CN114950438B - 提高生物质焦油低温重整性能的镍基催化剂的制备方法 - Google Patents
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Abstract
本发明涉及生物质焦油重整催化剂的制备技术领域，具体涉及提高生物质焦油低温重整性能的镍基催化剂的制备方法。具体技术方案为：提高生物质焦油低温重整性能的镍基催化剂的制备方法，以海相页岩固体干酪根为原料，通过提质预处理后，经干燥、研磨、筛分后与六水合硝酸镍溶液混合后制得催化剂前驱体；将催化剂前驱体在氮气氛围下高温煅烧后即得镍基催化剂。本发明解决现有镍基催化剂低温重整焦油性能较差的问题。
Description
技术领域
本发明涉及生物质焦油重整催化剂的制备技术领域，具体涉及提高生物质焦油低温重整性能的镍基催化剂的制备方法。
背景技术
精细化学品、燃料、药物、合成纤维、塑料、化肥等几乎所有人类所需的化学工业品主要源于煤炭、石油和天然气等化石能源，然而这些传统化石能源利用过程带来许多问题，包括污染生态环境、资源匮乏等，因此以可持续发展的新能源替代传统化石能源势在必行。
生物质能是仅次于煤炭、石油、天然气的世界第四大能源，是唯一可再生的碳资源。相对传统化石能源，生物质能具备资源丰富、分布广泛、可再生和碳零排放等优势。采用热解气化技术将丰富的生物质资源转化为清洁燃气，既可为生活生产直接燃用，也可并网发电，具有高效率、低成本和易于规模生产的优点，发展潜力十分广阔。然而，生物质气化过程不可避免产生焦油等副产物，降低气化效率，影响燃气质量。
催化裂解气化可显著降低焦油含量，提高能源转化效率。目前主要研究热点集中于焦油重整催化剂的合成与调控。镍基催化剂以其优异的活化C-C键能力被认为是最具应用潜力的焦油重整催化剂。其载体多为白云石、橄榄石等天然矿石或氧化铝、氧化镁等金属氧化物。然而这类镍基催化剂低温重整焦油性能较差，常采用提高重整温度以提高活性，导致焦油净化能耗过高，严重制约了生物质气化技术的推广应用。
干酪根是沉积岩中不溶非氧化型酸、碱和非极性有机溶剂的分散有机质，是原始有机物质经过生活作用和物化作用改造而成，且是页岩中有机质的主体。干酪根具有丰富的孔隙网络，较高的比表面积以及对有机物优良的吸附性。我国页岩气勘探开发主要集中于上扬子区下古生界龙马溪组页岩。因此，龙马溪组页岩干酪根具有作为催化剂载体的巨大潜质。
发明内容
针对现有技术的不足，本发明提供了一种提高生物质焦油低温重整性能的镍基催化剂的制备方法，以干酪根衍生碳材料负载纳米镍催化剂，解决现有镍基催化剂低温重整焦油性能较差的问题。
为实现以上目的，本发明通过以下技术方案予以实现：
本发明公开了提高生物质焦油低温重整性能的镍基催化剂的制备方法，以海相页岩固体干酪根为原料，通过提质预处理后，经干燥、研磨、筛分后与六水合硝酸镍溶液混合后制得催化剂前驱体；将催化剂前驱体在氮气氛围下高温煅烧后即得镍基催化剂。
优选的，所述海相页岩固体干酪根提质预处理的过程为：在水浴条件下，将海相页岩固体干酪根与硫酸混合搅拌，并用去离子水洗涤至中性，并用纳滤膜过滤以获得提质后的海相页岩固体干酪根。
优选的，在58～62℃的水浴条件下，海相页岩固体干酪根与15％硫酸按质量比1:14～1:15混匀并搅拌10～12h。
优选的，所述六水合硝酸镍溶液的浓度为2.5～5.5mol/L，所述海相页岩固体干酪根与六水合硝酸镍溶液的质量比为1:6～1:8。
优选的，所述催化剂前驱体在450～550℃下煅烧1.5～4h。
相应的，一种镍基催化剂，根据上述制备方法制备的镍基催化剂。
本发明具备以下有益效果：
1.本发明制备的镍基催化剂在500℃重整温度条件下对生物质气化焦油中典型难降解组分萘、蒽等多环芳烃的重整率均＞95％，所得小分子产物中H2体积分数高于60％。
2.本发明方法中以海相页岩固体干酪根为催化剂前驱体，变废为宝，原料成本低。因此，制备的催化剂具有成本低廉、制备方法简单、孔隙结构发达、以及优异的焦油低温重整活性和稳定性等特点。
3.本发明制备的镍基催化剂，可有效提高生物质焦油在低温条件下的重整降解效率，并将其转化为富氢可燃气，既可有效提高燃气热值，又大幅降低气化合成气净化能耗及成本。
附图说明
图1为实施例1制备的镍基催化剂的电镜扫描图；
图2为实施例1制备的镍基催化剂的透射电镜图；
图3为实施例4制备的镍基催化剂的电镜扫描图；
图4为实施例4制备的镍基催化剂的透射电镜图；
图5为实施例5制备的镍基催化剂的电镜扫描图；
图6为实施例5制备的镍基催化剂的透射电镜图。
具体实施方式
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
若未特别指明，实施举例中所用的技术手段为本领域技术人员所熟知的常规手段。
本发明公开了一种提高生物质焦油低温重整性能的镍基催化剂的制备方法，以海相页岩固体干酪根为原料，通过提质预处理后，经干燥、研磨、过100目筛筛分后与2.5～5.5mol/L的六水合硝酸镍溶液混合后制得催化剂前驱体，海相页岩固体干酪根与六水合硝酸镍溶液的质量比为1:6～1:8；将催化剂前驱体在氮气氛围下在450～550℃下煅烧1.5～4h即得镍基催化剂。
具体的：海相页岩固体干酪根原料要求：
a.热演化程度/热成熟度(R0)：1.1～1.4％(等效镜质体反射率分布频率)；
b.平均TOC含量2.0～2.3％；
c.化学成分元素原子比范围：O/C:0.14～0.16；H/C:0.75～0.79；
d.比表面积：4.95～7.58m2/g
海相页岩固体干酪根提质预处理的过程为：在58～62℃(优选为58℃)的水浴条件下，将海相页岩固体干酪根与15％的硫酸混合搅拌10～12h(优选为12h)，以去除碳酸盐和硅酸盐，海相页岩固体干酪根与硫酸的质量比为1:14～1:15(优选为1:15)；然后用去离子水洗涤至中性，并用纳滤膜截留已去除碳酸盐和硅酸盐的样品中的硫酸根以获得提质的海相页岩固体干酪根。
由于干酪根中碳酸盐和硅酸盐煅烧后生成的CaO、SiO2等氧化物会覆盖催化剂孔道结构中的活性位点，从而降低焦油分子在孔道内活性位点的重整反应速率，抑制催化剂低温重整焦油性能。因此，通过上述预处理步骤去除碳酸盐和硅酸盐，可有效提高干酪根前驱体中有机质含量，进而显著增强煅烧后所得镍基催化剂的金属-载体界面相互作用，从而提高镍基催化剂对生物质焦油的低温重整性能。
下面结合具体的实施例对本发明进行进一步的阐述。
实施例1
(1)催化剂前驱体制备：以海相页岩固体干酪根为原料，通过提质预处理后，经干燥、研磨、筛分(100目)处理，进而将其与2.5mol/L浓度的六水合硝酸镍溶液按质量1:7比例混合并搅拌均匀，制得混合物料。
(2)催化剂制备：将混合物料干燥后置入石英管式炉，在N2气氛下于500℃煅烧1.5h，获得镍基催化剂，其电镜扫描图如图1所示，透射电镜图如图2所示。从图1、2中可看出，孔隙结构非常丰富，纳米镍粒子分布的十分均匀，且尺寸分布较一致。
(3)焦油低温催化重整实验：选取多环芳烃萘、蒽为典型焦油难降解组分的模型化合物，以水蒸气发生器制备的高温水蒸气(180℃)为催化反应介质，开展镍基催化剂低温重整焦油反应实验，重整反应温度设置为500℃。
(4)焦油低温催化重整产物分析：利用集气袋收集焦油催化重整反应后的气相产物，依据国标GB/T10410-2008(人工煤气和液化石油气常量组分气相色谱分析法)对气相产物组分进行定量分析。
实施例2
催化剂前驱体制备中除了步骤(1)将提质预处理后的海相页岩固体干酪根与5.0mol/L浓度的六水合硝酸镍溶液按质量1:7比例混合并搅拌均匀，制得混合物料之外，其余与实施例1相同。
实施例3
催化剂制备中除了步骤(2)将混合物料干燥后置入石英管式炉，在N2气氛下于500℃煅烧3.5h，获得镍基催化剂之外，其余与实施例1相同。
对比例1
催化剂前驱体制备中除了步骤(1)将提质预处理后的海相页岩固体干酪根与1.2mol/L浓度的六水合硝酸镍溶液按质量1:9比例混合并搅拌均匀，制得混合物料之外，其余与实施例1相同。获得的镍基催化剂，其电镜扫描图如图3所示，透射电镜图如图4所示。从图3、4可看出，孔隙结构较少，纳米镍粒子分布不均匀，且尺寸分布不一致。
对比例2
催化剂制备中除了步骤(2)将混合物料干燥后置入石英管式炉，在N2气氛下于700℃煅烧5h，获得镍基催化剂之外，其余与实施例1相同。获得的镍基催化剂，其电镜扫描图如图5所示，透射电镜图如图6所示。从图5、6可看出，孔隙结构一般，纳米镍粒子分布相对均匀，但尺寸分布不一致。
对比例3
催化剂前驱体制备中除了将海相页岩固体干酪根原料换为常规镍基催化剂所用生物质废弃物前驱体木屑，其余与实施例1相同。
各实施例和对比例的检测结果见表1所示。
表1焦油低温重整转化效率及裂解小分子气体组分实验结果
以上所述的实施例仅是对本发明的优选方式进行描述，并非对本发明的范围进行限定，在不脱离本发明设计精神的前提下，本领域普通技术人员对本发明的技术方案做出的各种变形和改进，均应落入本发明权利要求书确定的保护范围内。
Claims (3)
1.提高生物质焦油低温重整性能的镍基催化剂的制备方法，其特征在于：以海相页岩固体干酪根为原料，通过提质预处理后，经干燥、研磨、筛分后与六水合硝酸镍溶液混合后制得催化剂前驱体；将催化剂前驱体在氮气氛围下高温煅烧后即得镍基催化剂；
所述海相页岩固体干酪根提质预处理的过程为：在水浴条件下，将海相页岩固体干酪根与硫酸混合搅拌，并用去离子水洗涤至中性，并用纳滤膜过滤以获得提质后的海相页岩固体干酪根；所述催化剂前驱体在450～550℃下煅烧1.5～4h；
所述海相页岩固体干酪根中，化学成分元素原子比范围：O/C:0.14～0.16；H/C:0.75～0.79，比表面积：4.95～7.58m2/g；热演化程度/热成熟度：1.1～1.4％，平均TOC含量2.0～2.3％；
所述六水合硝酸镍溶液的浓度为2.5～5.5mol/L，所述海相页岩固体干酪根与六水合硝酸镍溶液的质量比为1:6～1:8。
2.根据权利要求1所述的提高生物质焦油低温重整性能的镍基催化剂的制备方法，其特征在于：在58～62℃的水浴条件下，海相页岩固体干酪根与15％硫酸按质量比1:14～1:15混匀并搅拌10～12h。
3.一种镍基催化剂，其特征在于：根据权利要求1～2任一项所述方法制备的镍基催化剂。
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