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

doi:10.11949/0438-1157.20201771

Abstract

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

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

CLC Number:

TQ 317.4

CHEN Chen, WANG Mingming, WANG Zhigang, TAN Xiaoyao. Hydrogen production by ethanol autothermal reforming using nickel-based asymmetric hollow fiber membranes[J]. CIESC Journal, 2021, 72(S1): 482-493.

陈晨, 王明明, 王志刚, 谭小耀. 镍基非对称中空纤维膜用于乙醇自热重整制氢[J]. 化工学报, 2021, 72(S1): 482-493.

Figures/Tables 10

Fig.1 Experimental setup for ethanol autothermal reforming in metallic nickel hollow fiber membrane

Fig.2 Morphology of Ni hollow fiber membrane (1—section; 2—wall; 3—outer surface; 4—inner surface)

Fig.3 H2 permeation flux of Ni hollow fiber membrane as a function of temperature at different feed concentrations (H2-He feed rate=30 ml/min; N2 sweep rate=60 ml/min)

Fig.4 Ethanol autothermal reforming in Ni hollow fiber membrane reactor and blank reactor at different temperatures, ethanol conversion, hydrogen yield, product concentration of MR and Blank (Reaction conditions: S/C=4, O2/C=0.8, no sweep gas, feed flow rate=13 μl/min)

Fig.5 Effect of sweep gas flow rate on ethanol conversion, hydrogen yield, CO selectivity and hydrogen penetration flux at different temperatures (Reaction conditions: S/C=4, O2/C=0.8, sweep gas flow rate=0,30,50,70 ml/min, feed flow rate=13 μl/min)

Fig.6 Effect of S/C on ethanol conversion, hydrogen yield, CO selectivity and hydrogen penetration flux at different temperatures (Reaction conditions: S/C=3，4，5，6, O2/C=0.8, sweep gas flow rate=30 ml/min, feed flow rate=13 μl/min)

Fig.7 Effect of O2/C on ethanol conversion, hydrogen yield, CO selectivity and hydrogen penetration flux at different temperatures (Reaction conditions: S/C=4, O2/C=0，0.5，0.8，1, sweep gas flow rate=30 ml/min, feed flow rate=13 μl/min)

Fig.8 Effect of feed flow rate on ethanol conversion, hydrogen yield, CO selectivity and hydrogen permeation flux at different temperatures (Reaction conditions: S/C=4, O/C=0.8, sweep gas flow rate=30 ml/min, feed flow rate=13，19，26，39 μl/min)

Fig.9 XRD patterns of nickel hollow fiber membranes before and after ESR and EATR hydrogen permeation tests

Fig.10 Morphology of Ni hollow fiber membranes after ESR (a) and EATR (b) hydrogen permeation tests; EDS mappings (c) and EDS patterns (d) of nickel hollow fiber membranes before and after ESR and EATR hydrogen permeation tests

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