钨修饰对镍载氧体的沼气化学链重整制氢性能影响

doi:10.16085/j.issn.1000-6613.2022-1108

化工进展 ›› 2023, Vol. 42 ›› Issue (4): 2130-2141.DOI: 10.16085/j.issn.1000-6613.2022-1108

钨修饰对镍载氧体的沼气化学链重整制氢性能影响

龚陈俊¹^,²(), 梅道锋¹^,²^,³()

^1.华中农业大学农业农村部长江中下游农业装备重点实验室，湖北武汉 430070
^2.华中农业大学工学院，湖北武汉 430070
^3.查尔姆斯理工大学能源技术系，瑞典哥德堡 41296

收稿日期:2022-06-13 修回日期:2022-08-22 出版日期:2023-04-25 发布日期:2023-05-08
通讯作者: 梅道锋
作者简介:龚陈俊（1997—），男，硕士研究生，研究方向为化学链技术。E-mail：gcjifuli@126.com。
基金资助:
国家自然科学基金(51906083);国家重点研发计划(2018YFB0605402)

Effects of tungsten decoration on the performance of a Ni-based oxygen carrier during chemical looping reforming of biogas for hydrogen generation

GONG Chenjun¹^,²(), MEI Daofeng¹^,²^,³()

^1.Key Laboratory of Agricultural Equipment in Mid-lower Yangtze River, Ministry of Agriculture and Rural Affairs (Huazhong Agricultural University), Wuhan 430070, Hubei, China
^2.College of Engineering, Huazhong Agricultural University, Wuhan 430070, Hubei, China
^3.Department of Energy Technology, Chalmers University of Technology, Gothenburg 41296, Sweden

Received:2022-06-13 Revised:2022-08-22 Online:2023-04-25 Published:2023-05-08
Contact: MEI Daofeng

摘要/Abstract

摘要：

沼气中含有约60% CH₄和40% CO₂，可以作为化学链重整（chemical looping reforming，CLR）的原料。以高铝耐火砖为惰性载体负载Ni作为载氧体（oxygen carrier，OC），在无H₂S的条件H₂产率和CO产率较高，且沼气中的CH₄和CO₂能够完全转化。前期的研究显示沼气中含有的少量H₂S会对载氧体（OC）活性产生负面影响，导致载氧体失活。根据已有文献，钨元素能够抑制H₂S对催化剂的毒化作用。本文以高铝耐火砖为惰性载体，制备了同时含有W和Ni的载氧体、改变Ni和W的浸渍顺序，探究W对化学链重整制氢特性的影响。将1000μL/L H₂S和CH₄/CO₂为3/2的气氛混合来模拟含硫沼气，在批次进料流化床反应器中开展多种工况下的实验。结果显示，经钨修饰后载氧体的催化性能均有一定的降低，而不同的钨修饰顺序对重整性能也具有一定的影响。对于不掺杂H₂S的沼气，相对于OC-Ni=W（镍和钨同时负载）和OC-W-Ni（先负载钨后负载镍）而言，OC-Ni-W（先负载镍后负载钨）具有更高的催化性能。在沼气中掺杂1000μL/L H₂S后，相对于其他两种载氧体，OC-Ni-W载氧体具有更高的CO产率和H₂产率。

关键词: 化学链重整, 沼气, 镍载氧体, 钨修饰, 硫化氢

Abstract:

Biogas, typically containing around 60% CH₄and 40% CO₂, can be used as feedstock in chemical looping reforming (CLR) process. In our previous work, a Ni-based oxygen carrier (OC) using high-alumina firebrick as support has shown excellent performance of complete CH₄ and CO₂ conversion of biogas, thus resulting in high H₂ and CO yield in CLR. Nonetheless, that work also found that the presence of H₂S in biogas can poison the OC and then leads to decrease of the OC reactivity. Based on some literatures, tungsten is promising of lessening the sulfur poisoning on catalysts. In the present work, tungsten was used to decorate the Ni oxygen carrier and the impregnating sequence of Ni and W in the firebrick was changed to study the effects on the OC performance. An 1000μL/L H₂S was mixed with the biogas (the ratio of CH₄/CO₂ was 3/2) and experiments were carried out in a batch fluidized bed reactor under various reacting conditions. It is found that the W-decoration can lower catalytic activity of the oxygen carrier, and the sequence of Ni and W impregnation can also impact the reforming performance. In the case of no H₂S mixing, the OC-Ni-W (first with Ni impregnation, then W impregnation) oxygen carrier has better catalytic performance as compared to OC-Ni=W (Ni, W simultaneous impregnation) and OC-W-Ni (first W then Ni). With the presence of 1000μL/L H₂S, the OC-Ni-W has higher CO and H₂ yield as compared to OC-W-Ni and OC-Ni=W.

Key words: chemical looping reforming, biogas, Ni-based oxygen carrier, tungsten decoration, hydrogen sulfide

中图分类号:

TQ91

龚陈俊, 梅道锋. 钨修饰对镍载氧体的沼气化学链重整制氢性能影响[J]. 化工进展, 2023, 42(4): 2130-2141.

GONG Chenjun, MEI Daofeng. Effects of tungsten decoration on the performance of a Ni-based oxygen carrier during chemical looping reforming of biogas for hydrogen generation[J]. Chemical Industry and Engineering Progress, 2023, 42(4): 2130-2141.

图/表 16

图1 以CH4和CO2为燃料、NiO为活性成分的CLR原理

表1 新鲜载氧体特性

特征量	OC-Ni-W （先镍后钨）	OC-Ni=W （镍钨同时）	OC-W-Ni （先钨后镍）	10%NiO （未经W修饰）
Ni（质量分数）/%	7.85	7.85	7.85	7.85
W（质量分数）/%	0.79	0.79	0.79	0
载氧率R_OC（质量分数）/%	2.35	2.35	2.35	2.14
粒径/μm	106~300	106~300	106~300	106~300
堆积密度/g·cm^-3	2.4	2.5	2.5	2.5
破碎强度/N	3.72	3.63	4.09	4.4

图2 批次进料流化床示意图

表2 流化床实验条件

参数	数值
载氧体质量/g	300
温度/℃	950
还原气氛	15%CH₄+10%CO₂+25%H₂O+50%N₂或15%CH₄+10%CO₂+25%H₂O+50%N₂+1000μL/LH₂S
沼气中CH₄/CO₂摩尔比	3/2
水蒸气浓度/%	25
氧化气氛	100%Air（21%O₂+79%N₂）
还原时长/min	10
氧化时长/min	10
吹扫时长/min	2.5
气体流量/L·h^-1	200

图3 无H2S时10% NiO载氧体典型循环反应过程

图4 无H2S时载氧体典型循环反应过程

图5 无H2S沼气时未修饰载氧体（10% NiO）、OC-Ni-W、OC-Ni=W和OC-W-Ni的CO产率和H2产率

图6 负载10% NiO在掺杂1000μL/L H2S时典型循环过程

图7 OC-Ni-W、OC-Ni=W和OC-W-Ni为载氧体在掺杂1000μL/L H2S下典型循环过程

图8 载氧体典型循环的转化率

图9 含有1000μL/L H2S沼气时未修饰的载氧体（10% NiO）、OC-Ni-W、OC-Ni=W和OC-W-Ni的H2产率和CO产率

图10 有/无H2S的典型循环下10% NiO（无W修饰）、OC-Ni-W、OC-Ni=W和OC-W-Ni的积炭率

图11 新鲜载氧体的XRD图谱

图12 还原后载氧体XRD图谱

图13 ICP-OES测定反应前后Ni、S和W的元素含量

图14 在W修饰下OC-Ni-W、OC-Ni=W和OC-W-Ni载氧体反应前和1000μL/L H2S还原后的SEM形貌图

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钨修饰对镍载氧体的沼气化学链重整制氢性能影响

Effects of tungsten decoration on the performance of a Ni-based oxygen carrier during chemical looping reforming of biogas for hydrogen generation

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