CN110201706A - 一种Pt/NH2-MCM-41催化剂及其制备方法与应用 - Google Patents
一种Pt/NH2-MCM-41催化剂及其制备方法与应用 Download PDFInfo
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Abstract
本发明提供一种Pt/NH2‑MCM‑41催化剂及其制备方法与应用,旨在提供一种在硅氢加成反应中具有稳定性好、重复使用性好、活性高、回收便利、成本较低等优点的催化剂,其技术要点:该催化剂是以介孔硅MCM‑41为载体,γ‑氨丙基三乙氧基硅烷为改性剂,氯铂酸为铂源制得的;属于催化剂领域。
Description
技术领域
本发明涉及催化剂领域,具体涉及一种Pt/NH2-MCM-41催化剂,本发明还是涉及该催化剂的制备方法及其应用。
背景技术
硅氢加成反应最有效、最常用的铂催化剂为Speier催化剂和Karstedt催化剂,这两种催化剂对不饱和烃的硅氢加成反应具有良好的催化活性,但是两者都属均相催化剂反应体系,难以回收利用,导致贵金属铂的浪费。
目前,人们致力于研发非均相催化剂,采用含功能基团的试剂对载体进行改性,再将铂负载于载体上,形成高分子负载催化剂,可以回收重复利用,减小贵金属铂的流失,降低生产成本。
近年来,含磷、硫、砷功能基团的非均相催化剂被证实具有的催化活性,但磷硫在高温下不稳定,砷对人体有害。因此,有必要开发出一种稳定性好、重复使用性好、回收便利、绿色环保的铂催化剂以满足市场的需要。
发明内容:
本发明的第一个目的是提供一种Pt/NH2-MCM-41催化剂,该催化剂具有稳定性好、重复使用性好、活性高、回收便利、成本较低。
本发明的第二个目的是提供上述催化剂的制备方法。
本发明的第三个目的是提供上述催化剂的应用。
为了实现上述目的,本发明提供的第一个技术方案是这样的:
该催化剂是以介孔硅MCM-41为载体,γ-氨丙基三乙氧基硅烷为改性剂,氯铂酸为铂源制得的。
为制备上述催化剂,本发明提供的第二个技术方案是这样的:
一种Pt/NH2-MCM-41催化剂的制备方法,包括如下步骤:
1)介孔硅MCM-41的制备
加入1.2-1.8g模板剂十六烷基三甲基溴化铵、150mL蒸馏水和95-120mL浓氨水于三口烧瓶中,在55-65℃下恒温搅拌0.8-1.2h后加入7-8g正硅酸乙酯,55-65℃继续搅拌6-8h后停止反应,置于室温中晶化、过滤后收集滤饼,并且用蒸馏水洗涤滤饼、在50-60℃烘干12-24h得到将介孔硅;然后将介孔硅研磨分散,置于马弗炉中焙烧以除去模板剂十六烷基三甲基溴化铵,自然冷却即得到白色产物,记为介孔硅MCM-41;
2)氨基化介孔硅NH2-MCM-41的制备
称取1-3g经活化的介孔硅MCM-41和48-72mL甲苯于三口烧瓶中,缓慢滴加3-11mmol的γ-氨丙基三乙氧基硅烷,氮气保护下搅拌25-30min后加热至回流状态,反应20-28h,自然冷却后过滤并收集滤饼,分别用甲苯和乙醇(用甲苯洗涤多次后再用乙醇洗涤多次)洗涤多次,干燥(60℃,12-24h),制得氨基化介孔硅,记为NH2-MCM-41;
3)Pt/NH2-MCM-41催化剂的制备
称取1-3gNH2-MCM-41和30mL丙酮于三口烧瓶中,氮气保护下搅拌25-35min后添加3-15mL0.05mol/L的氯铂酸-乙醇溶液,回流搅拌8-12h,自然冷却后过滤并收集滤饼,真空干燥,制得淡黄色产物,记为Pt/NH2-MCM-41催化剂。
作为本发明的进一步优选,上述的Pt/NH2-MCM-41催化剂的制备方法,步骤1)所述焙烧温度为550℃,时间为6h。
作为本发明的进一步优选,上述的Pt/NH2-MCM-41催化剂的制备方法,步骤1)所述介孔硅MCM-41活化是介孔硅MCM-41在120℃真空干燥箱中干燥4h。
作为本发明的进一步优选,上述的Pt/NH2-MCM-41催化剂的制备方法,步骤4)所述氮气的纯度大于或等于99.999%。
作为本发明的进一步优选,上述的Pt/NH2-MCM-41催化剂的制备方法,步骤2)所述γ-氨丙基三乙氧基硅烷与介孔硅质量比为0.7749:1。
作为本发明的进一步优选,上述的Pt/NH2-MCM-41催化剂的制备方法,步骤3)所述氨基化介孔硅与氯铂酸的质量比为10:1。
本发明提供的第三个技术方案是上述催化剂作为硅氢加成反应催化剂的应用。
更为具体的地说是,上述的Pt/NH2-MCM-41催化剂作为七甲基三硅氧烷和丙烯醇聚氧乙烯醚的硅氢加成反应的催化剂的应用。
本发明的有益效果是:
1)本发明的所制备的介孔硅MCM-41具有大比表面积、有序的孔道结构、较好的化学稳定性及耐酸碱性,是良好的载体;
2)本发明以介孔硅MCM-41为载体,γ-氨丙基三乙氧基硅烷为改性剂,氯铂酸为铂源,制备的负载型Pt/NH2-MCM-41催化剂,有效地提高催化剂的稳定性和环保型,具有良好的重复使用性和催化活性,且回收利用方便,大大降低了生产成本;
3)本发明的Pt/NH2-MCM-41催化剂用于七甲基三硅氧烷和聚乙二醇烯丙基醚的催化硅氢加成反应时,七甲基三硅氧烷的转化率可达90%以上。
附图说明
图1是本发明提供的Pt/NH2-MCM-41催化剂的XRD图;
图2是本发明提供的Pt/NH2-MCM-41催化剂的TEM图;
图3是本发明提供的Pt/NH2-MCM-41催化剂的TG图。
具体实施方式
下面通过具体的实例对本发明的技术方案进行说明。
实施例1
本发明提供的一种Pt/NH2-MCM-41催化剂,是通过下述步骤制得的:
1)加入1.5g十六烷基三甲基溴化铵、150mL蒸馏水和105mL浓氨水于三口烧瓶中,在60℃下恒温搅拌1h后加入7.5g正硅酸乙酯,在60℃下继续搅拌7h后停止反应,置于室温中晶化、过滤后收集滤饼、滤饼用蒸馏水洗涤,在60℃烘干12h,然后将介孔硅研磨分散,置于马弗炉中,在550℃焙烧6h以除去模板剂十六烷基三甲基溴化铵,自然冷却即得到白色产物,记为MCM-41。
2)称取1g经活化(所述的活化是介孔硅MCM-41在120℃真空干燥箱中干燥4h)的介孔硅MCM-41和60mL甲苯于三口烧瓶中,缓慢滴加3.5mmol的γ-氨丙基三乙氧基硅烷,在纯度大于或等于99.999%氮气保护下搅拌30min后,加热80℃至回流状态,反应24h,自然冷却后过滤并收集滤饼,先用甲苯洗涤4次,在用乙醇洗涤4次,在60℃干燥12h,制得氨基化介孔硅,记为NH2-MCM-41。
3)称取1gNH2-MCM-41和30mL丙酮于三口烧瓶中,氮气保护下搅拌30min后添加4mL0.05mol/L的氯铂酸-乙醇溶液,在40℃温度下回流搅拌10h,自然冷却后过滤并收集滤饼,真空干燥,制得淡黄色产物,记为Pt/NH2-MCM-41催化剂。
实施例2
本发明提供的一种Pt/NH2-MCM-41催化剂,依次通过下述步骤制得的:
1)介孔硅MCM-41的制备
加入1.2g模板剂十六烷基三甲基溴化铵、150mL蒸馏水和95mL浓氨水于三口烧瓶中,在65℃下恒温搅拌0.8h后加入8g正硅酸乙酯,65℃继续搅拌6h后停止反应,置于室温中晶化、过滤后收集滤饼、滤饼用蒸馏水洗涤,55℃,20h烘干得到将介孔硅;然后将介孔硅研磨分散,置于马弗炉中,在550℃焙烧6h以除去模板剂十六烷基三甲基溴化铵,自然冷却即得到白色产物,记为MCM-41;
2)氨基化介孔硅NH2-MCM-41的制备
称取3g经活化的(所述的活化是介孔硅MCM-41在120℃真空干燥箱中干燥4h)介孔硅MCM-41和72ml甲苯于三口烧瓶中,缓慢滴加3mmol的γ-氨丙基三乙氧基硅烷,在纯度大于或等于99.999%氮气保护下搅拌30min后,加热80℃至回流状态,反应20h,自然冷却后过滤并收集滤饼,先用甲苯洗涤4次,在用乙醇洗涤4次,在60℃干燥24h,制得氨基化介孔硅,记为NH2-MCM-41;
3)Pt/NH2-MCM-41催化剂的制备
称取3gNH2-MCM-41和30mL丙酮于三口烧瓶中,氮气保护下搅拌25min后添加15mL0.05mol/L的氯铂酸-乙醇溶液,在40℃温度下回流搅拌8h,自然冷却后过滤并收集滤饼,真空干燥,制得淡黄色产物,记为Pt/NH2-MCM-41催化剂。
实施例3
本发明提供的一种Pt/NH2-MCM-41催化剂,依次通过下述步骤制得的:
1)介孔硅MCM-41的制备
加入1.8g模板剂十六烷基三甲基溴化铵、150mL蒸馏水和120mL浓氨水于三口烧瓶中,在55℃下恒温搅拌1.2h后加入7g正硅酸乙酯,55℃继续搅拌8h后停止反应,置于室温中晶化、过滤后收集滤饼、采用滤饼用蒸馏水洗涤、在50℃,烘干24h得到将介孔硅;然后将介孔硅研磨分散,置于马弗炉中,在550℃焙烧6h以除去模板剂十六烷基三甲基溴化铵,自然冷却即得到白色产物,记为MCM-41;
2)氨基化介孔硅NH2-MCM-41的制备
称取2g经活化的(所述的活化在120℃真空干燥箱中干燥4h)介孔硅MCM-41和48mL甲苯于三口烧瓶中,缓慢滴加11mmol的γ-氨丙基三乙氧基硅烷,在纯度大于或等于99.999%氮气保护下搅拌25min后,加热80℃至回流状态,反应28h,自然冷却后过滤并收集滤饼,先用甲苯洗涤4次,在用乙醇洗涤4次,在60℃干燥20h,制得氨基化介孔硅,记为NH2-MCM-41;
3)Pt/NH2-MCM-41催化剂的制备
称取2gNH2-MCM-41和30mL丙酮于三口烧瓶中,氮气保护下搅拌35min后添加3mL0.05mol/L的氯铂酸-乙醇溶液,在40℃温度下回流搅拌12h,自然冷却后过滤并收集滤饼,真空干燥,制得淡黄色产物,记为Pt/NH2-MCM-41催化剂。
实施例1至实施3其XRD、TEM、TG的表征,结果见图1至图3。其中,图1(A)、(B)为介孔硅、氨基化介孔硅和铂催化剂的小角和广角XRD图。从图1(A)可以看出,介孔硅MCM-41在2θ为2.40°、4.16°、4.81°处的衍射峰分别对应于(100)、(110)和(200)晶面,说明所合成的MCM-41具有高度有序的六方相结构。而NH2-MCM-41和Pt/NH2-MCM-41样品在(100)晶面的衍射峰强度有所降低,稍向高角度方向移动,且在(110)和(200)晶面的衍射峰几乎消失,说明有机物和铂金属成功修饰在介孔硅MCM-41的部分孔道中。由图1(B)可见,三个样品均在2θ=22.7°有一个宽广的特征衍射峰,这归属于MCM-41硅孔壁的非晶型特性。而曲线c未发现有Pt的特征衍射峰,说明铂以离子形式存在。
图2(A)-(E)为介孔硅、氨基化介孔硅和铂催化剂的TEM图。由图2(A)可看出,MCM-41呈现高度有序排列的孔道结构;图2(C)中,NH2-MCM-41样品也显示出规整有序的孔道结构,说明氨基化的MCM-41的整体结构未发生变化。而图2(E)中,Pt/NH2-MCM-41样品仍然保持了孔结构的特征,孔道均一,排列整齐。由图2(B)、(D)和(F)可以得知,三个样品的单个颗粒形状均为六方相。此外,在Pt/NH2-MCM-41样品中未发现有Pt晶粒,说明样品中的Pt以离子形式存在。
图3为介孔硅、氨基化介孔硅和铂催化剂的TG图。由图可看出,失重率大小为Pt/NH2-MCM-41>NH2-MCM-41>MCM-41。
应用例:
取Pt/NH2-MCM-41催化剂用于七甲基三硅氧烷和丙烯醇聚氧乙烯醚的催化硅氢加成反应:反应温度为90℃,催化剂质量为七甲基三硅氧烷质量的0.025%,反应物摩尔比n(丙烯醇聚氧乙烯醚)/n(七甲基三硅氧烷)为1.1:1。在反应3h后,七甲基三硅氧烷的转化率即达到92.16%。
以上实施例仅用以说明而非限制本发明的技术方案,尽管上述实施例对本发明进行了详细说明,本领域的相关技术人员应当理解:可以对本发明进行修改或者同等替换,但不脱离本发明精神和范围的任何修改和局部替换均应涵盖在本发明的权利要求范围内。
Claims (9)
1.一种Pt/NH2-MCM-41催化剂,其特征在于,该催化剂是以介孔硅MCM-41为载体,γ-氨丙基三乙氧基硅烷为改性剂,氯铂酸为铂源制得的。
2.权利要求1所述的Pt/NH2-MCM-41催化剂的制备方法,其特征在于,依次包括如下步骤:
1)介孔硅MCM-41的制备
加入1.2-1.8g模板剂十六烷基三甲基溴化铵、150mL蒸馏水和95-120mL浓氨水于三口烧瓶中,在55-65℃下恒温搅拌0.8-1.2h后加入7-8g正硅酸乙酯,55-65℃继续搅拌6-8h后停止反应,置于室温中晶化、过滤后收集滤饼,并且用蒸馏水洗涤滤饼、在50-60℃烘干12-24h,得到将介孔硅;然后将介孔硅研磨分散,置于马弗炉中焙烧以除去模板剂十六烷基三甲基溴化铵,自然冷却即得到白色产物,记为介孔硅MCM-41;
2)氨基化介孔硅NH2-MCM-41的制备
称取1-3g经活化的介孔硅MCM-41和48-72mL甲苯于三口烧瓶中,缓慢滴加3-11mmol的γ-氨丙基三乙氧基硅烷,氮气保护下搅拌25-30min后加热至回流状态,反应20-28h,自然冷却后过滤并收集滤饼,先用甲苯洗涤多次后,再用乙醇洗涤多次,在60℃干燥12-24h,制得氨基化介孔硅,记为NH2-MCM-41;
3)Pt/NH2-MCM-41催化剂的制备
称取1-3gNH2-MCM-41和30mL丙酮于三口烧瓶中,氮气保护下搅拌25-35min后添加3-15mL0.05mol/L的氯铂酸-乙醇溶液,回流搅拌8-12h,自然冷却后过滤并收集滤饼,真空干燥,制得淡黄色产物,记为Pt/NH2-MCM-41催化剂。
3.根据权利要求2所述的Pt/NH2-MCM-41催化剂的制备方法,其特征在于,步骤1)所述焙烧温度为550℃,时间为6h。
4.根据权利要求2所述的Pt/NH2-MCM-41催化剂的制备方法,其特征在于,步骤4)所述氮气的纯度大于或等于99.999%。
5.根据权利要求2所述的Pt/NH2-MCM-41催化剂的制备方法,其特征在于,步骤2)所述γ-氨丙基三乙氧基硅烷与介孔硅质量比为0.7749:1。
6.根据权利要求2所述的Pt/NH2-MCM-41催化剂的制备方法,其特征在于,步骤3)所述氨基化介孔硅与氯铂酸的质量比为10:1。
7.根据权利要求2所述的Pt/NH2-MCM-41催化剂的制备方法,其特征在于,所述的介孔硅MCM-41的活化方法为将介孔硅MCM-41在120℃真空干燥箱中干燥4h。
8.权利要求1所述的Pt/NH2-MCM-41催化剂作为硅氢加成反应催化剂的应用。
9.根据权利要求8所述的Pt/NH2-MCM-41催化剂作为硅氢加成反应催化剂的应用,所述的硅氢加成反应指的是七甲基三硅氧烷和丙烯醇聚氧乙烯醚的硅氢加成反应。
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