石油炼制与化工 ›› 2026, Vol. 57 ›› Issue (9): 87-98.

• 催化剂 • 上一篇    下一篇

3D打印制备NiCu基多孔催化剂及其催化柴油重整性能

薛涛1,2,3,刘太楷2,宋琛2,文魁2,毛杰2,邓春明2,刘敏2,贺欣怡1,3,刘靓怡1,3,廖汉林4,李聪1,3   

  1. 1. 长沙理工大学能源与动力工程学院
    2. 广东省科学院新材料研究所现代材料表面国家工程实验室,广东省现代材料表面工程重点实验室
    3. 长沙理工大学电网防灾减灾全国重点实验室
    4. 贝尔福-蒙贝利亚技术大学
  • 收稿日期:2026-03-30 修回日期:2026-05-29 出版日期:2026-09-12 发布日期:2026-08-21
  • 通讯作者: 刘太楷;李聪 E-mail:liutaikia@gdinm.com;licong@csust.edu.cn
  • 基金资助:
    国家重点研发计划项目;国家自然科学基金;广东省现代表面工程技术重点实验室;广东省科学院新材料研究所人才育引和资源配置改革行动专项资金项目

PREPARATION OF NiCu-BASED POROUS CATALYSTS BY 3D PRINTING AND THEIR PERFORMANCE IN DIESEL REFORMING

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  • Received:2026-03-30 Revised:2026-05-29 Online:2026-09-12 Published:2026-08-21

摘要: 针对现有柴油重整催化剂制备过程复杂、传质传热性能差、机械强度低、抗积炭和硫中毒能力不足等问题,基于选区激光熔化3D打印技术制备了NiCu基催化剂,并通过高温氧化处理技术在催化剂表面引入富含晶格氧的活性氧化层,实现了结构-功能一体化柴油重整催化剂的一步成型。性能评价结果表明:与空气氧化处理样品相比,氧气氧化处理可以有效提升催化剂样品的重整活性和稳定性;在800℃、水碳摩尔比为4.9:1的条件下,使用氧气氧化处理的催化剂样品催化柴油蒸汽重整反应,柴油转化率高达99.61%、氢气产率达68.71%,且催化剂稳定性优异。X射线衍射、扫描电镜-能量色散荧光光谱、X射线光电子能谱表征结果发现:催化剂表面氧化层中CuO的(002)晶面是具有高催化活性的晶面,其特殊的原子排布和电子结构能选择性促进柴油组分分子的吸附与活化,加速柴油重整反应;同时,表面氧化层中的晶格氧能参与催化剂表面的氧化-还原循环反应,及时清除催化剂表面积炭,保持其催化活性。

关键词: 重整催化剂, 柴油清洁化, 3D打印, 结构-功能一体化, 晶格氧, 晶面, 氧化-还原循环反应

Abstract: Aiming at the problems of complex preparation process, poor mass and heat transfer performance, low mechanical strength, and insufficient resistance to coking and sulfur poisoning of existing diesel reforming catalysts, porous NiCu-based catalysts were prepared based on selective laser melting 3D printing technology. An active oxide layer rich in lattice oxygen was introduced onto the porous catalyst surface through high-temperature oxidation treatment, achieving one-step forming of structurally and functionally integrated diesel reforming porous catalysts. Performance evaluation results showed that, compared with air high-temperature oxidation treated samples, oxygen high-temperature oxidation could effectively improve the reforming activity and stability of the catalyst samples. Under the conditions of 800 °C and a steam-to-carbon molar ratio of 4.9:1, the sample treated by oxygen high-temperature oxidation achieved a diesel conversion of 99.61% and a hydrogen yield of 68.71% in catalyzing diesel steam reforming reaction, with excellent catalyst stability. Characterization results from XRD, SEM-EDS, and XPS revealed that the (002) crystal facet of CuO has a special atomic arrangement and electronic structure, which is a highly catalytically active facet that can selectively promote the adsorption and activation of diesel component molecules and accelerate the diesel reforming reaction. The lattice oxygen in the oxide layer can participate in the oxidation-reduction cycle reaction on the catalyst surface, timely removing surface coke deposits and maintaining catalyst activity.

Key words: reforming catalyst, clean utilization of diesel, 3D printing, structural-functional integration, lattice oxygen, crystal facet, oxidation-reduction cycle reaction