CN113210008A - 一种用于肉桂醛加氢反应的Pt负载型分子筛催化剂的制备方法 - Google Patents
一种用于肉桂醛加氢反应的Pt负载型分子筛催化剂的制备方法 Download PDFInfo
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- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 title claims abstract description 32
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Abstract
本发明属于多相催化领域，具体涉及一种用于肉桂醛选择性加氢反应的Pt负载型分子筛催化剂的制备方法，该方法以微孔分子筛HZSM‑5、HMCM‑22、Hβ为基体，采用常温浸渍法将Pt负载在微孔分子筛上，并通过碱处理的方法将催化剂脱硅扩孔。本发明所制成的催化剂用于肉桂醛选择性加氢生成肉桂醛反应中，在反应温度为100‑120℃、反应时间为0.5‑1h，反应釜压力2MPa，转速1000rpm时，有良好的催化性能，且该Pt负载型分子筛加氢催化剂合成方法简单、成本低廉。
Description
技术领域
本发明涉及用于选择性加氢反应中多相催化剂的制备领域，具体涉及用于α,β-不饱和醛如肉桂醛选择性加氢反应中含Pt负载型分子筛催化剂的制备方法。
技术背景
肉桂醛是一种典型的α,β-不饱和醛，其加氢产物是重要的精细化工产品，在医药、香料领域有极大的应用价值。并且肉桂醛加氢反应常作为α,β-不饱和醛选择性加氢的模型反应。在肉桂醛生成肉桂醇选择性加氢反应中，碳碳双键加氢在热力学上比碳氧双键更有利，更容易生成3-苯丙醛而非肉桂醇，需克服碳碳双键加氢以及碳碳双键与碳氧双键的共轭效应，氢化碳氧双键，同时保持碳碳双键，从而生成肉桂醇。
肉桂醛加氢反应中常使用的就是Pt催化剂，其中含铂均相催化剂难分离不易回收，更常采用Pt负载型催化剂，而微孔分子筛作为载体有水热稳定性好、孔道可调控等优点，如Pt/HZSM-5、Pt/HMCM-22、Pt/Hβ分子筛。但是单纯的微孔分子筛做催化剂时在选择性加氢反应中对产物的选择性不高，而想要进一步提高肉桂醛加氢过程中对肉桂醇的选择性，就要对催化剂进行改性处理，从而诱导碳氧双键加氢。
一般的改性处理方法有：一是增大孔径，有利于反应物扩散；二是Lewis酸存在会活化碳氧双键，促进碳氧双键转化；三是增大Pt粒径，有利于提高Pt(111)晶面，Pt(111)与碳碳双键排斥，抑制碳碳双键吸附；四是引入第二金属如Fe、Sn等，作为电子供体来提高Pt电子密度，或者作亲电位或Lewis酸，活化碳氧双键。而增大Pt粒径可能会使Pt纳米粒子聚集，降低分散度导致催化活性降低；引入第二金属操作比较繁琐复杂，能耗较高，不能应用于工厂化大规模使用。
因此，开发一种高效的Pt负载型分子筛催化剂，使其能更加有效地提高肉桂醛加氢过程中对肉桂醇的选择性具有重要的应用价值。
发明内容
本发明要解决的技术问题是在肉桂醛选择性加氢生成肉桂醇的反应过程中，针对催化效果低、催化剂制备过程复杂等问题，提供一种合成方法简单、成本低廉、催化效果好，且选择性高的Pt负载型分子筛催化剂的制备方法。
本发明解决其问题所采用的技术方案是：
(1)将微孔分子筛加入到去离子水中，室温搅拌10min，其中微孔分子筛与去离子水的质量比为1:10-1:20；
(2)向步骤(1)所得的混合物中逐滴加入与步骤(1)中微孔分子筛质量比为1:0.04的氢氧化钠溶液，继续室温搅拌30min，其中氢氧化钠溶液的浓度为0.1mol·L-1；
(3)向步骤(2)所得的混合物中逐滴加入用丙酮配制的氯铂酸溶液，继续室温搅拌2h，其中氯铂酸中Pt的质量为溶液中微孔分子筛质量的1％；
(4)将步骤(3)所得的混合物在空气中老化8h，在80℃下干燥12h，冷却后研磨成粉状，在550℃下焙烧4h，得氧化态催化剂；
(5)将步骤(4)得到的氧化态催化剂在400℃的H2/Ar气氛下，以5℃/min升温速率还原2h，即得到经碱处理的Pt负载型分子筛催化剂。
作为对本发明的限定，本发明所述的微孔分子筛为HZSM-5、HMCM-22或Hβ分子筛。
作为对本发明的再次限定，本发明所述的催化剂可用于肉桂醛选择性加氢生成肉桂醇的过程中，其具体反应条件为：0.2g催化剂，0.5mL肉桂醛，20mL无水乙醇作溶剂，反应温度100℃，反应时间1h，反应釜压力2MPa，转速1000rpm。
本发明所述的微孔分子筛HZSM-5制备方法如下：
将12.5g氢氧化钠放入288mL去离子水中搅拌至完全溶解；随后向溶液中加入3.7g偏铝酸钠和195mL四丙基氢氧化铵溶液，并剧烈搅拌；在强烈搅拌下将195mL硅胶溶液缓慢滴加到溶液中，继续强烈搅拌30min。随后将白色凝胶移入聚四氟乙烯内衬的晶化釜中，在烘箱160℃晶化3天；过滤，洗涤至pH＝9.0，在110℃下烘干24h，随后在马弗炉中550℃焙烧8h得微孔分子筛NaZSM-5。将NaZSM-5用2mol/L NH4NO3溶液(10mg/g催化剂)于80-100℃回流交换2次，每次4h，经抽滤、去离子水洗涤、烘干(120℃)，最后在马弗炉中550℃焙烧制得HZSM-5分子筛。
本发明所述的微孔分子筛HMCM-22制备方法如下：
将13.3g氢氧化钠溶于443mL去离子水中；随后向上述溶液中加入4g偏铝酸钠和38mL六亚甲基亚胺，并剧烈搅拌；在强烈搅拌下将195mL硅溶胶缓慢滴加到上述溶液，继续强烈搅拌30min。将所得白色凝胶移入聚四氟乙烯内衬的晶化釜中，在烘箱150℃晶化7天；然后过滤，洗涤至pH＝8.0，在110℃下烘干24h，随后在马弗炉中550℃焙烧8h，即得微孔分子筛NaMCM-22。将NaMCM-22用2mol/L NH4NO3溶液(10mg/g催化剂)于80-100℃回流交换2次，每次4h，经抽滤、去离子水洗涤、烘干(120℃)，最后在马弗炉中550℃焙烧制得HMCM-22分子筛。
本发明所述的微孔分子筛Hβ制备下：
将5.3g氢氧化钠放入162mL去离子水中搅拌至完全溶解；随后向上述溶液中加入5.4g偏铝酸钠和79mL四乙基氢氧化铵，并剧烈搅拌；在强烈搅拌下将195mL硅溶胶缓慢滴加到上述溶液，继续强烈搅拌30min。将所得白色凝胶移入聚四氟乙烯内衬的晶化釜中，在烘箱140℃晶化3天；晶化完成后，使反应釜自然冷却至室温，抽滤，用去离子水洗涤至中性，烘干后得到β沸石原粉。将β沸石用2mol/L NH4NO3溶液(10mg/g催化剂)于80-100℃回流交换2次，每次4h，经抽滤、去离子水洗涤、烘干(120℃)，最后在马弗炉中550℃焙烧制得Hβ分子筛。
采用上述技术方案后，本发明取得的有益效果是：
本发明所述Pt负载型分子筛加氢催化剂合成方法简单、成本低廉。
同时本发明对微孔分子筛进行改性，用氢氧化钠对催化剂进行脱硅处理，既能对微孔分子筛进行扩孔，产生部分介孔结构，使反应物能更好的进行扩散，又能保留催化剂结构中的Lewis酸性位点，从而使碱处理后的Pt负载型分子筛催化剂对肉桂醛选择性加氢生成肉桂醇有更好的转化率和更高的选择性。
附图说明
图1是未经处理前分子筛和碱处理后分子筛的氮气吸脱附等温线，其中Cat 1、Cat3和Cat5分别是未经处理分子筛Pt/HZSM-5、Pt/HMCM-22和Pt/Hβ；Cat 2、Cat4和Cat 6分别是经过氢氧化钠改性的分子筛Pt/HZSM-5、Pt/HMCM-22和Pt/Hβ。
从图1可以看出，图中Cat 1、Cat 3和Cat 5呈Ⅰ型等温线，是典型的微孔结构；而经过氢氧化钠处理后的分子筛Cat 2、Cat 4和Cat 6，等温线是Ⅳ型等温线，具有滞后环出现，说明有介孔结构存在，可见此方法可以有效对微孔分子筛进行脱硅产生部分介孔结构。
图2是未经处理前Pt/HZSM-5(图2左图)和碱处理后Pt/HZSM-5(图2右图)的TEM图。
由图2可见，未经处理分子筛Pt/HZSM-5(左图)即Cat 1结构完整，Pt纳米粒子在分子筛中出现轻微团聚；而经过碱处理后的Pt/HZSM-5(右图)即Cat 2有轻微塌陷，证实了此方法可以产生部分介孔，同时Pt纳米粒子分散均匀且大小基本一致。
具体实施方式
本发明将就以下实施例作进一步说明，但应了解的是，这些实施例仅为例示说明之用，而不应被解释为本发明实施的限制。
实施例1(对比例)
将0.5g微孔分子筛HZSM-5加入到10mL去离子水中，在室温下搅拌30min，再逐滴加入1.34mL用丙酮配制的氯铂酸溶液，继续室温搅拌2h，所得的混合物在空气中老化8h，在80℃下干燥12h，冷却后研磨成粉状，在550℃下焙烧4h，得氧化态催化剂，在400℃的H2/Ar下以5℃/min升温速率还原2h，即得到Pt/HZSM-5，记为Cat 1。
实施例2
将0.5g微孔分子筛HZSM-5加入到5mL去离子水中，室温搅拌10min，向上述混合物中，逐滴加入5mL配制成0.1mol/L的氢氧化钠溶液，继续室温搅拌30min，再逐滴加入1.34mL用丙酮配制的氯铂酸溶液，继续室温搅拌2h，所得的混合物在空气中老化8h，在80℃下干燥12h，冷却后研磨成粉状，在550℃下焙烧4h，得氧化态催化剂，在400℃的H2/Ar下以5℃/min升温速率还原2h，即得到碱处理后的Pt/HZSM-5(碱)，记为Cat 2。
实施例3(对比例)
将0.5g微孔分子筛HMCM-22加入到10mL去离子水中，在室温下搅拌30min，再逐滴加入1.34mL用丙酮配制的氯铂酸溶液，继续室温搅拌2h，所得的混合物在空气中老化8h，在80℃下干燥12h，冷却后研磨成粉状，在550℃下焙烧4h，得氧化态催化剂，在400℃的H2/Ar下以5℃/min升温速率还原2h，即得到Pt/HMCM-22，记为Cat 3。
实施例4
将0.5g微孔分子筛HMCM-22加入到5mL去离子水中，室温搅拌10min，向上述混合物中，逐滴加入5mL配制成0.1mol/L的氢氧化钠溶液，继续室温搅拌30min，再逐滴加入1.34mL用丙酮配制的氯铂酸溶液，继续室温搅拌2h，所得混合物在空气中老化8h，在80℃下干燥12h，冷却后研磨成粉状，在550℃下焙烧4h，得氧化态催化剂，在400℃的H2/Ar下以5℃/min升温速率还原2h，即得到碱处理的Pt/HMCM-22(碱)，记为Cat 4。
实施例5(对比例)
将0.5g微孔分子筛Hβ加入到10mL去离子水中，室温搅拌30min，再逐滴加入1.34mL用丙酮配制的氯铂酸溶液，继续室温搅拌2h，所得混合物在空气中老化8h，在80℃下干燥12h，冷却后研磨成粉状，在550℃下焙烧4h，得氧化态催化剂，在400℃的H2/Ar下以5℃/min升温速率还原2h，即得到Pt/Hβ，记为Cat 5。
实施例6
将0.5g微孔分子筛Hβ加入到5mL去离子水中，室温搅拌10min，向上述混合物中，逐滴加入5mL配制成0.1mol/L的氢氧化钠溶液，继续室温搅拌30min，再逐滴加入1.34mL用丙酮配制的氯铂酸溶液，继续室温搅拌2h，所得的混合物在空气中老化8h，在80℃下干燥12h，冷却后研磨成粉状，在550℃下焙烧4h，得氧化态催化剂，在400℃的H2/Ar下以5℃/min升温速率还原2h，即得到碱处理的Pt/Hβ(碱)，记为Cat 6。
将上述实施例中得到的碱处理Pt负载型分子筛催化剂用于肉桂醛选择性加氢反应中，以肉桂醛为原料，无水乙醇作为溶剂，反应温度100-120℃时，加入Pt负载型分子筛催化剂，其中肉桂醛与Pt负载型分子筛催化剂的质量比为5：2～3，反应时间0.5-1h，反应釜压力2MPa，转速1000rpm的条件下反应。
将上述Cat1～6应用在下述具体的反应中：0.2g催化剂，0.5mL肉桂醛，20mL无水乙醇作溶剂，反应温度100℃，反应时间1h，反应釜压力2MPa，转速1000rpm。
各催化剂的催化性能如表1所示：
表1 Pt负载型分子筛催化剂的催化性能
| 催化剂 | 肉桂醛转化率(％) | 肉桂醇选择性(％) |
| Cat 1(对比例) | 52.3 | 73.1 |
| Cat 2 | 95.8 | 90.7 |
| Cat 3(对比例) | 16.0 | 46.6 |
| Cat 4 | 83.0 | 82.3 |
| Cat 5(对比例) | 12.2 | 33.7 |
| Cat 6 | 85.4 | 85.6 |
由表1结果可见，本发明所发明的碱处理Pt负载型分子筛催化剂对肉桂醛选择性加氢生成肉桂醛有良好的反应催化性能，不仅对肉桂醛有较高的转化率，同时对肉桂醇也有优异的选择性。
以上述依据本发明的理想实施例为启示，通过上述的说明内容，相关工作人员完全可以在不偏离本项发明技术思想的范围内，进行多样的变更以及修改。本项发明的技术性范围并不局限于说明书上的内容，必须要根据权利要求范围来确定其技术性范围。
Claims (4)
1.一种用于肉桂醛加氢反应的Pt负载型分子筛催化剂的制备方法，其特征在于该Pt负载型分子筛催化剂的制备方法是以微孔分子筛为基体，采用常温浸渍法将Pt负载在微孔分子筛上，并通过碱处理的方法将催化剂脱硅扩孔得到的。
2.一种用于肉桂醛加氢反应的Pt负载型分子筛催化剂的制备方法，其特征在于该制备方法是按照下列步骤进行的：
(1)将微孔分子筛加入到去离子水中，其中微孔分子筛与去离子水的质量比为1:10-1:20；
(2)向步骤(1)所得的混合物中逐滴加入与步骤(1)中微孔分子筛质量比为1:0.04的氢氧化钠溶液，其中氢氧化钠溶液的浓度为0.1mol·L-1；
(3)向步骤(2)所得的混合物中逐滴加入用丙酮配制的氯铂酸溶液，其中氯铂酸中Pt的质量为溶液中微孔分子筛质量的0.5～0.8％；
(4)将步骤(3)所得的混合物在空气中老化、干燥12h，冷却后研磨成粉状，在550℃下焙烧4h，得氧化态催化剂；
(5)将步骤(4)得到的氧化态催化剂在400℃的H2/Ar气氛下，以5℃/min升温速率还原2h，即得到经碱处理的Pt负载型分子筛催化剂。
3.根据权利要求1中所述的一种用于肉桂醛加氢反应的Pt负载型分子筛催化剂的制备方法，其特征在于所述的微孔分子筛为HZSM-5、HMCM-22或Hβ分子筛。
4.根据权利要求1中所述的一种用于肉桂醛加氢反应的Pt负载型分子筛催化剂的制备方法，其特征在于所述Pt负载型分子筛催化剂在肉桂醛选择性加氢生成肉桂醇反应具体应用方法如下：
以肉桂醛为原料，无水乙醇作为溶剂，反应温度100-120℃时，加入Pt负载型分子筛催化剂，其中肉桂醛与Pt负载型分子筛催化剂的质量比为5：2～3，反应时间0.5-1h，反应釜压力2MPa，转速1000rpm的条件下反应。
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