化学链干重整联合制氢热力学分析及实验

doi:10.11949/j.issn.0438-1157.20181424

化工学报 ›› 2019, Vol. 70 ›› Issue (6): 2244-2251.DOI: 10.11949/j.issn.0438-1157.20181424

化学链干重整联合制氢热力学分析及实验

朱珉¹(),陈时熠¹,李蒙²,宋业恒³,张磊²,向文国¹()

1. 东南大学能源与环境学院，能源热转换及其过程测控教育部重点实验室，江苏南京 210096
2. 中石化南京工程有限公司，江苏南京 211100
3. 中石化炼化工程（集团）股份有限公司洛阳技术研发中心，河南洛阳 471003

收稿日期:2018-11-29 修回日期:2019-01-17 出版日期:2019-06-05 发布日期:2019-06-05
通讯作者: 向文国
作者简介:<named-content content-type="corresp-name">朱珉</named-content>（1986—），男，博士研究生，<email>tomzhumin@163.com</email>
基金资助:
国家自然科学基金项目(51606038);江苏省科技计划青年基金项目(BK20160672)

Thermodynamic and experimental analysis of chemical looping dry reforming with hydrogen production system

Min ZHU¹(),Shiyi CHEN¹,Meng LI²,Yeheng SONG³,Lei ZHANG²,Wenguo XIANG¹()

1. Key Laboratory of Energy Thermal Conversion and Control of Ministry of Education, School of Energy and Environment, Southeast University, Nanjing 210096, Jiangsu, China
2. Sinopec Nanjing Engineering & Construction Incorporation, Nanjing 211100, Jiangsu, China
3. Luoyang R&D Center of Technology, Sinopec Engineering (Group) Co. Ltd, Luoyang 471003, Henan, China

Received:2018-11-29 Revised:2019-01-17 Online:2019-06-05 Published:2019-06-05
Contact: Wenguo XIANG

摘要/Abstract

摘要：

提出了一种化学链甲烷干重整联合制氢工艺。该工艺由还原反应器、干重整反应器、蒸汽反应器和空气反应器组成，在实现制氢的同时获得可变H₂/CO比的合成气。借助ASPEN plus软件和小型流化床实验台，在等温条件下，温度900℃，采用Fe₂O₃/Al₂O₃载氧体，对该工艺进行热力学分析和实验验证。结果显示，当铁氧化物被还原至FeO/Fe时，干重整反应器内甲烷转化率可以达到98%，CO产率可以达到94%。干重整反应器中同时发生甲烷干重整和部分氧化反应，载氧体内部晶格氧可以有效降低积炭并提高合成气H₂/CO比。积炭发生于晶格氧消耗殆尽时。积炭进入蒸汽反应器，发生气化反应，降低氢气纯度。

关键词: 甲烷, 制氢, 二氧化碳捕集, 合成气

Abstract:

A chemical chain methane dry reforming combined hydrogen production process was proposed. The process consists of a reduction reactor, a dry reforming reactor, a steam reactor and an air reactor to obtain a synthesis gas having a variable H₂/CO ratio while achieving hydrogen production. In this study, thermodynamic validation was carried out at 900℃ and 1.01×10⁵ Pa, and experiments were performed to verify the feasibility of the process in a fluidized-bed reactor using Fe₂O₃/Al₂O₃ oxygen carrier. It was found that a high conversion of CO₂ and CH₄ to syngas can be achieved on the reduced iron oxygen carrier. When the reduction extent of the oxygen carrier was 33%, the CH₄ conversion and CO yield over 98% and 94%, respectively. During the dry reforming stage, the ratio of CH₄/CO₂ was variable. Partial oxidation of excess CH₄ by active lattice oxygen increased H₂/CO molar ratio of syngas and reduced the carbon deposition. Carbon deposition formed since the active lattice oxygen has been depleted, which would react with steam in the next steam oxidizer and causing the hydrogen purity reduced.

Key words: methane, hydrogen production, CO₂ capture, syngas

中图分类号:

TE 646

朱珉, 陈时熠, 李蒙, 宋业恒, 张磊, 向文国. 化学链干重整联合制氢热力学分析及实验[J]. 化工学报, 2019, 70(6): 2244-2251.

Min ZHU, Shiyi CHEN, Meng LI, Yeheng SONG, Lei ZHANG, Wenguo XIANG. Thermodynamic and experimental analysis of chemical looping dry reforming with hydrogen production system[J]. CIESC Journal, 2019, 70(6): 2244-2251.

图/表 11

图1 化学链燃烧

Fig.1 Schematic of chemical looping combustion

图2 化学链干重整联合制氢技术

Fig.2 Schematic of chemical looping dry reforming with hydrogen generation process

图3 干重整反应器进口固体物流为Fe2O3，气体物流CH4/CO2为3时，[O]/CH4比对碳分布和铁氧化物相态的影响

Fig.3 Effect of [O]/CH4 on iron oxide distribution and carbon distribution during reaction of Fe2O3 with CH4 and CO2 mixed gases (ratio of CH4 to CO2 was 3)

图4 干重整反应器进口固体物流为FeO，气体物流CH4/CO2为3时，[O]/CH4比对CO和H2收率的影响

Fig.4 Effect of [O]/CH4 on yield of CO and H2 during reaction of FeO with CH4 and CO2 mixed gases (ratio of CH4 to CO2 was 3)

图5 混合气与FeO反应，[O]/CH4比和CH4 /CO2比对合成气H2/CO摩尔比的影响

Fig.5 Effect of [O]/CH4 and CH4 /CO2 ratio on H2/CO molar ratio of yield syngas during reaction of FeO with CH4 and CO2 mixed gases

图6 混合气与FeO反应，[O]/CH4比和CH4 /CO2比对合成气产率的影响

Fig.6 Effect of [O]/CH4 and CH4 /CO2 ratio on syngas yield during reaction of FeO with CH4 and CO2 mixed gases

图7 混合气与FeO反应中[O]/CH4比和CH4 /CO2比对蒸汽反应器制氢产率和纯度的影响

Fig.7 Effect of [O]/CH4 and CH4/CO2 ratio in dry reforming reactor on hydrogen yield and purity in next steam oxidation reactor

图8 铁氧化还原深度随反应时间的变化

Fig.8 Reduction extent of iron as function of reduction time

图9 铁氧化物还原程度对干重整反应器甲烷转化率和CO产率的影响（CH4/CO2 = 1）

Fig.9 Effect of reduction extent of iron on methane conversion and CO yield during dry reforming reactor（CH4/CO2 = 1）

图10 干重整反应器，合成气H2/CO摩尔比随反应时间的变化

Fig.10 Effect of reaction time on H2/CO molar ratio of syngas during dry reforming reactor

图11 蒸汽氧化反应器中氢气产量和纯度随干重整阶段反应时间的变化

Fig.11 Purity and production of hydrogen in steam oxidation reactor as function of duration of dry reforming reactor

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化学链干重整联合制氢热力学分析及实验

Thermodynamic and experimental analysis of chemical looping dry reforming with hydrogen production system

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