CN106925346B - 一种高催化活性的il@sba-15材料及制备方法和用途 - Google Patents
一种高催化活性的il@sba-15材料及制备方法和用途 Download PDFInfo
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- B01J31/0285—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre also containing elements or functional groups covered by B01J31/0201 - B01J31/0274
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Abstract
本发明提供了一种高催化活性的IL@SBA‑15材料及制备方法和用途,制备方法如下:步骤1、制备SBA‑15;步骤2、制备含磺酸基的离子液体IL;步骤3、制备高催化活性的IL@SBA‑15材料:将含磺酸基的离子液体溶于无水甲醇中,滴入到分散有SBA‑15的无水甲醇中;室温下搅拌反应,反应结束后,蒸去无水甲醇得到产物负载有磺酸基的离子液体的SBA‑15,即高催化活性的IL@SBA‑15材料,记为IL@SBA‑15。本发明得到的催化剂对苯酚与叔丁醇的烷基化均具有较高的催化活性。
Description
技术领域
本发明是以嵌段共聚物P123(聚环氧乙烯-聚环氧丙烯-聚环氧乙烯)为模板剂、正硅酸乙酯为硅源、正己烷作为胶束膨胀剂和NH4NO3作为结构辅助剂,水热合成法制得了具有不同孔径、有序的六方中孔二氧化硅材料,具体为一种高催化活性的IL@SBA-15材料及制备方法和用途,属于无机纳米复合材料的技术领域。
背景技术
有序硅基介孔分子筛与其他微孔分子筛材料相比,具有比表面较大,孔径易调节及表面易修饰等优点,在吸附,催化,离子交换等方面具有较好的应用前景。纯有序硅基介孔分子筛上基本没有酸性,氧化及还原等催化活性,为了考察其在一些催化方面的应用,必须将具有活性的物质引进纯有序硅基介孔分子筛中。离子液体(硫酸氢[1-丙基磺酸基-3-甲基咪唑])作为一种磺酸咪唑基B酸,在许多反应中表现出高催化活性。例如,Gui等人首先报道了一系列官能化的离子液体催化叔丁醇和苯酚的烷基化反应,反应物以合适的比例得到高的转化率和高的2,4-DTBP选择性(Gui J等,J.Mol.Catal.A:Chem.2005,225,27-31)。然而,它的高粘度和吸湿性限制了它们的应用(Vafaeezadeh M等,Chem.Eng.J.2014,250,34–41)。此外,从反应混合物中分离和回收使用的离子液体将消耗大量能量(Valkenberg M等,Green Chem.2002,4:88–93)。这些问题限制了它更广泛的应用。为了克服这些问题,可以在高表面积材料上载负官能化离子液体。通过这种方式,离子液体的均相催化反应转化为非均相催化反应,同时减少离子液体的消耗并再循环利用来实现高催化剂效率。
本研究主要是在有序硅基介孔分子筛中引入具有催化活性的离子液体,结合有序硅基介孔分子筛与离子液体的优势,用浸渍法将离子液体(硫酸氢[1-丙基磺酸基-3-甲基咪唑])负载在有序硅基SBA-15孔道上得到复合材料IL@SBA-15催化剂,考察该催化剂对苯酚与叔丁醇烷基化的催化活性。同时有序硅基介孔复合材料作为苯酚与叔丁醇的烷基化反应的催化剂时,反应物以及产物会在介孔分子筛上吸附/脱附。而对于孔径可调节的小孔型的介孔分子筛,其孔径大小是影响反应物及产物的吸附/脱附程度因素之一。狭小的孔径会使分子筛孔道堵塞而失活,而过大的孔径降低了反应物与活性组分的接触率。针对这个特点,我们将硫酸氢[1-丙基磺酸基-3-甲基咪唑]离子液体负载在不同孔径的SBA-15上,考察SBA-15的孔径对苯酚与叔丁醇烷基化的催化影响。
本发明首先合成出-SO3H官能化的B酸性离子液体(硫酸氢[1-丙基磺酸基-3-甲基咪唑])。通过加入扩孔剂正己烷和结构辅助剂硝酸铵成功的合成了三种不同孔径的SBA-15。将硫酸氢[1-丙基磺酸基-3-甲基咪唑]负载到具有不同孔径的有序硅基介孔分子筛上得到IL@SBA-15(5,8,12nm)固体酸催化剂。通过反应温度,载体孔径对苯酚与叔丁醇烷基化反应的转化率和选择性的影响,得到了最佳的载体孔径。
发明内容
本发明的目的是通过浸渍法将硫酸氢[1-丙基磺酸基-3-甲基咪唑]离子液体负载在不同孔径的有序的SBA-15上而得到IL@SBA-15(5,8,12nm)固体酸催化剂。实验表明:用于苯酚烷基化反应最合适的SBA-15载体孔径为8nm。具体方案如下:
一种高催化活性的IL@SBA-15材料,所述高催化活性的IL@SBA-15材料是由硫酸氢[1-丙基磺酸基-3-甲基咪唑]离子液体负载在SBA-15上形成的,所述高催化活性的IL@SBA-15材料具有有序的中孔结构;以高催化活性的IL@SBA-15材料用于苯酚与叔丁醇的烷基化反应时,苯酚的转化率达到了85.5%。
一种高催化活性的IL@SBA-15材料的制备方法,步骤如下:
步骤1、制备SBA-15;
步骤2、制备含磺酸基的离子液体IL;
步骤3、制备高催化活性的IL@SBA-15材料:将含磺酸基的离子液体溶于无水甲醇中,滴入到分散有SBA-15的无水甲醇中;室温下搅拌反应,反应结束后,蒸去无水甲醇得到产物负载有磺酸基的离子液体的SBA-15,即高催化活性的IL@SBA-15材料,记为IL@SBA-15。
步骤1中,所述SBA-15的孔径为5~12nm。
当SBA-15的孔径为5nm时,制备SBA-15的方法为:称取2g P123加入到60mL去离子水中溶解,搅拌至澄清,加入10mL浓HCl(37%)搅拌至无泡沫,缓慢滴入4.5mL TEOS,35℃下搅拌24h;转移到聚四氟乙烯水热反应釜中,100℃下水热晶化48h;对产物抽滤,洗涤,干燥,干燥后的样品置于马弗炉中550℃下焙烧6h以除去模板剂,得到SBA-15。
当SBA-15的孔径为8nm、12nm时,制备SBA-15的方法为:分别取4g P123,20mL浓HCl(37%)加入到120mL去离子水中溶解至澄清,加入0.0968g NH4NO3,20℃下搅拌两小时,加入正己烷;再加入9mL TEOS,恒温下继续搅拌24h,装入水热反应釜中,100℃下水热晶化48h;对产物抽滤,洗涤,干燥,干燥后的样品置于马弗炉中550℃下焙烧6h以除去模板剂,得到不同孔径的SBA-15分子筛;所加入的正己烷为1mL时,得到孔径为8nm的SBA-15,记为SBA-15(8nm);所加入的正己烷为4mL时,得到孔径为12nm的SBA-15,记为SBA-15(12nm)。
所制备的高催化活性的IL@SBA-15材料作为苯酚与叔丁醇烷基化反应的催化剂的用途。
有益效果:
本发明的优点:使用正己烷作为胶束膨胀剂和NH4NO3作为结构辅助剂,在控制温度不变的条件下,通过调节胶束膨胀剂的用量制得了不同孔径的有序的六方中孔二氧化硅材料(SBA-15)。再将离子液体([PSMim][HSO4])通过浸渍法负载到有序的不同孔径SBA-15上得到酸催化剂(IL@SBA-15(5nm,8nm,12nm))。得到的三种孔径不同的催化剂对苯酚与叔丁醇的烷基化均具有较高的催化活性。其中,1-IL@SBA-15(8nm)在80℃的温度下显示出最高的苯酚转化率85.5%和2,4-DTBP的选择性为60.0%。与同为载体的SBA-15(5nm,12nm)相比,载体SBA-15(8nm)具有优越的催化活性和选择性。
附图说明
图1:实施例1制备样品的FT-IR图;
图2:实施例1制备样品的热重图;
图3:实施例2制备样品的比表面图;
图4:实施例2制备样品的XRD图;
图5:实施例2制备样品的TEM图((A)SBA-15(5nm);(B)SBA-15(8nm);(C)SBA-15(12nm);(D)1-IL@SBA-15(5nm));
图6:反应温度以及载体的孔径对苯酚的转化率及产物的选择性的影响(催化剂:(a)1-IL@SBA-15(5nm),(b)1-IL@SBA-15(8nm),(c)1-IL@SBA-15(12nm),n(叔丁醇):n(苯酚)=2,反应时间为2h,空速为2h-1)。
具体实施方式
下面就具体实施例对本发明做进一步说明
实施例1
首先按照参考文献中的方法制备出SBA-15(5nm)以及离子液体IL,再将1g IL溶于5mL无水甲醇中,将其逐滴加入到1g不同孔径的SBA-15和50mL无水甲醇混合溶液中,室温下搅拌6h,反应结束后,蒸去溶剂甲醇得到白色固体,记为1-IL@SBA-15(5nm)。IL,SBA-15(5nm),1-IL@SBA-15(5nm)的红外光谱如图1。在1058cm-1处的吸收峰是SBA-15(5nm)SiO2结构峰。在3153cm-1和3113cm-1的吸收带属于IL咪唑环的吸收峰,1575cm-1伸缩振动特征峰归属于IL咪唑上的C-H键。在1060cm-1和1172cm-1的振动吸收峰分别是-SO3H和HSO4 -的特征峰。另外,对1-IL@SBA-15(5nm)的热重曲线如图2。图中从265℃至600℃的热损失35.9%为IL的实际负载量。
实施例2
按照实施例1的方法制备了SBA-15(5nm)以及离子液体IL,再在制备SBA-15过程中加入正己烷作为胶束膨胀剂和NH4NO3作为结构辅助剂,得到不同孔径的SBA-15(8nm),SBA-15(12nm)。再将IL负载在不同孔径的SBA-15上,得到不同催化剂。具体制备步骤为:分别取4g P123,20mL浓HCl(37%)加入到120mL去离子水中溶解至澄清,加入0.0968g NH4NO3,20℃下搅拌两小时,加入正己烷1mL,4mL。再加入9mLTEOS,恒温下继续搅拌24h,装入水热反应釜中,100℃下水热晶化48h。抽滤,洗涤,干燥。干燥后的样品置于马弗炉中550℃下焙烧6h以除去模板剂,得到不同孔径的SBA-15分子筛。所得样品分别标记为SBA-15(8nm),SBA-15(12nm)。再将1g IL溶于5mL无水甲醇中,将其逐滴加入到1g不同孔径的SBA-15和50mL无水甲醇混合溶液中,室温下搅拌6h,反应结束后,蒸去溶剂甲醇得到白色固体,分别记为1-IL@SBA-15(5nm),1-IL@SBA-15(8nm),1-IL@SBA-15(12nm)。所得样品的比表面图见图3,所有材料清晰的显示具有H1型滞后环典型的Ⅳ型吸附-脱附等温线。图4的XRD图中所有样品在2θ=0.5-3°范围内均有(100),(110),(200)三种清楚的衍射峰。图5的TEM图中样品均显示出良好有序中孔结构。这些都表明无论是扩孔后SBA-15或负载离子液体之后样品的有序典型棒条形结构保持完好。
实施例3
按照实施例2的方法,得到三种催化剂分别记为1-IL@SBA-15(5nm),1-IL@SBA-15(8nm),1-IL@SBA-15(12nm)。将它们作为苯酚与叔丁醇烷基化反应的催化剂,测定苯酚的转化率及产物的选择性。具体步骤如下:以实验制得的三种材料1-IL@SBA-15(5nm),1-IL@SBA-15(8nm),1-IL@SBA-15(12nm)作为催化剂,分别将0.8g的三种催化剂装入连续流动固定床反应器中,反应液叔丁醇与苯酚(n(叔丁醇):n(苯酚)=2)由注射泵注入预热器中,以氮气作为载气和保护气,在反应温度范围为60-100℃、反应时间为2h和空速为2h-1下测定烷基化反应的结果。从图6实验结果可以看出:1-IL@SBA-15(8nm)在80℃的温度下显示出最高的苯酚转化率85.5%和2,4-DTBP的选择性为60.0%。
Claims (4)
1.一种高催化活性的IL@SBA-15材料,其特征在于,所述高催化活性的IL@SBA-15材料是由硫酸氢[1-丙基磺酸基-3-甲基咪唑]离子液体负载在SBA-15上形成的,所述高催化活性的IL@SBA-15材料具有有序的中孔结构;当SBA-15的孔径为5nm时,制备SBA-15的方法为:称取2gP123加入到60ml去离子水中溶解,搅拌至澄清,加入10ml浓HCl搅拌至无泡沫,缓慢滴入4.5mlTEOS,35℃下搅拌24h;转移到聚四氟乙烯水热反应釜中,100℃下水热晶化48h;对产物抽滤,洗涤,干燥,干燥后的样品置于马弗炉中550℃下焙烧6h,得到孔径为5nm的SBA-15;当SBA-15的孔径为8nm、12nm时,制备SBA-15的方法为:分别取4gP123,20ml浓HCl加入到120ml去离子水中溶解至澄清,加入0.0968gNH4NO3,20℃下搅拌两小时,加入正己烷;再加入9mlTEOS,恒温下继续搅拌24h,装入水热反应釜中,100℃下水热晶化48h;对产物抽滤,洗涤,干燥,干燥后的样品置于马弗炉中550℃下焙烧6h,得到不同孔径的SBA-15分子筛;所加入的正己烷为1mL时,得到孔径为8nm的SBA-15,记为SBA-15(8nm);所加入的正己烷为4mL时,得到孔径为12nm的SBA-15,记为SBA-15(12nm)。
2.根据权利要求1所述的IL@SBA-15材料,其特征在于,以高催化活性的IL@SBA-15材料用于苯酚与叔丁醇的烷基化反应时,苯酚的转化率达到了85.5%。
3.一种如权利要求1所述的高催化活性的IL@SBA-15材料的制备方法,其特征在于,步骤如下:
步骤1、制备SBA-15;
步骤2、制备含磺酸基的离子液体IL;
步骤3、制备高催化活性的IL@SBA-15材料:将含磺酸基的离子液体溶于无水甲醇中,滴入到分散有SBA-15的无水甲醇中;室温下搅拌反应,反应结束后,蒸去无水甲醇得到产物负载有磺酸基的离子液体的SBA-15,即高催化活性的IL@SBA-15材料,记为IL@SBA-15;当SBA-15的孔径为5nm时,制备SBA-15的方法为:称取2gP123加入到60ml去离子水中溶解,搅拌至澄清,加入10ml浓HCl搅拌至无泡沫,缓慢滴入4.5mlTEOS,35℃下搅拌24h;转移到聚四氟乙烯水热反应釜中,100℃下水热晶化48h;对产物抽滤,洗涤,干燥,干燥后的样品置于马弗炉中550℃下焙烧6h,得到孔径为5nm的SBA-15;当SBA-15的孔径为8nm、12nm时,制备SBA-15的方法为:分别取4gP123,20ml浓HCl加入到120ml去离子水中溶解至澄清,加入0.0968gNH4NO3,20℃下搅拌两小时,加入正己烷;再加入9mlTEOS,恒温下继续搅拌24h,装入水热反应釜中,100℃下水热晶化48h;对产物抽滤,洗涤,干燥,干燥后的样品置于马弗炉中550℃下焙烧6h,得到不同孔径的SBA-15分子筛;所加入的正己烷为1mL时,得到孔径为8nm的SBA-15,记为SBA-15(8nm);所加入的正己烷为4mL时,得到孔径为12nm的SBA-15,记为SBA-15(12nm)。
4.权利要求3所述方法制备的高催化活性的IL@SBA-15材料作为苯酚与叔丁醇烷基化反应的催化剂的用途。
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