发明的多级孔SAPO‑34分子筛单个晶体中花瓣间有多级孔结构和较大的孔体积,晶体平均粒径为2‑4um,单片花瓣厚度为50‑100nm,比表面积高达679.33m2/g,可为反应提供更多的活性位点。在甲醇、二甲醚制烯烃的催化反应过程中可以极大地提高反应物及产物的扩散速率。
Description
技术领域
本发明涉及无机纳米材料技术领域,尤其涉及一种多级孔花瓣状SAPO-34分子筛及其制备与应用。
背景技术
分子筛因具有规整的孔道结构对反应物和产物具有择形性,因此作为催化剂被广泛的应用于石油化工领域。具有CHA拓扑结构的SAPO-34分子筛由于其在甲醇、二甲醚制烯烃反应中表现出优异的催化性能,引起了科研工作者的关注。同时也由于晶体结构中有较大的CHA笼以及较小的孔道结构,使其在反应过程中限制了反应物和产物的向外扩散,进而导致大量有机物的积存,形成积碳,覆盖催化剂的活性位点,最终导致催化剂失活。
因此如何解决催化剂积碳失活成为了广大科研工作者的研究重点。研究结果表明,减小晶体尺寸可缩短反应物及产物的扩散路径,制备多级孔道结构SAPO-34分子筛可有效降低反应物及产物的扩散限制,从而提高了催化剂的抗积碳能力延长了催化剂寿命。
专利201410444908.1介绍了一种薄层状形貌SAPO-34分子筛的合成方法。该专利通过使用双头胺阳离子表面活性剂为共模板作用制备出层状SAPO-34分子筛,但双头胺阳离子表面活性剂中含有氯盐、溴盐和胺,在样品处理过程中容易造成环境污染。
专利201610915336.X介绍了一种层状SAPO-34分子筛的制备方法。该专利使用四乙基氢氧化铵为模板剂制备层状SAPO-34分子筛,然而四乙基氢氧化铵价格昂贵且用用量大,严重增加了催化剂的制备成本。
因此寻找一种简单、绿色、低成本的合成方法,制备小晶粒、多级孔道结构的SAPO-34分子筛催化剂具有重大意义及实用价值。
发明内容
本发明的目的在于提供一种多级孔花瓣状SAPO-34分子筛及其制备以解决现有技术存在的问题。
为了实现上述的目的,采用如下的技术方案:
一种多级孔花瓣状SAPO-34分子筛的制备方法,主要包括以下步骤:
(1)Mor-PEG结构导向剂的制备:将PEG溶于去离子水中,然后加热搅拌滴加Mor溶液,得到Mor-PEG结构导向剂溶液A;
(2)前驱体溶液的制备:将铝源、硅源、磷源和去离子水混合,加热搅拌2-4h,得前驱体溶液B;
(3)将Mor-PEG结构导向剂溶液A加入到前驱体溶液B中,加热搅拌4-8h,得溶胶C;
(4)将溶胶C 装入反应釜中,在160~180℃温度下晶化24~48h,反应结束后,将所得产品过滤、洗涤、干燥、焙烧,即得到多级孔花瓣状SAPO-34分子筛。
优选的,所述PEG为PEG-20000。
优选的,所述Mor与 PEG-20000的摩尔比为1:0.005~0.015。
优选的,所述前驱体溶液制备的原料摩尔比为,1.5~2Al2O3:0.8~1.2P2O5:0.4~0.6SiO2:50~100 H2O。
优选的,所述的铝源为拟薄水铝石、活性氧化铝中的一种;所述的硅源为正硅酸四乙酯、白炭黑、硅溶胶中的一种;所述的磷源为磷酸溶液。
优选的,步骤(1)、(2)和步骤(3)中所述的加热搅拌的加热温度为35℃、搅拌速度为300-400r/min。
优选的,步骤(4)中所述的干燥条件为120℃干燥8h以上;所述的焙烧条件为550℃焙烧8h。
一种多级孔花瓣状SAPO-34分子筛,根据上述制备方法制备而得。
上述多级孔花瓣状SAPO-34分子筛的应用,主要作为催化剂应用于甲醇、二甲醚制烯烃反应中。
与现有技术相比,本发明使用结构导向合成法,PEG-20000在溶液中先形成胶束,并缠绕在吗啉表面,相互作用与之形成Mor-PEG结构导向剂。再通过Mor-PEG结构导向剂的诱导作用使晶体生长成多级孔花瓣状SAPO-34分子筛,为合成特殊形貌的材料提供了借鉴意义。本发明所使用的Mor溶液和PEG均绿色且廉价易得,与传统的微孔SAPO-34分子筛相比,本发明的多级孔SAPO-34分子筛单个晶体中花瓣间有多级孔结构和较大的孔体积,晶体平均粒径为2-4um,单片花瓣厚度为50-100nm,在催化反应过程中可以极大地提高反应物及产物的扩散速率;同时还具有较大的比表面积,比表面积高达679.33m2/g,可为反应提供更多的活性位点。在甲醇、二甲醚制烯烃的催化反应过程中表现出较长的催化寿命和较高的低碳烯烃选择性,具有较好的工业应用前景。
附图说明
图1为实施例1所得多级孔花瓣状SAPO-34分子筛的X射线粉末衍射谱图;
图2为实施例1所得多级孔花瓣状SAPO-34分子筛的的SEM图;
图3为实施例1所得多级孔花瓣状SAPO-34分子筛的TEM图;
图4为实施例2所得多级孔花瓣状SAPO-34分子筛的TEM图
图5为本发明的多级孔花瓣状SAPO-34分子筛形成过程原理图。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚,下面将结合附图对本发明作进一步地详细描述。
实施例1
称取2.0g PEG-20000加入到烧杯中,然后在烧杯中加入6.8ml的去离子水,搅拌加热至35℃待PEG-20000完全溶解,再加入1.3ml吗啉溶液,保持恒温继续搅拌2h得Mor-PEG结构导向剂溶液A;称取1.456g拟薄水铝石于另一烧杯,然后依次加入7ml的去离子水,0.65ml的磷酸溶液和0.66ml的正硅酸四乙酯,35℃恒温搅拌2.5h得前驱体溶液B;然后将Mor-PEG结构导向剂溶液A加入到前驱体溶液B中,35℃恒温搅拌4h得溶胶C。将溶胶C转入到带有聚四氟乙烯内衬的反应釜中,装釜完毕后将反应釜移入到烘箱中,在180℃条件下晶化48h。晶化完成后冷却至室温,然后将样品抽滤、洗涤至最后一次滤液呈中性。收集样品,在120℃鼓风干燥箱内干燥10h;把所得的干燥样品放进马弗炉,以2℃/min的升温速度升温至550℃,焙烧8h,冷却至室温,即得到多级孔花瓣状SAPO-34分子筛。图1为样品的X射线粉末衍射谱图,由图可知,所合成的样品具有典型的CHA拓扑结构的SAPO-34 特征衍射峰,衍射峰强度表明样品有较高的结晶度。图2为样品的SEM照片,SEM图显示了样品呈花瓣状。图3样品的TEM照片同样也展示出样品为花瓣状。结合图2和图3可以看出单个晶体中花瓣间有多级孔结构和较大的孔体积,单片花瓣厚度为50-100nm,在二甲醚制烯烃催化反应过程中可以极大地提高反应物及产物的扩散速率。将所制备的SAPO-34应用于二甲醚制烯烃反应,二甲醚的转化率达到100%,乙烯和丙烯双烯选择性达到83.7%。图5展示了多级孔花瓣状SAPO-34的形成过程原理,PEG-20000在溶液中先形成胶束,并缠绕在吗啉表面,相互作用与之形成Mor-PEG结构导向剂(溶液)。
实施例2
称取2.0g PEG-20000加入到烧杯中,然后在烧杯中加入6.8ml的去离子水,搅拌加热至35℃待PEG-20000完全溶解,再加入1.3ml吗啉溶液,保持恒温继续搅拌2h得Mor-PEG结构导向剂溶液A;称取1.456g拟薄水铝石于另一烧杯,然后依次加入7ml的去离子水,0.65ml的磷酸溶液和0.66ml的正硅酸四乙酯,35℃恒温搅拌2.5h得前驱体溶液B;然后将Mor-PEG结构导向剂溶液A加入到前驱体溶液B中,35℃恒温搅拌4h得溶胶C。将溶胶C转入到带有聚四氟乙烯内衬的反应釜中,装釜完毕后将反应釜移入到烘箱中,在180℃条件下晶化36h。晶化完成后冷却至室温,然后将样品抽滤、洗涤至最后一次滤液呈中性。收集样品,在120℃鼓风干燥箱内干燥10h;把所得的干燥样品放进马弗炉,以2℃/min的升温速度升温至550℃,焙烧8h,冷却至室温,同样得到多级孔花瓣状SAPO-34分子筛。得到的X射线粉末衍射谱图、SEM图与实施例1的图1和图2相似。图4为本实施例所得样品的TEM照片,结合图2、图3和图4我们可以看出单个晶体中花瓣间有多级孔结构和较大的孔体积,单片花瓣厚度为50-100nm,在催化反应过程中可以极大地提高反应物及产物的扩散速率。
实施例3
本实施例中的步骤与实施例1完全相同。不同的是:在Mor-PEG结构导向剂制备过程中,所加PEG-20000由2.0g改变为2.5g。所制备的样品同样为多级孔花瓣状SAPO-34分子筛。得到的X射线粉末衍射谱图、SEM图与TEM照片与实施例1的图1-图2相似。
实施例4
本实施例中的步骤与实施例1完全相同。不同的是:在前驱体溶液制备过程中,所加铝源由1.456g的拟薄水铝石改变为1.2g的活性氧化铝。所制备的样品同样为多级孔花瓣状SAPO-34分子筛。得到的X射线粉末衍射谱图、SEM图与TEM照片与实施例1的图1-图3相似。
实施例5
本实施例中的步骤与实施例1完全相同。不同的是:在前驱体溶液制备过程中,所加去离子水由7.0ml改为7.66ml。所制备的样品同样为多级孔花瓣状SAPO-34分子筛。得到的X射线粉末衍射谱图、SEM图与TEM照片与实施例1的图1-图3相似。
实施例6
本实施例中的步骤与实施例1完全相同。不同的是:在前驱体溶液制备过程中,所加磷酸溶液由0.65ml改为0.615ml。所制备的样品同样为多级孔花瓣状SAPO-34分子筛。得到的X射线粉末衍射谱图、SEM图与TEM照片与实施例1的图1-图3相似。
实施例7
本实施例中的步骤与实施例1完全相同。不同的是:在Mor-PEG结构导向剂制备过程中,所加PEG-20000由2.0g改变为0.5g。不能制备出多级孔花瓣状SAPO-34分子筛。
实施例8
本实施例中的步骤与实施例1完全相同。不同的是:在Mor-PEG结构导向剂制备过程中,不加入PEG-20000。不能制备出多级孔花瓣状SAPO-34分子筛。
以上所述,进一步用详细的实施步骤和试验对本发明作了详尽的描述,这只能作为对本发明的一种说明而不能限制本发明,因此在不偏离本发明精神的基础上所做的修改或改进,均属于本发明要求保护的范围。
Claims (7)
1.一种多级孔花瓣状SAPO-34分子筛的制备方法,其特征在于,主要包括以下步骤:
(1)Mor-PEG结构导向剂的制备:将PEG溶于去离子水中,然后加热搅拌滴加Mor溶液,得到Mor-PEG结构导向剂溶液A;
(2)前驱体溶液的制备:将铝源、硅源、磷源和去离子水混合,加热搅拌2-4h,得前驱体溶液B;
(3)将Mor-PEG结构导向剂溶液A加入到前驱体溶液B中,加热搅拌4-8h,得溶胶C;
(4)将溶胶C装入反应釜中,在160~180℃温度下晶化36~48h,反应结束后,将所得产品过滤、洗涤、干燥、焙烧,即得到多级孔花瓣状SAPO-34分子筛;所述PEG为PEG-20000;所述Mor与PEG-20000的摩尔比为1:0.005~0.015。
2.根据权利要求1所述的制备方法,其特征在于,所述前驱体溶液制备的原料摩尔比为,1.5~2Al2O3:0.8~1.2P2O5:0.4~0.6SiO2:50~100H2O。
3.根据权利要求1所述的制备方法,其特征在于,所述的铝源为拟薄水铝石、活性氧化铝中的一种;所述的硅源为正硅酸四乙酯、白炭黑、硅溶胶中的一种;所述的磷源为磷酸溶液。
4.根据权利要求1所述的制备方法,其特征在于,步骤(1)、(2)和步骤(3)中所述的加热搅拌的加热温度为35℃、搅拌速度为300-400r/min。
5.根据权利要求1所述的制备方法,其特征在于,步骤(4)中所述的干燥条件为120℃干燥8h以上;所述的焙烧条件为550℃焙烧8h。
6.一种多级孔花瓣状SAPO-34分子筛,其特征在于,根据权利要求1-5任一项所述制备方法制备而得。
7.根据权利要求6所述多级孔花瓣状SAPO-34分子筛的应用,其特征在于,主要作为催化剂应用于甲醇、二甲醚制烯烃反应中。
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