CN116139910A - 一种镍基再羟基化硅基催化剂的新用途 - Google Patents
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Abstract
本发明公开一种镍基再羟基化硅基催化剂在甲烷干重整制备合成气中的应用；所述镍基再羟基化硅基催化剂是将硅基载体置于体积浓度2%‑10%的过氧化氢溶液中，室温浸泡处理10‑15h，固液分离后，固体用去离子水清洗至洗液为中性，干燥获得硅基‑OH载体，将硅基‑OH载体研磨筛分后与乙酰丙酮镍混合，混合物置于甲烷干重整设备中在无水空气气氛下原位煅烧，煅烧产物在氢气气氛、700‑800℃下还原处理制得；本发明制得的催化剂活性金属利用率高，抗烧结能力强，在甲烷干重整反应中具有优异的反应活性和稳定性；该催化剂在750℃高温条件下稳定催化反应150h未明显失活，且反应后保持了较小的镍颗粒尺寸，在能源和环境方面具有一定意义和良好的应用前景。
Description
技术领域
本发明属于能源与环境催化剂领域，具体涉及一种镍基再羟基化硅基催化剂在甲烷干重整制备合成气中的应用。
背景技术
甲烷干重整（DRM）是一种非常有前景的反应，它可以将两种主要的温室气体CH4和CO2转化为有价值的合成气CO和H2。产品合成气是一种重要的工业中间体，可优先用于合成有价值的能源化学品，如烯烃、烷烃和液态碳氢化合物。Ni基催化剂具有较高的催化活性和成本效益，是DRM反应的首选催化剂。由于DRM反应是一个强热力学吸热反应，需要在高温下进行。然而，高温不仅促进了Ni纳米颗粒的烧结，而且加速了CH4分解产生积碳。两者都能导致镍基催化剂的快速失活。为了避免烧结和结焦，分散性良好的Ni颗粒以及金属-载体的强相互作用被认为是提供高效稳定的DRM催化剂的有效方法。
硅基载体尤其是有序SBA-15材料被认为是Ni纳米颗粒的理想载体，它能提供高比表面积和丰富孔道结构可以约束效应抑制金属颗粒聚集。虽然目前在这一领域进行了大量的研究，但这种催化剂的制备仍然具有挑战性。Ni/SBA-15催化剂的制备通常采用镍水溶液浸渍载体的方法。然而，此方法会让部分镍颗粒会沉积在二氧化硅的外表面，容易聚集。因此，如果使用简单浸渍，浸渍后的催化剂在高温煅烧以及反应条件下，金属很容易发生镍烧结，导致催化剂失活。
发明内容
针对现有技术存在的不足，本发明提供了一种镍基再羟基化硅基催化剂的新用途，即其在甲烷干重整制备合成气中的应用，所述镍基再羟基化硅基催化剂是将硅基载体置于体积浓度2%-10%的过氧化氢溶液中，在室温浸泡处理10-15h，固液分离后，固体用去离子水清洗至洗液为中性，干燥获得硅基-OH载体，将硅基-OH载体研磨筛分后与乙酰丙酮镍混合，混合物放入反应设备中通入无水空气原位煅烧，煅烧产物在氢气气氛、700-800℃下还原处理制得镍基再羟基化硅基催化剂；本发明中镍通过气相扩散的方法并在羟基的作用下均匀地分布在硅基-OH表面以及孔道内，在150h的甲烷干重整性能测试中，镍基再羟基化硅基催化剂显示了高DRM转化率和出色的DRM稳定性；
所述乙酰丙酮镍和硅基-OH载体的质量比为0.05-0.3:1。
所述煅烧是以10℃/min的升温速率升温至300-500℃保持1-3h后降至室温，煅烧过程中是以8-12mL/min的流速持续通入无水空气条件下进行。
所述硅基载体选自SBA-15、SiO2、MCM-41，为市售产品或按常规方法制得的试剂。
与现有技术相比，本发明具有以下有益效果：
1、催化剂制备方法简单易行，可重复性高，硅基载体经过再羟基化处理后再通过混合负载活性金属镍即可制得高性能甲烷干重整催化剂；
2、本发明催化剂较好地解决了目前甲烷干重整反应当中催化剂烧结失活，转化速率低等问题，通过再羟基化处理后制备的高性能镍基再羟基化硅基催化剂在甲烷干重整反应中取得了较高的催化活性和超长的稳定性，与现有文献相比处于较高水平；
3、催化剂制备成本较低，适用于工业化生产和市场推广应用。
附图说明
图1为实施例1不同方法制得的催化剂进行甲烷干重整反应的甲烷转化率结果（a图）和二氧化碳转化率结果（b图）；
图2为实施例1不同方法制得的催化剂进行甲烷干重整反应的H2/CO结果示意图；
图3为实施例1不同方法制得的催化剂的H2-TPR谱图；
图4为实施例1不同方法制得的催化剂的H2-化学吸附计算出的镍分散度（a图）和镍颗粒尺寸（b图）；
图5为实施例2的催化剂5Ni/SBA15-OH的甲烷和二氧化碳转化率结果；
图6为实施例2的催化剂5Ni/SBA15-OH的H2/CO结果示意图。
具体实施方式
下面通过实施例对本发明作进一步详细说明，但本发明保护范围不局限于所述内容，实施例中方法如无特殊说明均为常规方法，试剂如无特殊说明均为常规试剂或按常规方法配制的试剂；
下述实施例中SBA15是将24g Pluronic P123三嵌段聚合物（PEO-PPO-PEO，Aldrich）溶解在蒸馏水（650 mL）和盐酸（140 mL）混合液中，在室温下搅拌30min，直到P123完全溶解，接着，在持续搅拌的情况下一滴一滴地加入55mL正硅酸四乙酯（TEOS），并继续搅拌24h；然后，放入90℃的烘箱中晶化24h，将反应产物过滤、洗涤，并在80℃下干燥24h，最后以1℃/min的速率升温至550 ℃并焙烧6 h制得；
实施例1
1、将5g的SBA15置于2%过氧化氢溶液100mL中，在室温浸泡处理12h后，固液分离，固体去离子水洗涤至洗液为中性后，在室温下干燥12h制得SBA15-OH载体，并将SBA15-OH研磨筛分至40-60目；称取0.11g乙酰丙酮镍，加入1g筛分后的SBA15-OH载体，混合均匀；取0.1g混合物置于反应炉的石英管中心，在无水空气气氛下（10mL/min的流速持续通入）以10℃/min的升温速率升至300℃并保持120min，最后在氮气气氛下以10℃/min的升温速率加热至750℃，用含10%H2的氩气还原预处理1h，制得镍基再羟基化SBA15催化剂（Ni/SBA15-OH）；
同时制备Ni/SBA15催化剂、Ni/SBA15-IWI催化剂作为对照；
其中Ni/SBA15催化剂是将普通SBA15研磨筛分至40-60目；称取0.11g乙酰丙酮镍，加入1g筛分后的SBA15载体，混合均匀；取0.1g混合物置于反应炉的石英管中心，以10 ℃/min的升温速率升至300℃并保持120min，即得催化剂Ni/SBA15；
Ni/SBA15-IWI催化剂是称取0.13g六水合硝酸镍溶于2mL去离子水中，然后加入1g普通SBA15，用玻璃棒搅拌30min，固体在80℃下干燥12h，产物置于马弗炉中，以10℃/min的升温速率升至500℃并保持360min，研磨筛分至40-60目制得；
2、镍基再羟基化SBA15催化剂的应用
（1）在石英管内合成镍基再羟基化SBA15催化剂后，以60mL/min的流速将甲烷-二氧化碳-氮气混合气（CH4:CO2:N2=1:1:1）通入反应器中的石英管内，在750 ℃、反应压力0.1M Pa，反应空速36000mL/g/h条件下进行甲烷干重整制备合成气，每隔2h取样，总反应时间是150h；用气相色谱仪器FID、TCD测量出CH4、CO2、H2、CO的峰面积，对其数据进行处理，计算转化率及H2/CO比值；
结果见图1、2，从图1、2中可以看出Ni/SBA15-OH催化剂在甲烷重整中，CH4和CO2的初始转化率分别达到了88%和96%，并且在150h的长时间反应中没有明显的失活，在150h时CH4和CO2分别下降了2.8%、2.0%，本发明催化剂具有稳定的催化活性，说明小颗粒，高分散的镍对催化性能起到了重要作用；Ni/SBA15-OH催化剂的初始H2/CO接近1，说明在反应过程中基本没有副反应的发生；
普通SBA15作为载体的催化剂（Ni/SBA15）的CH4和CO2的转化率明显低于Ni/SBA15-OH催化剂，初始转化率分别为73.2%和82.8%，且在100h的反应中出现了相对较快的失活，在100h时CH4和CO2分别下降了7.7%、7.3%，初始H2/CO也较低，为0.91；浸渍法的Ni/SBA15-IWI催化剂的CH4 和CO2 的初始转化率分别为78.8%和86.9%，在100h时CH4和CO2分别下降了24.6%、24.1%，发生了严重的失活，说明其表面镍是不稳定的，其初始H2/CO为0.93，随着时间增加H2/CO下降也较快。
（2）H2-TPR实验
采用天津鹏翔PX200吸附仪进行H2-TPR实验，通过该实验探索金属载体的作用力，吸附仪配备热导检测器(TCD)，将50mg催化剂放在U型管中的石英棉之间，在150℃下采用氩气 (30mL/min)预处理1小时，以去除物理吸附的水；然后将催化剂冷却至50℃后，以10℃/min的加热速率从50℃升温至800℃，同时以30mL/min流速通入含10% H2的氩气，同时记录TCD信号变化数据。
结果见图3，从图中可以看出Ni/SBA15催化剂和Ni/SBA15-IWI催化剂的还原温度都较低，主峰位置分别为350℃和338℃，这说明普通未经处理的SBA15载体与镍相互作用较弱，无法保证镍的稳定。Ni/SBA15-IWI在383℃出现还原峰，这证明本发明Ni/SBA15-OH催化剂具有更强的的金属-载体相互作用力，并且在383℃处还原峰面积要大于Ni/SBA15催化剂和Ni/SBA15-IWI催化剂，这些都意味着Ni/SBA15-OH催化剂上镍与载体作用力更强，分散性更好；
（3）H2化学吸附实验
为了获得催化剂表面活性Ni分散程度和平均粒径等信息，在天津鹏翔PX200吸附仪上对实施例1中不同方法制得的催化剂进行了H2化学吸附实验，实验前，100mg催化剂在U形管中以10% H2/Ar (30 mL/min)在750℃下还原1 h，得到金属Ni，在此温度下用Ar纯化1h，冷却至50℃。随后持续脉冲H2流，直至吸附饱和，脉冲峰面积保持不变。
通过数据处理得到的镍分散度和镍颗粒尺寸如图4所示，图4a的镍颗粒分散度柱状图可以看到三种催化剂Ni/SBA15-OH、Ni/SBA15和Ni/SBA15-IWI的镍分散度分别为37.2%、19.6 %和12.1%，图4b三种催化剂Ni/SBA15-OH、Ni/SBA15和Ni/SBA15-IWI的镍颗粒尺寸信息也符合规律，分别为2.2 nm、3.9nm和6.6nm，这些现象都说明了通过气象扩散的方法在再羟基化的SBA15上负载镍，可以促进镍的分散，形成小的镍颗粒，从而增强甲烷重整的性能。
实施例2
1、将5g的SBA15置于2%的100mL过氧化氢溶液中，在室温浸泡处理12h后，固液分离，固体去离子水洗涤至洗液为中性后，在室温下干燥12h制得SBA15-OH载体，并将SBA15-OH研磨筛分至40-60目；称取0.22g乙酰丙酮镍，加入1g筛分后的SBA15-OH载体，混合均匀；取0.1g混合物置于反应炉的石英管中心，以10mL/min的流速持续通入无水空气条件下，同时以10℃/min的升温速率升至300℃并保持120min，然后在氮气气氛下以10℃/min的升温速率加热至750℃，最后用含10%H2的氩气还原预处理1h，获得镍基再羟基化SBA15催化剂（5Ni/SBA15-OH）；
2、镍基再羟基化SBA15催化剂的应用
在石英管内合成镍基再羟基化SBA15催化剂后，以60mL/min的流速将甲烷-二氧化碳-氮气混合气（CH4:CO2:N2=1:1:1）通入反应器中的石英管内，在750℃、反应压力0.1M Pa，反应空速36000mL/g/h条件下进行甲烷干重整制备合成气，每隔2h取样，总反应时间是20h；用气相色谱仪器FID、TCD测量出CH4、CO2、H2、CO的峰面积，对其数据进行处理，计算转化率及H2/CO比值；结果见图5，从图5中可以看出5Ni/SBA15-OH催化剂在甲烷重整中表现较好的催化性能，CH4和CO2的初始转化率分别达到了91%和96%，并且在20h的反应中没有任何的下降趋势，从图6中可以看出5Ni/SBA15-OH的H2/CO达到了1，基本没有副反应的发生，这也证明了在高的金属负载量下，通过气相扩散法在再羟基化的SBA15上负载镍仍然可以制得分散均匀的镍，并保持稳定的催化活性。
Claims (4)
1.一种镍基再羟基化硅基催化剂在甲烷干重整制备合成气中的应用；
所述镍基再羟基化硅基催化剂是将硅基载体置于体积浓度2%-10%的过氧化氢溶液中，室温浸泡处理10-15h，固液分离后，固体用去离子水清洗至洗液为中性，干燥获得硅基-OH载体，将硅基-OH载体研磨筛分后与乙酰丙酮镍混合，混合物置于甲烷干重整设备中在无水空气气氛下原位煅烧，煅烧产物在氢气气氛、700-800℃下还原处理制得；
催化剂制得后原位进行甲烷干重整制备合成气。
2.根据权利要求1所述应用，其特征在于：乙酰丙酮镍和硅基-OH载体的质量比为0.05-0.3:1。
3.根据权利要求1所述应用，其特征在于：煅烧是在300-500℃下处理1-3h后，降至室温，煅烧过程中无水空气以8-12mL/min的流速持续通入。
4.根据权利要求1所述应用，其特征在于：硅基载体选自SBA-15、SiO2、MCM-41。
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