高等学校化学学报 ›› 2019, Vol. 40 ›› Issue (2): 201-209.doi: 10.7503/cjcu20180374

• 无机化学 • 上一篇    下一篇

高长径比管式反应器内壁SiO2与TiO2钝化层的原子层沉积制备及抗积碳性能

惠龙飞1,2, 李建国1,2, 龚婷1,2, 孙道安3, 吕剑3, 胡申林4, 冯昊1,2,3()   

  1. 1. 西安近代化学研究所火炸药燃烧国防科技重点实验室, 西安 710065
    2. 材料表面工程与纳米修饰实验室, 西安 710065
    3. 氟氮化工资源高效开发与利用国家重点实验室, 西安 710065
    4. 北京动力机械研究所, 北京 100074
  • 收稿日期:2018-05-21 出版日期:2019-02-10 发布日期:2018-10-08
  • 作者简介:

    联系人简介: 冯 昊, 男, 博士, 研究员, 博士生导师, 主要从事原子层沉积技术应用研究. E-mail: fenghao98@hotmail.com

  • 基金资助:
    国家“万人计划”青年拔尖人才支持计划(批准号: W02070370)资助

Fabrication of Silica and Titania Anti-coking Passivation Layers in High Aspect-ratio Tubular Reactors by Atomic Layer Deposition

HUI Longfei1,2, LI Jianguo1,2, GONG Ting1,2, SUN Daoan3, LÜ Jian3, HU Shenlin4, FENG Hao1,2,3,*()   

  1. 1. Science and Technology on Combustion and Explosion Laboratory, Xi’an 710065;
    2. Laboratory of Material Surface Engineering and Nanofabrication, Xi’an 710065;
    3. State Key Laboratory of Fluorine and Nitrogen Chemicals, Xi’an Modern Chemistry Research Institute, Xi’an 710065;
    4. Beijing Power Machinery Institute, Beijing 100074
  • Received:2018-05-21 Online:2019-02-10 Published:2018-10-08
  • Contact: FENG Hao E-mail:fenghao98@hotmail.com
  • Supported by:
    † Supported by the National Ten Thousand Talent Program for Young Top-notch Talent of China(No.W02070370)

摘要:

采用原子层沉积技术(ALD)在不锈钢微通道管式反应器内壁沉积二氧化硅(SiO2)和二氧化钛(TiO2)薄膜, 以抑制碳氢燃料热裂解过程中由于金属催化作用导致的结焦. 使用石英晶体微天平(QCM)测得SiO2和TiO2薄膜的生长速率分别为0.15 nm/周期和0.11 nm/周期, 因此可以通过改变沉积周期数精确控制钝化层的厚度. 在结焦实验中, 当钝化膜层较薄时, 其抗积碳钝化作用较弱; 随着钝化薄膜厚度的增加, 其钝化作用逐渐增强, 微通道反应器的运行寿命显著延长. 实验表明, TiO2薄膜的抗积碳钝化性能普遍优于SiO2薄膜. 沉积周期数为1000的TiO2膜层具有最佳的抗积碳钝化效果, 能够使反应器的运行时间延长4~5倍.

关键词: 原子层沉积(ALD), 表面钝化, 积碳, 二氧化钛(TiO2), 二氧化硅(SiO2)

Abstract:

Silica and titania thin films were deposited inside the micro channels of stainless steel tubular reactors by atomic layer deposition(ALD) to suppress the metal catalyzed coke formation during thermal cracking of hydrocarbon fuels. Quartz crystal microbalance measurements reveal that the average film growth rate is 0.15 nm/cycle for silica and 0.11 nm/cycle for titania. The thicknesses of the passivation layers can be precisely controlled by changing the number of ALD cycle. In coking experiments, very thin films of silica or titania only show modest anti-coking performances and thicker coatings can effectively enhance the run lengths of the micro channel reactors. Generally, ALD titainia coatings perform better than silica coatings. The best anti-coking performance is obtained with a 1000-cycles ALD titania passivation layer, which can extend the lifetime of the reaction system by a factor of 4 to 5.

Key words: Atomic layer deposition(ALD), Surface passivation, Coke suppression, Titania, Silica

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