CN116583347A - 过氧化氢合成以及再生催化剂 - Google Patents

过氧化氢合成以及再生催化剂 Download PDF

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CN116583347A
CN116583347A CN202180081469.0A CN202180081469A CN116583347A CN 116583347 A CN116583347 A CN 116583347A CN 202180081469 A CN202180081469 A CN 202180081469A CN 116583347 A CN116583347 A CN 116583347A
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catalyst
palladium
present
hydrogen peroxide
cerium
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姜东君
金浩东
崔贤雅
刘英山
徐正民
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Heesung Catalysts Corp
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Abstract

本发明涉及一种在将镁以及铈担载到活性氧化铝中并进行焙烧而对金属进行固定化之后再含浸钯并进行还原而获得的催化剂，可以在利用蒽醌法的过氧化氢的制造中适用于工作溶液的再生工程或加氢工程，从而达成高效的再生转换率或合成收率。

Description

过氧化氢合成以及再生催化剂
技术领域
本发明涉及一种利用蒽醌法制造过氧化氢以及再生工作溶液的催化剂。
背景技术
过氧化氢(H2O2)是在如抛光剂、消毒剂、医药品以及氧化剂等多种领域使用的化学制品。过氧化氢是通过利用氢气以及氧气的直接合成法以及利用蒽醌(anthraquinone)系列化合物连续执行加氢以及氧化工程的蒽醌法进行制造。接下来将对蒽醌法进行简单的描述。
过氧化氢可以通过对向烷基蒽醌(通常被称之为2-乙基-蒽醌、EAQ)溶解到适当的有机溶剂中而获得的工作溶液(working solution)反复执行加氢和氧化的方式进行制造。在重复执行如上所述的加氢以及氧化工程时，作为副产物的四氢蒽醌等将被蓄积在工作溶液中，而且会在催化剂上发生焦炭沉积，从而导致过氧化氢的制造以及再生效率的下降。尤其是，在将作为副产物的四氢蒽醌(THAQ)再生为蒽醌时，可以采用在工作溶液中使用通过在40～150℃的温度下将镁担载到活性氧化铝中并在焙烧之前利用氨进行处理而获得的催化剂的技术(公开编号10-2009-0006733)。
发明内容
目前仍然需要开发出一种可以在改善再生效率的同时在过氧化氢的制造中对加氢过程进行催化的催化剂。尤其是，需要开发出一种可以通过对载体的气孔结构进行控制而对活性金属的分散度以及粒子进行调节的高效的催化剂。因此，本发明拟达成的技术课题在于制造出一种可以在过氧化氢的再生以及合成反应中使用的具有优秀的催化活性的催化剂，而且为了克服在重复使用时发生的问题即因为摩擦而导致的活性金属的损失以及催化剂失活的问题，提供一种耐久性以及活性稳定性得到改善的环状钯催化剂。
本发明人开发出了一种通过使得钯活性层以环状形态位于对气孔结构进行控制的载体的内部而提升活性金属在载体内的密度，并通过导入镁以及铈而提升钯粒子的分散度的催化剂。此外，虽然在再生工程中碳会沉积在催化剂内部，但是通过导入铈成分，可以完全去除催化剂内部的残留碳并将钯的分散度损失最小化，从而获得可以维持再生效率的耐久性优秀的催化剂。此外，在所制造出的催化剂中，因为活性金属位于载体内部，因此可以通过对反应过程中的磨损所导致的活性金属的损失进行抑制而提升催化剂的耐久性。
本发明涉及一种不仅可以对利用蒽醌法的过氧化氢的制造工程中的加氢步骤进行催化，还可以改善工作溶液的再生效率的催化剂。
本发明人了解到，当在工作溶液的再生中使用通过将镁以及铈担载到γ氧化铝并焙烧之后含浸靶并经过还原而获得的催化剂时，可以有效地实现再生转化。本发明人还惊人地发现，所述催化剂还可以在蒽醌制造工程中作为作为加氢步骤的催化剂使用。
本发明作为利用包括加氢步骤的蒽醌法制造过氧化氢时在加氢步骤中适用的催化剂或用于对利用蒽醌法制造过氧化氢时所使用的工作溶液进行再生的催化剂，提供一种钯成分以环状形态分布到γ氧化铝粒子内部，且镁以及铈成分均匀地分布到γ氧化铝中的催化剂。非限制性地，根据本发明的催化剂是一种通过使得钯活性金属位于距离γ氧化铝载体表面的5～8μm之间而对其耐久性进行改善的环状形态，所述γ氧化铝具有6.0～9.0nm的气孔大小以及170～220m3/g的气孔体积。此外，钯在所述γ氧化铝载体中以0.023～0.071wt％/m2的活性密度存在，镁在所述γ氧化铝载体中以0.02～0.18wt％/m2的密度均匀存在，而铈在所述γ氧化铝载体中以0.001～0.008wt％/m2的密度均匀存在。此外，氯成分在所述γ氧化铝载体中以0.004～0.03wt％/m2的密度均匀存在。
在根据本发明的过氧化氢再生以及合成催化剂中，作为活性金属的钯在γ氧化铝载体中具有按照特定分布聚集的环状结构，γ氧化铝载体具有可供反应物以及生成物轻易通过的经过控制的内部气孔，而且可以通过在载体内导入镁以及铈而诱导钯的高分散化。根据本发明催化剂，可以通过抑制活性金属的凝聚并增加钯活性点数量而将反应活性极大化。此外，可以在利用硫化床反应器的催化剂反应中发生催化剂的物理性磨损时保持钯活性金属，因此具有高耐久性。
附图说明
图1是根据本发明的环状催化剂结构的概要图。
图2是用于对环状结构进行确认的扫描电子显微镜(SEM)以及电子探针X射线显微分析仪(EPMA)照片。
具体实施方式
接下来，将对本发明进行详细的说明。
本发明涉及一种在将镁以及铈担载到活性氧化铝中并进行焙烧而对金属进行固定化之后再含浸钯并进行还原而获得的催化剂，可以确认在将其适用于工作溶液的再生工程或加氢工程中时，可以达成有效的再生转换率或合成收率。本发明人通过对活性氧化铝的烧结温度进行调节而对载体的气孔结构以及作为活性物质的钯的担载结构进行控制，从而对钯的分散度进行调整。
实施例1
作为载体使用活性氧化铝，将勃姆石(制造企业：德国BASF，比表面积为270m2/g)以750℃进行焙烧之后使用。作为镁以及铈的前驱体使用了硝酸镁(Mg(NO3)2.6H2O)以及硝酸铈(Ce(NO3)3.6H2O)，而作为活性金属前驱体使用了四氯合钯酸(H2PdCl4)。
首先，将相当于催化剂整体重量的4.5％的硝酸镁以及相当于0.25％的硝酸铈混合到离子水中。将所制造出的镁-铈复合溶液利用干湿法含浸到载体中。将担载有镁-铈的组合物在空气环境下以550℃执行2小时的热处理过程，从而对金属进行固定。接下来，向200ml的水添加100g的担载有镁-铈的氧化铝组合物，然后添加与催化剂的整体重量相比相当于1.0％的钯前驱体和相当于1.0％的过氧化氢以及相当于0.2％的HCl并在搅拌的同时升温至80℃，接下来在所述温度下维持30分钟。
催化还原过程是通过向担载有镁-铈-钯的复合体投入还原剂的方式执行。作为还原剂，使用了甲酸钠(NaCOOH)。为了在还原时使得Na被离子化并生成足够的氢气，将温度升温至60℃并在所述温度下维持1小时。
在所制造出的催化剂中，镁以及铈被均匀分布到载体内部，而钯则主要呈现出了与载体外廓相距一定间隔并以10μm至20μm的厚度分布的环状(ring)结构体。所完成的催化剂的Pd密度的计算结果为0.0556％/m2。
实施例2
除了将在实施例1中使用的载体在850℃下进行烧结处理之外，按照与实施例1相同的方法执行而制造出催化剂。相应催化剂呈现出了与实施例1相同的环状结构体。所制造出的催化剂的Pd密度的计算结果为0.0714％/m2。
实施例3
将在实施例1中使用的载体在1,000℃下进行烧结处理之后使用，在担载钯时排除了过氧化氢，并将所投入的HCl增量至0.4％。相应催化剂与实施例1类似，镁以及铈被均匀地分布到载体内部，而钯在催化剂中呈现出卵-壳(Egg-shell)结构体。所完成的催化剂的Pd密度的计算结果为0.0233％/m2。
实施例4
将在实施例1中使用的载体在1,100℃下进行烧结处理之后使用，在担载钯时排除了过氧化氢，并将所投入的HCl增量至0.4％。在相应催化剂中，镁和铈以及钯都均匀地分布到载体内部。所完成的催化剂的Pd密度的计算结果为0.0309％/m2。
比较例1
将在实施例1中使用的载体在850℃下进行烧结处理，并在担载钯时投入了0.4％的HCl。相应催化剂与实施例1类似，镁以及铈被均匀地分布到载体内部，而钯在催化剂中呈现出卵-壳(Egg-shell)结构体。所制造出的催化剂的Pd密度的计算结果为0.0097％/m2。
比较例2
将在实施例1中使用的载体在850℃下进行烧结处理，并在担载钯时投入了0.75％的HCl。在相应催化剂中，镁和铈以及钯都均匀地分布到载体内部。所制造出的催化剂的Pd密度的计算结果为0.0057％/m2。
性能评估
在实施例以及比较例中进行烧结处理的载体的物理特性以及气孔结构如表1中的结果所示。
【表1】
载体氧化铝的结构取决于焙烧温度，温度越高，比表面积以及物理强度越低。在450～900℃的范围内，Al2O3呈现出γ相(Phase)，比表面积约为160～220m2/g。在900～1,100℃的范围内，Al2O3呈现出θ相(Phase)，比表面积约为30～140m2/g。根据本发明的氧化铝，可以具有6.0～9.0nm的气孔大小以及170～222m3/g的比表面积。在使用表1中的载体分别制造催化剂时，催化剂的结构以及Pd分析特性如表2所示。分散度以及Pd粒子的大小，是按照通过CO化学吸附分析(Pulse method)对吸附到Pd中的CO量进行测定的方式进行计算。
【表2】
参阅表2，在实施例1以及2中，钯以环状形态与催化剂的外廓相距5～8μm的间隔。参阅表2，钯的分散度伴随着载体的焙烧温度的升高而减小，而钯的粒子大小增加。利用载体的焙烧温度为1,100℃的αAl2O3制造的催化剂为均匀形态(Uniform type)，可以确认因为比表面积较低，因此钯的分散度也变得非常低。此外，在实施例1至3的催化剂中测定到的钯的密度为0.023～0.071wt％/m2，镁的密度为0.02～0.15wt％/m2，铈的密度为0.001～0.008wt％/m2，且选择性地氯的密度为0.005～0.03wt％/m2。此外，为了对催化剂的再生效率进行测定而执行了再生评估反应，而反应器利用不锈钢(SUS)材质的搅拌式反应系统进行了评估。向圆形搅拌式反应器投入镁条，接下来向)50g的在加氢反应时所产生的副产物工作溶液(Working solution)投入10g的催化剂并对其再生效率进行了测定。接下来，利用液相色谱仪(LC)进行测定。其结果如下述表3所示。
【表3】
关于实施例以及比较例的催化剂初始性能，环状钯催化剂最为优秀。可以确认实施例1以及2的环状钯催化剂与比较例1的卵-壳(Egg-Shell)以及比较例2的均匀(Uniform)结构体的催化剂相比，催化剂的初始性能以及再生后的性能均非常优秀。这主要归因于催化剂的较高的钯分散性。此外，在利用球磨机(Ball mill)施加24小时的物理性冲击之后，仅筛选出去除微粉之后的特定尺寸(Size)的催化剂执行了反应评估。在利用球磨(Ballmilling)方式持续性地向催化剂外部施加冲击时，催化剂会因为受到外部的物理性冲击时的表面粒子的破裂而发生损失，在商业工程中也具有相同的倾向。最终，对经过24小时的球磨(Ball milling)的催化剂进行评估的结果，可以确认如实施例1以及2等环状钯催化剂可以维持与初始性能类似的性能。通过催化剂内Pd含量分析结果可以确认，环状钯催化剂即使是在表面的一部分发生损失的情况下，在钯活性物质的损失方面比较有利，而在钯活性层与表面之间没有形成间隔的卵-壳(Egg-shell)或均匀形态(Uniform type)中，催化剂表面粒子的损失直接代表钯活性物质的损失。

Claims (8)

1.一种催化剂，
作为利用包括加氢步骤的蒽醌法制造过氧化氢时在加氢步骤中适用的催化剂，钯成分与γ氧化铝载体表面相隔一定距离并以环状分布，而镁以及铈成分均匀地分布到所述γ氧化铝载体内部。
2.一种催化剂，
作为对利用蒽醌法制造过氧化氢时所使用的工作溶液进行再生的催化剂，钯成分与γ氧化铝载体表面相隔一定距离并以环状分布，而镁以及铈成分均匀地分布到所述γ氧化铝载体内部。
3.根据权利要求1或权利要求2所述的催化剂，
所述氧化铝具有6.0～9.0nm的气孔大小以及170～222m3/g的比表面积。
4.根据权利要求1所述的催化剂，
所述载体中还包含氯成分。
5.根据权利要求1所述的催化剂，
所述钯在所述载体中以0.023～0.071wt％/m2的活性密度存在。
6.根据权利要求1所述的催化剂，
所述镁在所述载体中以0.02～0.15wt％/m2的密度均匀存在。
7.根据权利要求1所述的催化剂，
所述铈在所述载体中以0.001～0.008wt％/m2的密度均匀存在。
8.根据权利要求4所述的催化剂，
所述氯成分在所述载体中以0.005～0.03wt％/m2的密度均匀存在。
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