CN110483239B - 一种丙二醇的制备方法 - Google Patents
一种丙二醇的制备方法 Download PDFInfo
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- CN110483239B CN110483239B CN201910788729.2A CN201910788729A CN110483239B CN 110483239 B CN110483239 B CN 110483239B CN 201910788729 A CN201910788729 A CN 201910788729A CN 110483239 B CN110483239 B CN 110483239B
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- nanoparticles
- main catalyst
- catalyst
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- propylene glycol
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Abstract
本发明公开了一种丙二醇的制备方法,所述制备方法至少包括如下步骤,将糖类、主催化剂和助催化剂在反应器中形成混合体系。本发明能实现丙二醇的高选择性和高产率。
Description
技术领域
本发明属于环境化工领域,具体涉及一种丙二醇的制备方法。
背景技术
丙二醇(1,2-丙二醇或1,3-丙二醇)作为一种高附加值化学品,不但是一种化工产品可应用于食品、药物、化妆品、防冻剂等行业,而且可作为一种中间平台分子应用于不饱和树脂聚酯的生产,随着各行业需求的日益增长,世界对丙二醇需求越来越大。目前,工业上丙二醇的生产方法仍然依赖于石油化工,根据可持续发展的发展理念,实现糖类(如纤维素、淀粉、葡萄糖等)催化转化为丙二醇可以实现丙二醇的绿色生产。然而,目前同一催化剂条件下实现催化氢解糖类高效转化为丙二醇具有诸多难点(以葡萄糖为例):其一是葡萄糖单向异构化为果糖难;其二是C6单糖进行C3-C3断键控制难;其三是副反应抑制难,体系中涉及的各类初始物、中间产物和终产物发生的水解、异构化、断键和加氢四个过程的定向控制难。以上问题共同导致了糖类转化为丙二醇的选择性和产率处于较低水平。
发明内容
为了克服以上所述现有技术的缺点,本发明的目的在于提供一种丙二醇的制备方法,实现了丙二醇的高选择性和高产率。
为了实现上述目的或者其他目的,本发明是通过以下技术方案实现的,一种丙二醇的制备方法,所述制备方法至少包括如下步骤,
将糖类、主催化剂和助催化剂在反应器中形成混合体系;
将所述混合体系在还原性气体氛围中进行水热反应,获得所述丙二醇,其中,所述助催化剂形成结合在所述主催化剂表面的氢氧化镁,形成有催化活性的主催化剂-助催化剂复合催化剂。
在一实施例中,所述主催化剂的活性组分包括铂纳米颗粒、钯纳米颗粒、镍纳米颗粒、钌纳米颗粒、钴纳米颗粒、铑纳米颗粒、铱纳米颗粒、铜纳米颗粒、银纳米颗粒或者金纳米颗粒中的一种或多种组合。所述主催化剂的载体包括硅铝分子筛、氧化硅、氧化铝、氧化锆、碳或者碳化硅中的一种。
在一实施例中,所述助催化剂包括氢氧化镁或者氧化镁。
在一实施例中,所述进行加热处理步骤中的温度为140℃-250℃,所述还原性气体氛围的压力包括2-6MPa。所述还原性气体包括氢气。
在一实施例中,所述反应器包括釜式反应器或者固定床反应器中的一种。
在一实施例中,在所述釜式反应器中,所述助催化剂的用量包括0.5-2mg/mL,所述主催化剂与所述助催化剂的质量比包括10-40:1。
在一实施例中,所述固定床反应器中的空速包括0.12h-1至0.96h-1。
在一实施例中,在所述釜式反应器中,所述糖类包括葡萄糖、果糖、山梨糖、甘露糖、木糖、山梨醇、甘露醇、木糖醇、淀粉以及纤维素中的一种或多种组合。所述糖类的用量包括10-22.5mg/ml。
在一实施例中,在所述固定床反应器中,所述糖类包括葡萄糖、果糖、山梨糖、甘露糖、木糖、山梨醇、甘露醇以及木糖醇中的一种或多种组合。
在一实施例中,在所述釜式反应器中,所述混合体系的反应条件还包括反应时间为0.5小时-6小时以及搅拌速率为200-600转/分。
在一实施例中,所述主催化剂的制备方法包括,
对载体进行饱和吸水率测定;
将含有所述主催化剂的活性组分的前驱体溶解于去离子水中,获得前驱体水溶液;
将所述载体加入到所述前驱体水溶液中,获得主催化剂中间体;
对所述主催化剂中间体进行老化、干燥和焙烧,获得氧化态的主催化剂;
对所述氧化态的主催化剂进行还原处理,获得所述主催化剂;
其中,所述去离子水的体积与所述载体的质量的比值等于所述饱和吸水率,所述主催化剂的活性组分的负载量为0.5%-10%。
在一实施例中,所述进行还原处理步骤中的温度为80-300℃。
附图说明
图1为一实施例中丙二醇的制备方法流程示意图;
图2为一实施例中PtNPs/SiO2催化剂的TEM图;
图3为一实施例中PtNPs/SiO2催化剂的TEM图;
图4为一实施例中Mg-PtNPs/SiO2催化剂的TEM图;
图5为一实施例中Mg-PtNPs/SiO2催化剂的TEM图;
图6为一实施例中不同主催化剂-助催化剂复合材料的催化效果;
图7为一实施例中助催化剂投加量对葡萄糖产丙二醇产率的影响;
图8为一实施例中投加不同氧化物和氢氧化物对葡萄糖产丙二醇产率的影响;
图9为一实施例中无助催化剂条件下Pt/SiO2催化氢解葡萄糖的反应产物分布;
图10一实施例中在有助催化剂条件下Pt/SiO2催化氢解葡萄糖的反应产物分布;
图11为不同方法合成的催化剂在三次回用过程中丙二醇产率和催化剂中金属含量的变化示意图;
图12为一实施例中Mg-PtNPs/SiO2催化葡萄糖在固定床反应器中的催化效果图。
具体实施方式
以下通过特定的具体实施例说明本发明的实施方式,本领域技术人员可由本说明书所揭露的内容轻易地了解本发明的其他优点与功效。本发明还可以通过另外不同的具体实施方式加以实施或应用,本说明书中的各项细节也可以基于不同观点与应用,在没有背离本发明的精神下进行各种修饰或改变。需说明的是,在不冲突的情况下,以下实施例及实施例中的特征可以相互组合。还应当理解,本发明实施例中使用的术语是为了描述特定的具体实施方案,而不是为了限制本发明的保护范围。下列实施例中未注明具体条件的试验方法,通常按照常规条件,或者按照各制造商所建议的条件。
当实施例给出数值范围时,应理解,除非本发明另有说明,每个数值范围的两个端点以及两个端点之间任何一个数值均可选用。除非另外定义,本发明中使用的所有技术和科学术语与本技术领域的技术人员对现有技术的掌握及本发明的记载,还可以使用与本发明实施例中所述的方法、设备、材料相似或等同的现有技术的任何方法、设备和材料来实现本发明。
如图1所示,提供一种丙二醇的制备方法,所述制备方法至少包括如下步骤,
S1、将糖类、主催化剂和助催化剂在反应器中形成混合体系;
S2、将所述混合体系在还原性气体氛围中进行水热反应,获得所述丙二醇,其中,所述助催化剂形成结合在所述主催化剂表面的氢氧化镁,形成有催化活性的主催化剂-助催化剂复合催化剂。
下面具体从步骤S1和S2来说明本发明,
具体的,在步骤S1中,将糖类、主催化剂和助催化剂在反应器中形成混合体系,所述反应器包括釜式反应器或者固定床反应器中的一种。例如,在所述釜式反应器中,所述糖类的用量包括10-22.5mg/ml,所述主催化剂与所述助催化剂的质量比包括10-40:1。所述糖类包括葡萄糖、果糖、山梨糖、甘露糖、木糖、山梨醇、甘露醇、木糖醇、淀粉以及纤维素中的一种或多种组合。所述助催化剂包括氧化镁或者氢氧化镁。
所述主催化剂的制备方法包括,对载体进行饱和吸水率测定;将含有所述主催化剂的活性组分的前驱体溶解于去离子水中,获得前驱体水溶液;将所述载体加入到所述前驱体水溶液中,获得主催化剂中间体;对所述主催化剂中间体进行老化、干燥和焙烧,获得氧化态的主催化剂;对所述氧化态的主催化剂进行还原处理,获得所述主催化剂;其中,所述去离子水的体积与所述载体的质量的比值等于所述饱和吸水率,所述主催化剂的活性组分的负载量为0.5%-10%。所述进行还原处理步骤中的温度为80-300℃。所述老化的时间至少6小时,干燥的时间至少6小时,焙烧的温度为400-450℃,焙烧的时间为4-8小时。所述焙烧的步骤还包括在管式炉中进行,条件为静态空气、加热升温速率为1-2℃/分钟。
所述主催化剂的活性组分包括铂纳米颗粒、钯纳米颗粒、镍纳米颗粒、钌纳米颗粒、钴纳米颗粒、铑纳米颗粒、铱纳米颗粒、铜纳米颗粒、银纳米颗粒或者金纳米颗粒中的一种或多种组合。所述主催化剂的载体包括硅铝分子筛、氧化硅、氧化铝、氧化锆、碳或者碳化硅中的一种。
以铂纳米颗粒(PtNPs)负载于氧化硅、氧化铝、硅铝分子筛例如β-分子筛和蒙脱石分子筛即K-10分子筛4个载体S为例进行说明主催化剂的制备方法。
(1)活性组分负载到载体上
对氧化硅、氧化铝、β-分子筛、K-10分子筛载体进行饱和吸水率测定,称取1g完全干燥处理后的任一载体的粉末,逐滴加入去离子水,直至粉末表面湿润且无法吸收更多水分,记录吸水量为a ml,即aml/g为各个载体的饱和吸水率。
将bmg例如氯铂酸溶解于c ml去离子水中,配成均一溶液,将d mg上述载体加入上述氯铂酸溶液中搅拌均匀后超声处理15-20分钟。然后,将样品在常温空气中静置老化6小时以上,并于105-110℃干燥6小时以上。
在管式炉中静态空气氛围、温度为450-500℃的条件下焙烧4-6小时,加热升温速率为1-2℃/分钟。得到氧化态PtNPs/S主催化剂。上述a、b、c、d均应满足c/d=a,0.37b/d=0.5%-10%(PtNPs/S主催化剂的活性组分的负载量),其中a为常数。
(2)主催化剂还原活化
将一定量的PtNPs/S催化剂和水加入反应釜中,在2-6Mpa氢气压力、温度为80-300℃条件下还原4-6小时,得到还原态的PtNPs/S主催化剂。其他活性组分如钯纳米颗粒或镍纳米颗粒负载到载体上的过程与铂纳米颗粒负载到载体上的过程相同。
如图2-图3所示,展示了负载量为质量分数为5%的PtNPs/SiO2主催化剂的透射电子显微镜图(TEM)。
具体的,在步骤S2中,将所述混合体系在还原性气体氛围中进行水热反应,获得所述丙二醇,其中,所述助催化剂形成结合在所述主催化剂表面的氢氧化镁,形成有催化活性的主催化剂-助催化剂复合催化剂。例如,在釜式反应器中,充入氢气,在反应温度为140℃-250℃、反应时间为0.5小时-6小时、氢气压力为2-6Mpa、搅拌速率为200-600转/分的条件下进行反应。
以釜式反应器为例说明步骤S2中的反应过程,所述助催化剂包括氧化镁或者氢氧化镁,在釜式反应器中,氧化镁或者氢氧化镁在反应过程中均会在所述主催化剂表面形成氢氧化镁笼状包覆结构,形成主催化剂-助催化剂复合催化剂,所述主催化剂-助催化剂复合催化剂对反应起催化作用。具体的,将上述主催化剂与助催化剂例如氧化镁的粉末加入到釜式反应器中,在反应进行的同时氧化镁原位发生水解、重组、水热包覆。水热包覆的温度、搅拌速率均与混合体系的条件一致,温度为140℃-250℃,转速为200-600转/分。如图3所示,展示了主催化剂表面笼状包覆有氢氧化镁Mg(OH)2外壳的结构。
下面以一些实施例来具体说明本发明。釜式反应器以不锈钢反应釜为例进行说明。
实施例1
质量分数为5%-10%(以MgO计)氢氧化镁原位水热负载的过程包括,将200mg还原态PtNPs/SiO2、10mg轻质氧化镁粉末、112.5mg例如葡萄糖和10ml去离子水加入到例如50ml容积的不锈钢反应釜中密封。将进气阀打开,充入1Mpa氢气,再将气体放走,反复3次,使反应釜中空气被排空。最后,充入5Mpa氢气,关闭进气、出气阀门。将反应釜加热至180℃进行水热原位负载和反应。搅拌速率为400转/分,反应时间为4小时(以到达180℃开始计时)。反应结束并冷却至室温后,将固体、液体离心分离。液体进行液相色谱和气相色谱分析;固体去离子水清洗三次后进行回用或表征。如图4-图5所示,展示了原位水热负载5wt%氢氧化镁后的复合催化剂的透射电子显微镜图(TEM)。
实施例2
将200mg还原态PtNPs/Al2O3、PtNPs/SiO2、PtNPs/K-10、PtNPs/β-分子筛中的一种,10mg-100mg轻质氧化镁粉末,112.5mg例如葡萄糖和10-20ml去离子水加入到例如50ml容积的不锈钢反应釜中密封。将进气阀打开,充入1Mpa氢气,再将气体放走,反复3次,使反应釜中空气被排空。最后,充入5Mpa氢气,关闭进气、出气阀门。将反应釜加热至180℃进行水热原位负载和反应。搅拌速率为400转/分、反应时间为4小时(以到达180℃开始计时)。反应结束并冷却至室温后,将固体、液体离心分离。液体进行气相色谱分析,获得不同条件下丙二醇的产量,考察不同载体主催化剂-氢氧化镁助催化剂复合材料对葡萄糖氢解产丙二醇的影响,如图6所示。
实施例3
将200mg还原态PtNPs/SiO2,一定量的轻质氧化镁粉末例如0mg、5mg、10mg、15mg、20mg、25mg、50mg、100mg、150mg和200mg,112.5mg例如葡萄糖和10ml去离子水加入到例如50ml容积的不锈钢反应釜中密封。将进气阀打开,充入1Mpa氢气,再将气体放走,反复3次,使反应釜中空气被排空。最后,充入5Mpa氢气,关闭进气、出气阀门。将反应釜加热至180℃进行水热原位负载和反应。搅拌速率为400转/分,反应时间为4小时(以到达180℃开始计时)。反应结束并冷却至室温后,将样品离心分离,获得液体,将液体用甲醇溶剂中稀释25倍,进行气相色谱测试,获得不同条件下丙二醇的产量,考察不同助催化剂使用量对葡萄糖催化氢解产丙二醇的影响,如图7所示,当MgO投加量为10mg时,丙二醇产率为最大,达到53%。此外,以钯纳米颗粒、镍纳米颗粒、钌纳米颗粒、钴纳米颗粒、铑纳米颗粒、铱纳米颗粒、铜纳米颗粒、银纳米颗粒或者金纳米颗粒替代铂纳米颗粒,进行以上过程,可获得丙二醇产率分别为42.5%、46.2%、41.7%、19.5%、29.8%、32.6%、49.9%、22.8%、29.7%。
实施例4
将112.5mg葡萄糖、果糖、纤维素或甘露醇中的一种,200mg还原态PtNPs/SiO2,10mg轻质氧化镁粉末和10ml去离子水加入到例如50ml容积的不锈钢反应釜中密封,将进气阀打开,充入1Mpa氢气,再将气体放走,反复3次,使反应釜中空气被排空。最后,充入5Mpa氢气,关闭进气、出气阀门。将反应釜加热至160℃-300℃进行水热原位负载和反应。搅拌速率为200-600转/分,反应时间为0.5-6小时(以到达160℃-300℃开始计时)。反应结束并冷却至室温后,将样品离心分离,获得液体,将液体用甲醇溶剂中稀释25倍,进行气相色谱测试,获得不同条件下丙二醇的产量,考察不同糖类生物质催化效果,结果表明,葡萄糖在该条件下产丙二醇的产率为53.8%,果糖在该条件下产丙二醇的产率为52.2%,纤维素在该条件下产丙二醇的产率为39.6%,甘露醇在该条件下产丙二醇的产率为27.9%。
实施例5
将200mg还原态PtNPs/SiO2,10mg的例如氧化铍BeO、氧化镁MgO、氧化钙CaO、氧化锡SrO、氧化钡BaO、氢氧化铍Be(OH)2、氢氧化镁Mg(OH)2、氢氧化钙Ca(OH)2、氢氧化锡Sr(OH)2、氢氧化钡Ba(OH)2、氢氧化钠NaOH或氢氧化钾KOH中的一种,112.5mg例如葡萄糖和10ml去离子水加入到例如50ml容积的不锈钢反应釜中密封,将进气阀打开,充入1Mpa氢气,再将气体放走,反复3次,使反应釜中空气被排空。最后,充入5Mpa氢气,关闭进气、出气阀门。将反应釜加热至160℃-300℃进行水热原位负载和反应。搅拌速率为200-600转/分,反应时间为0.5-6小时(以到达160℃-300℃开始计时)。反应结束并冷却至室温后,将样品离心分离后,获得液体,将液体用甲醇溶剂中稀释25倍,进行气相色谱测试,获得不同条件下丙二醇的产量,考察不同氧化物和氢氧化物对葡萄糖催化氢解产丙二醇的影响。如图8所示,当MgO或氢氧化镁作为助催化剂时,获得了较高的丙二醇产率,其他氧化物或者氢氧化物与空白组比较,均不能获得较好的丙二醇产率,当MgO或氢氧化镁作为助催化剂时起作用的是MgO在水热条件下水解、重组后的无定型笼装氢氧化镁。与直接投加Mg(OH)2相比,MgO在水热条件下水解、重组后的氢氧化镁结构更有利于丙二醇的生成。
在釜式反应器中,有无助催化剂对Pt/SiO2催化氢解葡萄糖的反应产物分布的影响,如图9和图10所示,当不加MgO时(见图9),反应产物复杂且副产物量大,而丙二醇的峰面积仅占12.38%;而当加入MgO后(如图10),反应产物及其单一,丙二醇的选择性大大提升,峰面积占到85.74%,副产物种类和量都极具减少。此外,主要副产物1,2-己二醇的产率在加入MgO前后发生了显著改变,从峰面积22.97%下降至3.37%。发现在无MgO条件下,1,2-己二醇主要来自甘露醇,而在加入MgO后,甘露醇主要的反应产物为丙二醇,而不是1,2-己二醇。
在釜式反应器中,本发明的主催化剂和助催化剂形成一种复合催化剂,以铂纳米颗粒为例进行说明,铂纳米颗粒(PtNPs)负载于二氧化硅、β-分子筛等硅铝基载体,并笼状包覆例如氢氧化镁(Mg(OH)2)外壳,简写为Mg-PtNPs/S。所述铂纳米颗粒负载于载体是通过将前驱体例如氯铂酸等体积浸渍于载体中,并进行老化、干燥和焙烧;所述笼状包覆氢氧化镁外壳是通过在反应体系中加入氧化镁,在反应进行的同时原位进行水热包覆负载。通过使用该催化剂,糖类生物质可以定向转化为丙二醇。该催化剂合成方法简单,并可以实现助催化剂例如氢氧化镁的原位负载,充分利用例如助催化剂笼状氢氧化镁的催化活性,将糖类生物质转化为丙二醇产率大幅提升。
在釜式反应器中,本发明中助催化剂例如氢氧化镁或氧化镁在反应过程中实现原位水热包覆,具有操作便利、原位进行水热负载后直接参与反应、避免常规负载方式带来的多次焙烧的问题、避免影响原有催化剂的性能、原位负载可以形成笼状结构的氢氧化镁外壳,氢氧化镁外壳具有结构疏松、具有间隙以及不阻碍反应物进入催化剂内部进行催化反应等优势。本发明所述方法与传统石油化工途径相比,具有绿色、可持续、环境友好等优势,能够实现糖类生物质定向转化为丙二醇,为丙二醇生产的工业化新路径提供技术支持。
本发明的催化剂有良好的回用效果,例如,将本发明在釜式反应器中合成的Mg-PtNPs/SiO2催化剂与其他三种常用传统方法合成的催化剂进行回用对比。如图11所示,展示了用不同方法合成的催化剂在三次回用过程中丙二醇产率和催化剂中金属含量的变化,图中,Mg-PtNPs/SiO2为本发明所述方法;Mg-Pt/SiO2(CI)为醋酸镁、氯铂酸同时浸渍于SiO2载体;Mg-Pt/SiO2(PtF)是指氯铂酸先浸渍,焙烧后再浸渍醋酸镁;Mg-Pt/SiO2(MgF)是指醋酸镁先浸渍,焙烧后再浸渍氯铂酸,本发明合成的复合催化剂三次回用后丙二醇的产率依然保持在较高水平,而其他方法合成的各有劣势,主要原因是本发明合成的复合催化剂在回用中金属流失少,Pt元素损失最小,这是由于助催化剂例如氢氧化镁笼装结构能够在回用中给Pt纳米颗粒约束,使其较难脱离催化剂。
在固定床反应器中,本发明中的助催化剂会形成氢氧化镁结构与所述主催化剂进行结合,形成有催化活性的主催化剂-助催化剂复合催化剂。所述固定床反应器中的空速包括0.12h-1至0.96h-1。在所述固定床反应器中,所述糖类包括葡萄糖、果糖、山梨糖、甘露糖、木糖、山梨醇、甘露醇以及木糖醇中的一种或多种组合。
在一实施例中,在固定床反应器中,将5gPt/SiO2和0.25g氧化镁粉末混合压制成颗粒,填入固定床反应器中,空速为0.12h-1,反应温度为180℃,5wt%葡萄糖溶液,H2与葡萄糖之间的摩尔比为22.6:1。稳定运行200小时以上,转化率保持在90%以上,1,2-丙二醇选择性保持在50%以上。见图12。
此外应理解,本发明中提到的一个或多个方法步骤并不排斥在所述组合步骤前后还可以存在其他方法步骤或在这些明确提到的步骤之间还可以插入其他方法步骤,除非另有说明;还应理解,本发明中提到的一个或多个设备/装置之间的组合连接关系并不排斥在所述组合设备/装置前后还可以存在其他设备/装置或在这些明确提到的两个设备/装置之间还可以插入其他设备/装置,除非另有说明。而且,除非另有说明,各方法步骤的编号仅为鉴别各方法步骤的便利工具,而非为限制各方法步骤的排列次序或限定本发明可实施的范围,其相对关系的改变或调整,在无实质变更技术内容的情况下,当亦视为本发明可实施的范畴。
上述实施例仅例示性说明本发明的原理及其功效,而非用于限制本发明。任何熟悉此技术的人士皆可在不违背本发明的精神及范畴下,对上述实施例进行修饰或改变。因此,举凡所属技术领域中具有通常知识者在未脱离本发明所揭示的精神与技术思想下所完成的一切等效修饰或改变,仍应由本发明的权利要求所涵盖。
Claims (2)
1.一种丙二醇的制备方法,其特征在于,所述制备方法至少包括如下步骤,
将糖类、主催化剂和助催化剂在反应器中形成混合体系;
将所述混合体系在还原性气体氛围中进行水热反应,获得所述丙二醇,其中,所述助催化剂形成结合在所述主催化剂表面的氢氧化镁,形成有催化活性的主催化剂-助催化剂复合催化剂;
其中,所述主催化剂的活性组分包括铂纳米颗粒、钯纳米颗粒、镍纳米颗 粒、钌纳米颗粒、钴纳米颗粒、铑纳米颗粒、铱纳米颗粒、铜纳米颗粒、银纳米颗粒或者金纳米颗粒中的一种或多种组合;所述主催化剂的载体包括硅铝分子筛、氧化硅、氧化铝、氧化锆、碳或者碳化硅中的一种;所述反应器为釜式反应器;在所述釜式反应器中,所述糖类包括葡萄糖、果糖、山梨糖、甘露糖、木糖、山梨醇、甘露醇、淀粉以及纤维素中的一种或多种组合;所述助催化剂包括氧化镁或者氢氧化镁,在釜式反应器中,氧化镁或者氢氧化镁在反应过程中均会在所述主催化剂表面形成氢氧化镁笼状包覆结构,形成主催化剂-助催化剂复合催化剂;当助催化剂为氧化镁时,所述笼状包覆氢氧化镁外壳,是通过在反应进行的同时原位进行水热包覆负载获得;
其中,在所述釜式反应器中,所述助催化剂的用量包括0.5-2mg/mL,所述主催化剂与所述助催化剂的质量比包括10-40:1。
2.根据权利要求1所述的制备方法,其特征在于,所述进行水热反应步骤中的温度为140℃-250℃,所述还原性气体氛围的压力包括2-6MPa。
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