CN112403474B - 一种负载型co2加氢催化剂及其制备方法 - Google Patents
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Abstract
本发明涉及催化剂制备技术领域，具体涉及一种负载型CO2加氢催化剂及其制备方法，将铜负载物负载在空心球载体的外表面。本发明解决了现有技术合成CO2加氢催化剂比表面积低、铜分散度差、原料转化率低的技术问题。能够有效控制载体的形貌，形成片层堆叠的空心球结构。过程简单、产率高、无需使用结构导向剂、对设备无特殊要求，适用于大规模生产。
Description
技术领域
本发明涉及环境化学领域，具体涉及一种负载型CO2加氢催化剂 及其制备方法。
背景技术
温室效应是当今世界重点关注的问题，将CO2转化为液态燃料(如 甲醇)是最有效的减排方式之一，传统CO2加氢催化剂比表面积低、 铜分散度差，而负载型催化剂可在一定程度上解决该问题。
在现有载体制备技术中，共沉淀法、水热合成法、阴离子交换法 和溶胶凝胶法是常见的合成方法。例如，发明专利201610999397.9 公开了一种制备粒径分布均匀的水滑石的方法，使用超重力旋转床、 开启循环泵使物料在系统中循环至料浆的pH值稳定，再经过120～ 160℃晶化6小时以上获得产品。与之相比，本发明在产品性能方面 有明显改进，表现为产品粒径均匀，具备空心球形貌，且简化了合成 步骤。为了控制合成过程以获得特殊的催化剂形貌，现有技术往往通 过外加载体或结构导向剂的方法实现。发明专利201810802983.9以 氧化石墨为载体制备了三维层状双金属氢氧化物/石墨烯复合光催化剂，发明专利201811592305.0以二维纳米片为载体制备了一种镍钴 双金属氢氧化物纳米片上花，发明专利201810247388.3以荧光增白 剂为载体制备了一种层状双金属氢氧化物基多功能纸张表面施胶剂， 发明专利201711178601.1以石墨烯为载体制备了一种用于处理污水 的层状双金属氢氧化物微球，Chandrasekaran等人分别以纳米二氧 化硅为硬模板(结构导向剂)制备了Ni-Al-Mg的LTH空心球 (Chandrasekaran,et al.Mater Chem andPhys,2017)、以 TEOS+CTAB为软模板(结构导向剂)制备了Mn-Cu-Al的LTH空心球(Chandrasekaran,et al.Int J Hydrogen Energy,2017)。目前， 以简单方法直接制备高效负载型CO2加氢催化剂仍是亟待攻克的技 术难题，尚未见到不使用载体或结构导向剂直接合成具有空心结构的 高效负载型CO2加氢催化剂的报道。
发明内容
针对现有技术合成CO2加氢催化剂比表面积低、铜分散度差、原 料转化率低的技术问题，本发明提出一种负载型CO2加氢催化剂及其 制备方法。
具体技术方案如下：
一种负载型CO2加氢催化剂，所述催化剂化学式表示为 CunAlxMgyM1-x-yCx/ 2H2O1.5x+2，其中，Cu为负载物， AlxMgyM1-x-yCx/2H2O1.5x+2为载体，M为二价金属阳离子，包括Zn2 +、 Ni2+、Fe2+、Sr2+、Ba2+、Mn2+、Co2+；0＜n＜x，0.25＜x＜0.5，且0.5×(1-x) ＜y＜1.25×(1-x)，保证所得催化剂结构与性能稳定；所述载体由片层 状基本结构单元自组装交错堆叠构成，表面呈片状凸起，外表面积丰 富；载体整体为大小均一、高度分散的规则球体，外径约为10～20 微米，具有空心结构；铜负载物负载在空心球外表面，平均粒径在 200纳米以下。
一种负载型CO2加氢催化剂的制备方法，具体包括如下步骤：
(1)按Mg2++M2+：Al3+＝1.25～0.5：1的金属元素摩尔比配制 Mg2+-M2+-Al3+三元混合金属盐溶液；
(2)在连续搅拌条件下向步骤(1)得到的三元混合金属盐溶液 中加入过量的尿素，室温下连续搅拌直至充分溶解，获得澄清的前驱 体混合液；
(3)将步骤(2)得到的前驱体混合液转移至均相反应器中，在 高温、搅拌条件下进行反应；
(4)过滤步骤(3)得到的反应后溶液，将所得滤渣充分洗涤、 干燥后获得自组装载体；
(5)将步骤(4)得到的自组装载体活化后均匀分散在铜离子溶 液中，在水浴条件下缓慢加入还原剂溶液，进行液相还原；
(6)液相还原结束后，反复洗涤沉淀物，过滤、干燥后得到负 载型CO2加氢催化剂。
步骤(1)中，对混合金属盐溶液进行超声处理，时间为5～30 分钟。
步骤(2)中尿素的摩尔数为溶液中金属阳离子总摩尔数的 1.1～1.5倍。
步骤(3)中均相反应的反应温度为100～150℃，进行反应的同 时伴随搅拌操作。
步骤(5)中，所得载体在使用前需要煅烧活化。煅烧温度为 250～450℃，煅烧时间为4～6小时，煅烧气氛为空气、氮气、氩气、 氦气或其混合气。
步骤(5)中所述铜离子溶液包括硝酸铜、硫酸铜、氯化铜、醋 酸铜或其混合溶液。
步骤(5)中所述还原剂溶液包括维生素C溶液、柠檬酸钠溶液、 硼氢化钠溶液、油酸、水合肼、N，N-二甲基甲酰胺、甲醛、盐酸羟 胺。
与现有技术相比，本发明具有如下有益技术效果：
本发明提供的负载型CO2加氢催化剂，在现有技术基础上，以液 相还原取代传统热还原，有效减少了铜负载物的烧结和团聚，显著改 善了催化剂的微观形貌。该新型催化剂拥有丰富的比表面积，有利于 调控酸碱位点、强化传热传质性能，因而在催化领域具有广阔的应用 前景。目前，尚未见到关于类似负载型CO2加氢催化剂的相关报道。
此外，本发明还提供了制备上述催化剂的方法，能够有效控制载 体的形貌，形成片层堆叠的空心球结构。本发明的制备方法过程简单、 产率高、无需使用结构导向剂、对设备无特殊要求，适用于大规模生 产。
附图说明
图1为负载型CO2加氢催化剂载体的扫描电镜图；
图2为负载型CO2加氢催化剂剖面扫描电镜图。
具体实施方式
下面结合附图和实施例对本发明进行详细说明，但本发明的保护 范围不受附图和实施例所限。
实施例1
本实施例提供一种自组装空心球载体，按如下步骤制备：将3.42g Mg(NO3)2·3H2O、1.98g Zn(NO3)2·6H2O和3.75g Al(NO3)3·9H2O粉末 溶于50mL去离子水，配制成混合金属盐溶液，超声处理30分钟，取 出后搅拌至完全溶解；将7.21g尿素加入混合金属盐溶液，并继续搅 拌，直至完全溶解；将所得溶液转移到均相反应器中，在120℃下反 应24小时；将反应后溶液冷却、抽滤，洗涤、干燥所得滤渣，成功 制备了自组装空心球载体。
实施例2
对实施例1中得到的自组装空心球载体进行表征：附图1为其扫 描电镜图，结果表明其表面呈现片状凸起，整体大小均一、形状规则， 直径约为12微米；附图2为其剖面的扫描电镜图，可以证明合成的 产品具有空心结构，空心部分直径约为5微米，占为球体外径的41.7％； 通过低温氮气吸-脱附测试可以计算，该自组装空心球载体活化后的 BET比表面积达到193.5m2/g，处于较高水平。
实施例3
取1g实施例1得到的自组装空心球载体，在350℃空气气氛中 活化4小时。将活化后的载体均匀分散在500mL浓度为0.5mol/L的 硝酸铜溶液中，持续搅拌至浆液均匀，在70℃水浴条件下倒入50mL 氢氧化钠-维生素C混合溶液(pH＝～8)，反应30min后过滤、洗涤、干燥，获得负载型CO2加氢催化剂。
实施例4
对实施例3中得到的负载型CO2加氢催化剂进行表征分析和催化 性能测试，结果表明：铜负载物被成功负载在载体表面，且粒度均一、 分散良好，平均粒径约为50nm，产品表现出良好的催化活性，在250℃、 3.0MPa的反应条件下，其单程CO2转化率不低于20％，产物中甲醇选 择性不低于75％。
Claims (7)
1.一种负载型CO2加氢催化剂，其特征在于：所述催化剂化学式表示为CunAlxMgyM1-x- yCx/2H2O1.5x+2，其中，Cu为负载物，AlxMgyM1-x-yCx/2H2O1.5x+2为载体，M为二价金属阳离子，包括Zn2+、Ni2+、Fe2+、Sr2+、Ba2+、Mn2+、Co2+；0＜n＜x，0.25＜x＜0.5，且0.5×(1-x)＜y＜1.25×(1-x)，保证所得催化剂结构与性能稳定；所述载体由片层状基本结构单元自组装交错堆叠构成，表面呈片状凸起，外表面积丰富；载体整体为大小均一、高度分散的规则球体，外径为10~20微米，具有空心结构；铜负载物负载在空心球外表面，平均粒径在200纳米以下。
2.一种如权利要求1所述的负载型CO2加氢催化剂的制备方法，其特征在于，具体包括如下步骤：
（1）按Mg2++M2+：Al3+=1.25~0.5：1的金属元素摩尔比配制Mg2+-M2+-Al3+三元混合金属盐溶液；
（2）在连续搅拌条件下向步骤（1）得到的三元混合金属盐溶液中加入过量的尿素，室温下连续搅拌直至充分溶解，获得澄清的前驱体混合液；
（3）将步骤（2）得到的前驱体混合液转移至均相反应器中，在搅拌条件下进行反应，反应温度为100~150 ℃；
（4）过滤步骤（3）得到的反应后溶液，将所得滤渣充分洗涤、干燥后获得自组装载体；
（5）将步骤（4）得到的自组装载体活化后均匀分散在铜离子溶液中，在水浴条件下缓慢加入还原剂溶液，进行液相还原；
（6）液相还原结束后，反复洗涤沉淀物，过滤、干燥后得到负载型CO2加氢催化剂。
3.根据权利要求2所述的负载型CO2加氢催化剂的制备方法，其特征在于：步骤（1）中，对混合金属盐溶液进行超声处理，时间为5~30分钟。
4.根据权利要求2所述的负载型CO2加氢催化剂的制备方法，其特征在于：步骤（2）中尿素的摩尔数为溶液中金属阳离子总摩尔数的1.1~1.5倍。
5.根据权利要求2所述的负载型CO2加氢催化剂的制备方法，其特征在于：步骤（5）中，所得载体在使用前需要煅烧活化；煅烧温度为250~450oC，煅烧时间为4~6小时，煅烧气氛为空气、氮气、氩气、氦气或其混合气。
6.根据权利要求2所述的负载型CO2加氢催化剂的制备方法，其特征在于：步骤（5）中所述铜离子溶液包括硝酸铜、硫酸铜、氯化铜、醋酸铜或其混合溶液。
7.根据权利要求2所述的负载型CO2加氢催化剂的制备方法，其特征在于：步骤（5）中所述还原剂溶液包括维生素C溶液、柠檬酸钠溶液、硼氢化钠溶液、油酸、水合肼、N，N-二甲基甲酰胺、甲醛、盐酸羟胺。
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