CN109126876A - 一种石墨烯负载型燃油脱硫催化剂及其制备方法 - Google Patents

一种石墨烯负载型燃油脱硫催化剂及其制备方法 Download PDF

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CN109126876A
CN109126876A CN201811080441.1A CN201811080441A CN109126876A CN 109126876 A CN109126876 A CN 109126876A CN 201811080441 A CN201811080441 A CN 201811080441A CN 109126876 A CN109126876 A CN 109126876A
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张改
任菁菁
田敏
马爱洁
陈卫星
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Xian Technological University
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Abstract

本发明涉及一种石墨烯负载型燃油脱硫催化剂的制备方法，将氧化石墨烯、邻苯二甲腈和金属盐混合均匀加入到烧杯中，加入催化剂1,8‑二氮杂二环十一碳‑7‑烯（DBU），溶剂N,N‑二甲基甲酰胺（DMF），超声混合；所得溶液转入高压反应釜内，在170℃条件下，反应24h；反应结束后冷却至室温后过滤，对所得产物分别用蒸馏水、无水乙醇进行离心洗涤，并烘干，得到MPcR4/GO复合材料，为石墨烯负载型燃油脱硫催化剂。本发明制备方法简单，对设备要求及实验条件要求较低，产率高，制得的石墨烯负载型燃油脱硫催化剂产品纯度高且质量稳定，在室温通空气氧化燃油就能达到很好的脱硫效果，且不需要辅助催化剂。

Description

一种石墨烯负载型燃油脱硫催化剂及其制备方法
技术领域
本发明涉及能源与环境保护技术领域，具体涉及一种石墨烯负载型燃油脱硫催化剂及其制备方法。
背景技术
随着全球范围内机动车数目的激增，因此引发的环境污染情况也日益严峻，世界各国对机动车用燃油中的硫含量不断提出了更高的要求。现在欧美国家已经采取欧IV排放标准，我国要求从2003年开始车用燃油硫含量低于800 μg·g-1，2010年力争达到国际标准(硫含量为15 μg·g-1)。我国现在燃油含硫量约350 μg·g-1，远高于国际标准，因此提 高燃油的脱硫效率在我国显得尤为迫切。
传统的氧化脱硫方法在氧化效果和无污染方面两者难以兼备，使得氧化法脱硫技术难以适应现代工业发展的要求。因此，寻求一种效果好、经济效益显著、无毒无污染的脱硫催化剂显得尤为重要。
目前，国内外已有多家工厂使用以酞菁配合物为催化剂的脱硫技术，工艺简单、成本低，但需要与其他助剂配合使用，工业运行不稳定。中国公开专利CN201810079258将石墨烯引入金属酞菁脱硫催化剂，但制备过程需要多种复杂原料，工艺复杂，步骤繁琐。还有文献中所述催化过程在水相中进行，双氧水为催化剂，必须增加后续油水相分离工艺，导致工艺复杂，步骤繁琐。
发明内容
本发明的目的是要提供一种石墨烯负载型燃油脱硫催化剂及其制备方法，制备方法原料简单、工艺简洁、易实现工业化生产，制得的石墨烯负载型燃油脱硫催化剂产品纯度高，脱硫效率达到90%以上。
为了达到上述目的，本发明提供的一种石墨烯负载型燃油脱硫催化剂的制备方法，包括以下步骤：
称取氧化石墨烯0.200g、邻苯二甲腈0.400g和金属盐，所述金属盐与邻苯二甲腈摩尔比为1: 4；将上述原料混合均匀加入到烧杯中，加入催化剂1,8-二氮杂二环十一碳-7-烯（DBU）0.5 mL，溶剂N,N-二甲基甲酰胺（DMF）10 mL，超声混合2h；所得溶液转入高压反应釜内，在170℃条件下，反应24h；反应结束后冷却至室温后过滤，对所得产物分别用蒸馏水、无水乙醇进行离心洗涤，并在50℃条件下烘干，得到MPcR4 / GO复合材料，为石墨烯负载型燃油脱硫催化剂。
上述步骤中金属盐为过渡金属（M = Mn2+，Fe2+，Co2+，Ni2+，Cu2+，Zn2+）的乙酸盐、氯化盐、硝酸盐或硫酸盐。
上述步骤中烘干操作在真空干燥箱中进行。
上述步骤得到的MPcR4/GO复合材料中，R为酞菁环上的取代基，R= -H, -COOH, -CONH2，-NH2，-NO2，-Cl。
如上述的制备方法制得的石墨烯负载型燃油脱硫催化剂。
与现有的脱硫催化剂及其制备技术相比，本发明的有益效果是：
1）本发明制备方法简单，水热法一步合成，且对设备要求及实验条件要求较低，产率高，适合进行大量的合成，易实现工业化；
2）本发明制得的石墨烯负载型燃油脱硫催化剂在室温通空气氧化燃油就能达到很好的脱硫效果，且不需要辅助催化剂；
3）本发明制得的石墨烯负载型燃油脱硫催化剂产品纯度高且质量稳定，脱硫效率达到90%以上；
4）本发明制备方法催化反应在非水相的常压自然光照射下进行，利用氧气为氧化剂，简化了催化工艺，降低了生产成本。
附图说明
图1为本发明的一种石墨烯负载金属酞菁燃油脱硫催化剂的制备方法；
图2为不同中心金属的石墨烯负载金属酞菁脱硫催化剂氧化模拟燃油脱硫活性实验结果；
图3为石墨烯负载金属酞菁燃油脱硫催化剂的循环稳定性试验的实验结果。
具体实施方式
下面将结合具体实施例对本发明作进一步详细的描述，但本发明的实施方式包括但不限于以下实施例表示的范围。
参见图1，一种石墨烯负载金属酞菁燃油脱硫催化剂的制备方法，称取氧化石墨烯0.200g、4-硝基邻苯二甲腈0.400g和金属盐，所需金属盐中金属离子与邻苯二甲腈摩尔比为1: 4；将上述原料混合均匀加入到烧杯中，加入催化剂1,8-二氮杂二环十一碳-7-烯（DBU）0.5 mL，溶剂N,N-二甲基甲酰胺（DMF）10 mL，在超声波清洗器中超声混合2h；所得溶液转入100 mL的高压反应釜内在170℃条件下，反应24h；反应停止后冷却至室温，对产物分别用蒸馏水、无水乙醇进行离心洗涤，并在50℃的真空干燥箱里烘干，得到MPc / GO复合材料。
实施例，上面所说制备方法所采用的金属盐以乙酸盐M(COOH)2·nH2O(M = Mn2+，Fe2+，Co2+，Ni2+，Cu2+，Zn2+)为例，得到对应的石墨烯负载无取代金属酞菁复合材料MPc/GO，（R= -H，M = Mn2+，Fe2+，Co2+，Ni2+，Cu2+，Zn2+)。
所述复合材料MPc/GO中，金属酞菁并不仅仅局限于无取代金属酞菁即MPc（R= -H），还应包括酞菁环上取代基为R= -COOH, -CONH2，-NH2，-NO2，-Cl等不同取代基的复合材料MPcR4/GO。
制得石墨烯负载金属酞菁MPc/GO，（R= -H，M = Mn2+，Fe2+，Co2+，Ni2+，Cu2+，Zn2+)燃油脱硫催化剂，它们的模拟燃油脱硫活性参见图2。其中未加催化剂模拟燃油的脱硫率为16.35%，石墨烯负载金属酞菁复合催化剂MnPc /GO，FePc/GO，CoPc/GO，NiPc/GO，CuPc/GO，ZnPc/GO脱硫率分别提高至94.46%, 90.89%, 96.01%, 96.98%, 97.43%, 97.51%。3h的脱硫效率都达到90%以上， 其中ZnPc/GO的脱硫效率最高，可高达97.51%，达到了深度脱硫的要求。
石墨烯负载金属酞菁燃油脱硫催化剂的稳定性以催化活性最高的ZnPc/GO为例进行研究，参见图3，ZnPc/GO催化剂经过5次循环使用后，脱硫催化活性减弱，但是减弱不明显，依然高达87%以上，说明本发明制得的石墨烯负载金属酞菁燃油脱硫催化剂性能稳定，多次循环后仍然能保持较好的脱硫效果。

Claims (5)

1.一种石墨烯负载型燃油脱硫催化剂的制备方法，其特征在于：
包括以下步骤：
称取氧化石墨烯0.200g、邻苯二甲腈0.400g和金属盐，所述金属盐与邻苯二甲腈摩尔比为1: 4；将上述原料混合均匀加入到烧杯中，加入催化剂1,8-二氮杂二环十一碳-7-烯（DBU）0.5 mL，溶剂N,N-二甲基甲酰胺（DMF）10 mL，超声混合2h；所得溶液转入高压反应釜内，在170℃条件下，反应24h；反应结束后冷却至室温后过滤，对所得产物分别用蒸馏水、无水乙醇进行离心洗涤，并在50℃条件下烘干，得到MPcR4 / GO复合材料，为石墨烯负载型燃油脱硫催化剂。
2.根据权利要求1所述的一种石墨烯负载型燃油脱硫催化剂的制备方法，其特征在于：
所述金属盐为过渡金属M的乙酸盐、氯化盐、硝酸盐或硫酸盐，M = Mn2+，Fe2+，Co2+，Ni2+，Cu2+，Zn2+。
3.根据权利要求1所述的一种石墨烯负载型燃油脱硫催化剂的制备方法，其特征在于：
所述烘干操作的设备为真空干燥箱。
4.根据权利要求1所述的一种石墨烯负载型燃油脱硫催化剂的制备方法，其特征在于：
所述MPcR4/GO复合材料中，R为酞菁环上的取代基，R= -H, -COOH, -CONH2，-NH2，-NO2，-Cl。
5.如权利要求1所述的制备方法制得的石墨烯负载型燃油脱硫催化剂。
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CN111111786A (zh) * 2020-01-14 2020-05-08 西安工业大学 一种MOFs负载型燃油脱硫催化剂及其制备方法、用途

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