CN110961109A - 一种超声-微波协同辅助制备Ni-Al2O3催化剂的方法及其在CO2加氢中的应用 - Google Patents
一种超声-微波协同辅助制备Ni-Al2O3催化剂的方法及其在CO2加氢中的应用 Download PDFInfo
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Abstract
本发明公开了一种超声‑微波协同辅助制备Ni‑Al2O3催化剂的方法及其在CO2加氢中的应用。该方法将Ni(NO3)2·6H2O、γ‑Al2O3和PVP混合加入60mL去离子水并搅拌均匀,然后转移至100 mL反应釜,将釜置于微波超声组合反应器中,设定微波功率为400‑600 W,超声波功率为800‑1000W,温度为120‑150℃,在自生压力下恒温反应15‑30 min;冷却后,再进行离心、干燥,煅烧后,H2气氛中还原,得到Ni‑Al2O3催化剂;本发明解决了浸渍法制备催化剂时反应时间长和活性组分分散不均的问题,能够有效提高催化剂的分散性及其在CO2加氢反应中的活性。
Description
技术领域
本发明属于CO2催化技术领域,特别涉及一种超声-微波协同辅助制备Ni-Al2O3催化剂的方法及其在CO2加氢中的应用。
背景技术
近几十年来,CO2排放引起的全球变暖引起广泛的关注,CO2催化加氢制甲烷能同时实现碳减排和燃料转化,成为研究热点,开发高效、廉价的催化剂是实现其工业化的关键。在众多催化剂中,贵金属催化剂积碳少、活性高,然而高成本限制了其应用。Ni-Al2O3催化剂作为典型的非贵金属催化剂,具有强度高、成本低和和活性好等优点,在CO2甲烷化反应中表现出良好的前景。浸渍法制备的Ni-Al2O3催化剂通常存在活性组分分散性较差的问题,严重影响其催化性能。借助辅助技术改进催化剂制备方法可以有效地实现活性组分的高分散负载。
研究表明,超声波和微波技术可以提高活性组分在载体表面的分散效果,从而提高催化剂的活性。在催化剂制备过程中,超声产生的微环境能够促进界面间的反应、传质和传热过程,微波产生的高频变换能量场可以是分子由无需运动变为有序的高频运动,通过将分子动能转换成热能来实现加热,其特殊的加热方式可极大地缩短反应时间,同时也能改善活性组分的分散性。超声-微波组合技术将两者无干扰结合,实现了两者的协同处理,被广泛用于萃取以及纳米材料合成领域,在催化剂制备和活性组分负载中的研究报道较少。
申请号201810111083.X 公开了一种负载型臭氧高级氧化催化剂的制备方法,包括以下步骤:S1.选取γ-Al2O3球体为载体;S2.将硝酸镍与去离子水混合搅拌得到稳定硝酸镍溶液,将硝酸铜与去离子水混合搅拌得到稳定硝酸铜溶液,所述硝酸镍与硝酸铜的质量比为1-9:1;S3.将步骤S2配制好的硝酸镍溶液和硝酸铜溶液与步骤S1选取的载体混合,并持续摇晃震荡4-8h;S4.滤去步骤S3浸渍后的浸渍液后干燥;S5.将步骤S4制备得到的γ-Al2O3球体以恒定的升温速率恒温焙烧,得到以γ-Al2O3球体为载体,NiO和CuO为活性组分的负载型臭氧高级氧化催化剂。本发明的臭氧高级氧化催化剂同时具有吸附和活化协同作用,既能高效吸附水中有机污染物,同时又能催化活化臭氧分子,取得很好的催化臭氧氧化效果。
申请号201610953960.9公开了一种CeO2 ,NiO-ZSM-5/γ- Al2O3催化剂制备,硝酸镍,硝酸铈,异丙醇铝,氢氧化钠 ,无水乙醇,硅溶胶,三乙胺等主要原料来合成,并通过,磁力,氦气氛围,等特殊操作改性制得CeO2 ,NiO-ZSM-5/γ-Al2O3脱硫脱硝催化剂。制得的催化剂脱硫脱硝效果好,且再生效果好。
虽然上述两件现有技术,在催化剂成分相似,制备方法不同,均存在反应时间长,活性组分分布不均匀的问题。
发明内容
针对现有技术的不足,本发明的目的在于提供一种超声-微波协同辅助制备Ni-Al2O3催化剂的方法及其在CO2加氢中的应用,以解决现有浸渍法存在的反应时间长和活性组分分散不均匀的问题,是一种高效的制备方法,能够有效提高催化剂的分散性及其在CO2加氢反应中的活性。
为实现上述目的,本发明采用的技术方案为:
一种超声-微波协同辅助制备Ni-Al2O3催化剂的方法,包括以下步骤:
步骤1,将Ni(NO3)2·6H2O、γ-Al2O3和PVP按照加入60mL去离子水,搅拌均匀后,转移至100 mL聚四氟乙烯反应釜中;
步骤2,将步骤1中的反应釜转移至微波超声组合反应器中,设定微波功率为400-600W,超声波功率为800-1000W,温度为120-150℃,在自生压力下恒温反应15-30 min;
步骤3,将步骤2的反应产物冷却至室温后,对产物进行离心、干燥,400-500℃煅烧4 h,得到前驱体NiO-Al2O3;
步骤4,将前驱体NiO-Al2O3在H2/N2混合气体的气氛中400℃还原,得到高分散的Ni-Al2O3催化剂。
作为改进的是,所述步骤1中Ni(NO3)2·6H2O、γ-Al2O3按照Ni: γ-Al2O3 = 10%-30 wt%进行混合,倒入内部设置压力传感器的聚四氟乙烯反应釜中,加入60 mL、0.1 mol/L的PVP溶液,然后磁力搅拌5 min。
作为改进的是,所述步骤3中煅烧时升温速率设置为2℃/min,避免温度飙升引起活性组分团聚。
所述步骤4中对催化剂前驱体NiO-Al2O3进行还原时,需采用H2/N2混合气体在400℃进行处理,还原时间为30-60 min,所述H2/N2混合气体中体积比为20/30。
上述方法制备的Ni-Al2O3催化剂在CO2加氢中的应用。
有益效果:
与现有技术相比,本发明一种超声-微波协同辅助制备Ni-Al2O3催化剂的方法及其在CO2加氢中的应用,该催化剂通过采用超声-微波反应器和添加PVP分散剂进行制备,通过两者的协同作用,减少浸渍法中Ni的负载时间。采用表面活性剂聚乙烯吡咯烷酮(PVP)来提高活性组分Ni在载体表面的分散性,选择具有高的介电损耗因子(δ)的蒸馏水作为溶剂,以便于微波加热。与浸渍法相比,大大缩短了时间,同时有效提高了Ni-Al2O3催化剂表面活性组分Ni的分散性及其在CO2加氢反应中的催化活性。
附图说明
图1为不同方法制备的Ni-Al2O3催化剂的SEM形貌图,其中,(a)为20%Ni/Al2O3-CW,(b)为20%Ni/Al2O3-JZ。
具体实施方式
下面结合附图和具体实施例对本发明作进一步描述。
实施例1
一种超声-微波协同辅助制备Ni-Al2O3催化剂的方法,包括以下步骤:
(1)将Ni(NO3)2·6H2O、γ-Al2O3和PVP按照一定比例加入60mL去离子水中,其中,Ni(NO3)2·6H2O、γ-Al2O3按照Ni: γ-Al2O3 = 10% wt%进行混合,PVP的浓度为0.1 mol/L,然后磁力搅拌5 min,将溶液转移至100 mL设置压力传感器的聚四氟乙烯反应釜;
(2)将步骤(1)中反应釜转移至微波超声组合反应器中,在此之前检查反应釜内部垫片的完整性,设定微波功率为500 W,超声波功率为800W,温度为130℃,在自生压力下恒温反应20min;
(3)步骤(2)反应结束后,待釜内温度冷却至室温方可从微波超声组合反应器取出,将产物从反应釜内取出,进行离心、干燥,450 °C煅烧4 h,得到催化剂的前驱体NiO-Al2O3;
(4)将步骤(3)得到的催化剂前驱体NiO-Al2O3在H2/N2 (20/30, v/v)混合气氛中和400℃下还原30-60 min,得到高分散的Ni-Al2O3催化剂,标记为10%Ni/Al2O3-CW,其中“10%”代表Ni的负载量,“CW”代表采用的制备方法为超声-微波协同辅助法。
实施例2
(1)将Ni(NO3)2·6H2O、γ-Al2O3和PVP按照一定比例加入60mL去离子水中,其中Ni(NO3)2·6H2O、γ-Al2O3按照Ni: γ-Al2O3 = 20% wt%进行混合,PVP的浓度为0.1 mol/L,然后磁力搅拌5 min,将溶液转移至100 mL设置压力传感器的聚四氟乙烯反应釜;
(2)将步骤(1)中反应釜转移至微波超声组合反应器中,在此之前检查反应釜内部垫片的完整性,设定微波功率为400-600 W,超声波功率为1000W,温度为120℃,在自生压力下恒温反应30 min;
(3)步骤(2)反应结束后,待釜内温度冷却至室温方可从微波超声组合反应器取出,将产物从反应釜内取出,进行离心、干燥,450℃煅烧4h,得到催化剂的前驱体NiO-Al2O3;
(4)将步骤(3)得到的催化剂前驱体NiO-Al2O3在H2/N2 (20/30, v/v)混合气氛中和400℃下还原30-60 min,得到高分散的Ni-Al2O3催化剂,标记为20%Ni/Al2O3-CW,其中“20%”代表Ni的负载量,“CW”代表采用的制备方法为超声-微波协同辅助法。
实施例3
(1)将Ni(NO3)2·6H2O、γ-Al2O3和PVP按照一定比例加入60mL去离子水中,其中Ni(NO3)2·6H2O、γ-Al2O3按照Ni: γ-Al2O3 = 30% wt%进行混合,PVP的浓度为0.1 mol/L,然后磁力搅拌5 min,将溶液转移至100 mL设置压力传感器的聚四氟乙烯反应釜;
(2)将步骤(1)中反应釜转移至微波超声组合反应器中,在此之前检查反应釜内部垫片的完整性,设定微波功率为600W,超声波功率为1000W,温度为120℃,在自生压力下恒温反应30 min;
(3)步骤(2)反应结束后,待釜内温度冷却450℃煅烧4 h,得到催化剂的前驱体NiO-Al2O3;
(4)将步骤(3)得到的催化剂前驱体NiO-Al2O3在H2/N2 (20/30, v/v)混合气氛中和400℃下还原30-60 min,得到高分散的Ni-Al2O3催化剂,标记为30%Ni/Al2O3-CW,其中“30%”代表Ni的负载量,“CW”代表采用的制备方法为超声-微波协同辅助法。
对比例1
(1)将Ni(NO3)2·6H2O、γ-Al2O3和PVP按照一定比例加入60mL去离子水中,其中Ni(NO3)2·6H2O、γ-Al2O3按照Ni: γ-Al2O3 = 10% wt%进行混合,将混合物转移至坩埚中,然后磁力搅拌5 min;
(2)将步骤(1)中的坩埚转移至水浴锅中,在60℃恒温条件下磁力搅拌作用6 h;
(3)步骤(2)反应结束后,将坩埚从水浴锅转移至干燥箱中干燥,然后在450℃煅烧4 h,得到催化剂的前驱体NiO-Al2O3;
(4)将步骤(3)得到的催化剂前驱体NiO-Al2O3在H2/N2 (20/30, v/v)混合气氛中和400℃下还原30-60 min,得到Ni-Al2O3催化剂,标记为10%Ni/Al2O3-JZ,其中“10%”代表Ni的负载量,“JZ”代表采用的制备方法为浸渍法。
对比例2
(1)将Ni(NO3)2·6H2O、γ-Al2O3和PVP按照一定比例加入60mL去离子水中,其中Ni(NO3)2·6H2O、γ-Al2O3按照Ni: γ-Al2O3 = 20% wt%进行混合,将混合物转移至坩埚中,然后磁力搅拌5 min;
(2)将步骤(1)中的坩埚转移至水浴锅中,在60℃恒温条件下磁力搅拌作用6 h;
(3)步骤(2)反应结束后,将坩埚从水浴锅转移至干燥箱中干燥,然后在450℃煅烧4 h,得到催化剂的前驱体NiO-Al2O3;
(4)将步骤(3)得到的催化剂前驱体NiO-Al2O3在H2/N2 (20/30, v/v)混合气氛中和400℃下还原30-60 min,得到Ni-Al2O3催化剂,标记为20%Ni/Al2O3-JZ,其中“20%”代表Ni的负载量,“JZ”代表采用的制备方法为浸渍法。
对比例3
(1)将Ni(NO3)2·6H2O、γ-Al2O3和PVP按照一定比例加入60mL去离子水中,其中Ni(NO3)2·6H2O、γ-Al2O3按照Ni: γ-Al2O3 = 30% wt%进行混合,将混合物转移至坩埚中,然后磁力搅拌5 min;
(2)将步骤(1)中的坩埚转移至水浴锅中,在60℃恒温条件下磁力搅拌作用6 h;
(3)步骤(2)反应结束后,将坩埚从水浴锅转移至干燥箱中干燥,然后在400-500℃煅烧4 h,得到催化剂的前驱体NiO-Al2O3;
(4)将步骤(3)得到的催化剂前驱体NiO-Al2O3在H2/N2 (20/30, v/v)混合气氛中和400℃下还原30-60 min,得到Ni-Al2O3催化剂,标记为30%Ni/Al2O3-JZ,其中“30%”代表Ni的负载量,“JZ”代表采用的制备方法为浸渍法。
上述催化剂选取20%Ni/Al2O3-JZ和20%Ni/Al2O3-CW进行测试。采用FEI Quanta250F型扫描电子显微镜测试催化剂的SEM形貌;催化剂的Ni颗粒平均粒径是通过对透射电镜图片中的Ni颗粒粒径进行统计而获得;活性组分Ni的分散性是由H2-TPD测试的H2吸附量、催化剂样品中Ni的质量百分数以及H2-TPR测得的催化剂样品中Ni组分的还原度等进行计算得到的;催化剂的CO2加氢制甲烷的催化性能在固定床反应器上进行评价,管式反应器的内径为5 mm,催化剂装填量1.0 g,反应气为H2 : CO2 : N2 = 4 : 1 : 4的90 mL/min混合气体,空速(GHSV)为4200 mL/h·gcat。
上述实施例制备催化剂的Ni颗粒平均粒径、分散性及其在CO2加氢反应中转化率达到50%时所对应的温度如表1所示:
表1 催化剂的Ni颗粒平均粒径、分散性及其在CO2加氢反应中转化率达到50%时所对应的温度
a转化率达到50%时所对应的温度
由表1可见,20%Ni/Al2O3-JZ和20%Ni/Al2O3-CW的Ni颗粒平均粒径分别为15.3 nm和9.6nm,活性组分Ni的分散性分别为14.8%和27.3%。由此可见,与浸渍法相比,超声-微波辅助制备的Ni-Al2O3催化剂具有更小的Ni颗粒和更高的Ni分散性。因此两种催化剂在CO2加氢反应中转化率达到50%时所对应的温度分别为261℃和223℃,后者在较低温度下的催化性能优于前者。
Claims (5)
1.一种超声-微波协同辅助制备Ni-Al2O3催化剂的方法,其特征在于,包括以下步骤:
步骤1,将Ni(NO3)2·6H2O、γ-Al2O3和PVP按照加入60mL去离子水,搅拌均匀后,转移至100 mL聚四氟乙烯反应釜中;
步骤2,将步骤1中的反应釜转移至微波超声组合反应器中,设定微波功率为400-600W,超声波功率为800-1000W,温度为120-150℃,在自生压力下恒温反应15-30 min;
步骤3,将步骤2的反应产物冷却至室温后,对产物进行离心、干燥,400-500℃煅烧4 h,得到前驱体NiO-Al2O3;
步骤4,将前驱体NiO-Al2O3在H2/N2混合气体的气氛中400 ℃还原,得到高分散的Ni-Al2O3催化剂。
2.根据权利要求1所述的一种超声-微波协同辅助制备Ni-Al2O3催化剂的方法,其特征在于:
所述步骤1中Ni(NO3)2·6H2O、γ-Al2O3按照Ni: γ-Al2O3 = 10%-30 wt%进行混合,倒入内部设置压力传感器的聚四氟乙烯反应釜中,加入60 mL、0.1 mol/L的PVP溶液,然后磁力搅拌5 min。
3.根据权利要求1所述的一种超声-微波协同辅助制备Ni-Al2O3催化剂的方法,其特征在于:步骤3中煅烧时升温速率设置为2℃/min。
4.根据权利要求1所述的一种超声-微波协同辅助制备Ni-Al2O3催化剂的方法,其特征在于:
所述步骤4中对催化剂前驱体NiO-Al2O3进行还原时,需采用H2/N2混合气体在400℃进行处理,还原时间为30-60 min,所述H2/N2混合气体中体积比为20/30。
5.基于权利要求1-4中任一种方法制备得到的一种超声-微波协同辅助制备Ni-Al2O3催化剂在CO2加氢中的应用。
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