化工学报 ›› 2021, Vol. 72 ›› Issue (S1): 482-493.doi: 10.11949/0438-1157.20201771

• 能源和环境工程 • 上一篇    下一篇

镍基非对称中空纤维膜用于乙醇自热重整制氢

陈晨(),王明明,王志刚(),谭小耀()   

  1. 天津工业大学化学与化工学院，天津 300387
  • 收稿日期:2020-12-09 修回日期:2021-01-15 出版日期:2021-06-20 发布日期:2021-06-20
  • 通讯作者: 王志刚,谭小耀 E-mail:LuckyChency@163.com;wangzhigang@tiangong.edu.cn;tanxiaoyao@tiangong.edu.cn
  • 作者简介:陈晨（1995—），女，硕士研究生，LuckyChency@163.com
  • 基金资助:
    国家自然科学基金项目(91745116);天津市自然科学基金项目(17JCZDJC36900)

Hydrogen production by ethanol autothermal reforming using nickel-based asymmetric hollow fiber membranes

CHEN Chen(),WANG Mingming,WANG Zhigang(),TAN Xiaoyao()   

  1. Department of Chemistry and Chemical Engineering, Tiangong University, Tianjin 300387, China
  • Received:2020-12-09 Revised:2021-01-15 Published:2021-06-20 Online:2021-06-20
  • Contact: WANG Zhigang,TAN Xiaoyao E-mail:LuckyChency@163.com;wangzhigang@tiangong.edu.cn;tanxiaoyao@tiangong.edu.cn

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摘要：

采用纺丝-烧结技术制备了具有内表面致密皮层的外支撑式金属镍非对称中空纤维膜，并用于乙醇自热重整（EATR）制氢，研究了温度、进料流速、吹扫气流速、水醇比（S/C）以及氧醇比（O2/C）等操作条件对膜制氢性能的影响。结果表明，金属镍非对称中空纤维膜既具有优异的EATR催化活性，又有良好的透氢性能。在500～1000℃、S/C=4、O2/C=0.8的条件下乙醇可完全转化，H2产率和H2渗透通量可分别达到81.59%和13.99 mmol/（m2·s），增加进料中氧气含量可显著抑制膜表面积炭，但同时也会降低氢气产率和一氧化碳选择性。

关键词: 乙醇自热重整, 制氢, 膜, 中空纤维, 催化

Abstract:

Metallic nickel asymmetric hollow fiber membranes with an inner dense skin on the outer porous layer were fabricated by spinning-phase inversion technique. The membrane was used to produce hydrogen via autothermal reforming of ethanol. The operating conditions including temperature, feeding flow rate, sweeping rate, steam-to-carbon molar ratio (S/C) and oxygen-to-carbon ratio (O2/C) were investigated and optimized. The results have shown that the asymmetric nickel hollow fibers have excellent catalytic activity to EATR and high hydrogen permeation performance as well. Operated at 500—1000℃ with a steam-to-carbon ratio of 4 and an oxygen-to-carbon molar ratio of 0.8, the ethanol was completely consumed with 81.59% hydrogen yield, and the hydrogen permeation rate reached up to 13.99 mmol/(m2·s). With the increase of oxygen concentration in feed, the carbon deposition on the membrane surface was remarkably inhibited, while the hydrogen yield and CO selectivity were decreased.

Key words: ethanol autothermal reforming, hydrogen production, membrane, hollow fiber, catalysis

中图分类号: 

  • TQ 317.4

图1

金属镍中空纤维膜乙醇自热重整试验装置"

图2

镍中空纤维膜的形貌（1—截面；2—膜壁；3—外表面；4—内表面）"

图3

不同进料浓度下镍中空纤维膜的H2渗透通量与温度的关系（H2-He进料速率= 30 ml/min；N2吹扫速率= 60 ml/min）"

图4

镍中空纤维膜反应器和空白反应器中乙醇自热重整反应乙醇转化率、H2产率,MR产物浓度和Blank产物浓度随温度的变化（反应条件：S/C=4，O2/C=0.8，无吹扫气，进料流速为13 μl/min）"

图5

不同吹扫气流速对乙醇自热重整反应乙醇转化率、H2产率、CO选择性和H2渗透通量的影响（反应条件：S/C=4，O2/C=0.8，吹扫气流速分别为0、30、50、70 ml/min，进料流速为13 μl/min）"

图6

不同蒸汽/乙醇比对乙醇自热重整反应乙醇转化率、H2产率、CO选择性和H2渗透通量的影响（反应条件：S/C=3、4、5、6，O2/C=0.8，吹扫气流速为30 ml/min，进料流速为13 μl/min）"

图7

不同氧气/乙醇比对乙醇自热重整反应乙醇转化率、H2产率、CO选择性和H2渗透通量的影响（反应条件：S/C=4，O2/C=0、0.5、0.8、1，吹扫气流速为30 ml/min，进料流速为13 μl/min）"

图8

不同进料流速对乙醇自热重整反应乙醇转化率、H2产率、CO选择性和H2渗透通量的影响（反应条件：S/C=4，O2/C=0.8，吹扫气流速为30 ml/min，进料流速分别为13、19、26、39 μl/min）"

图9

ESR、EATR氢气渗透测试前后镍中空纤维膜的XRD谱图"

图10

ESR、EATR氢气渗透测试后镍中空纤维膜的形貌（a）、（b），ESR、EATR氢气渗透测试前后镍中空纤维的EDS映射（c）和元素分析（d）"

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