基于NiO/Ca2Al2SiO7的沼气自热化学链重整制氢热分析动力学模拟

doi:10.11949/j.issn.0438-1157.20181282

化工学报 ›› 2019, Vol. 70 ›› Issue (S1): 193-201.DOI: 10.11949/j.issn.0438-1157.20181282

基于NiO/Ca₂Al₂SiO₇的沼气自热化学链重整制氢热分析动力学模拟

梅道锋^1,²(),赵海波³,晏水平^1,²()

1. 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. 华中科技大学煤燃烧国家重点实验室，湖北武汉 430074

收稿日期:2018-10-31 修回日期:2018-12-03 出版日期:2019-03-31 发布日期:2019-03-31
通讯作者: 晏水平
作者简介:<named-content content-type="corresp-name">梅道锋</named-content>（1986—），男，博士，讲师，<email>dmei@mail.hzau.edu.cn</email>|晏水平（1980—），男，博士，教授，<email>yanshp@mail.hzau.edu.cn</email>
基金资助:
湖北省自然科学基金项目(2018CFB376);国家自然科学基金项目(51576077，51676080，51776073);中央高校基本科研业务费专项基金(2662016QD043，2015PY077)

Thermodynamics simulation of biogas fueled chemical looping reforming for H₂ generation using NiO/Ca₂Al₂SiO₇

Daofeng MEI^1,²(),Haibo ZHAO³,Shuiping YAN^1,²()

1. Key Laboratory of Agricultural Equipment in Mid-lower Yangtze River, Ministry of Agriculture and Rural Affairs, Wuhan 430070, Hubei, China
2. College of Engineering, Huazhong Agricultural University, Wuhan 430070, Hubei, China
3. State Key Laboratory of Coal Combustion, Huazhong University of Science & Technology, Wuhan 430074, Hubei, China

Received:2018-10-31 Revised:2018-12-03 Online:2019-03-31 Published:2019-03-31
Contact: Shuiping YAN

摘要/Abstract

摘要：

以水泥的主要成分Ca₂Al₂SiO₇为惰性载体，采用热分析动力学研究了NiO/Ca₂Al₂SiO₇氧载体作用下沼气的化学链重整(chemical looping reforming, CLR)制氢性能。通过自编的MATLAB^?代码计算得到430种工况下CLR模拟结果，充分考虑NiO负载率y_NiO、氧载体循环流率F_s、氧载体转化率变化ΔX_s、水蒸气浓度 $x H 2 O$ 及空气反应器温度T_AR的影响。调节氧载体循环流率，可实现对(xNiO+Ca₂Al₂SiO₇)/biogas质量比的控制，进而调整系统总焓变化ΔH，实现自热化学链重整(CLRa)，即ΔH=0。在CLRa状态下，T_AR和ΔX_s的升高均导致H₂产率降低，而F_s增加则有助于提高H₂产率。模拟结果表明，当NiO含量低于10%(质量)、T_AR接近1150 K、ΔX_s小于0.25、F_s大于2 kg?s^-1、 $x H 2 O$ 小于54.5%（体积）时，H₂产率可达最优值1.57(m³ H₂)?(m³ biogas)^-1。对系统的热量平衡分析显示，CLRa能够在自热状态下运行，且反应器出口处气流携带热量能够满足进口处气流的预热需求。

关键词: 制氢, CO₂捕集, NiO基氧载体, 生物燃料, 热力学

Abstract:

Thermodynamics analyses were carried out in biogas fueled chemical looping reforming (CLR) process for H₂ generation, where the main component of cement Ca₂Al₂SiO₇ was used as a support for NiO/Ca₂Al₂SiO₇ oxygen carrier. Around 430 cases for CLR were studied via a home-built MATLAB^? code, considering the effects of NiO loading y_NiO, oxygen carrier circulation rate F_s, oxygen carrier conversion variation ΔX_s, steam concentration $x H 2 O$ and air reactor temperature T_AR. The global enthalpy variation ΔH can be easily tuned to ΔH=0, i.e. CLRa state, by varying the (NiO+Ca₂Al₂SiO₇)/biogas ratio. Under CLRa state, increase of T_AR and ΔX_s can lead to the decrease of H₂ yield, while rising of F_s would result in the higher H₂ yield. The simulation suggests that the optimized H₂ yield of 1.57 (m³ H₂)?(m³ biogas)^-1 can be achieved with NiO loading lower than 10%(mass), T_AR close to 1150 K, ΔX_s lower than 0.25, F_s higher than 2 kg?s^-1 and $x H 2 O$ lower than 54.5%(vol). Heat balance of the global FR, AR and WGS reactors showed that the CLRa can be run under auto-thermal condition, meanwhile heat at exits of reactors can be recovered to be used in the preheating of gases entering reactors.

Key words: hydrogen production, CO₂ capture, NiO based oxygen carrier, biofuel, thermodynamics

中图分类号:

TK 16

梅道锋, 赵海波, 晏水平. 基于NiO/Ca₂Al₂SiO₇的沼气自热化学链重整制氢热分析动力学模拟[J]. 化工学报, 2019, 70(S1): 193-201.

Daofeng MEI, Haibo ZHAO, Shuiping YAN. Thermodynamics simulation of biogas fueled chemical looping reforming for H₂ generation using NiO/Ca₂Al₂SiO₇[J]. CIESC Journal, 2019, 70(S1): 193-201.

图/表 10

图1 以NiO为氧载体沼气(biogas)为燃料的CLRa过程

Fig. 1 Schematic diagram of CLRa using NiO as oxygen carrier and biogas as fuel

表1 各气固组分i对应的h0i及常数ai、bi及ci的取值

Table 1 Values of h0, ai, bi and ci for component i in gaseous and solid phases

组分类别	h₀_i / (kJ?mol^-1)	a_i / (J?(mol?K)^-1)	b_i / (J?(mol?K)^-1)	c_i / (J?(mol?K)^-1)
NiO	-212.51	56.05	-1.03×10^-2	8.50×10^-6
Ni	15.42	20.38	1.59×10^-2	8.50×10^-6
Ca₂Al₂SiO₇	-3904.86	237.58	8.50×10^-3	-2.00×10^-5
CH₄	-74.87	19.86	6.04×10^-2	-1.07×10^-5
H₂O^①	-241.83	30.41	9.54×10^-3	1.18×10^-6
CO₂	-393.51	33.81	2.32×10^-2	-4.65×10^-6
CO	-110.54	26.88	6.94×10^-3	-8.21×10^-7
H₂	0	29.41	-1.55×10^-3	2.35×10^-6
O₂	0	27.65	7.99×10^-3	-1.37×10^-6
N₂	0	27.33	5.13×10^-3	3.97×10^-8

表2 主要模拟条件及相应参数取值

Table 2 Main parameters and values used for simulations

项目	值
氧载体组成/%（质量）	NiO: 10～100, Ca₂Al₂SiO₇: 0～90
沼气组成/%(体积)	CH₄: 60, CO₂: 40
氧载体循环流率F_s/(kg?s^-1)	0.2~10.2
氧载体转化率变化ΔX_s	0.1~1.0
FR进口处水蒸气浓度 $x H 2 O$ /%（体积）	37.5~78.2
AR温度T_AR/K	1150~2500
FR温度T_FR/K	1150

表2 主要模拟条件及相应参数取值

Table 2 Main parameters and values used for simulations

项目	值
氧载体组成/%（质量）	NiO: 10～100, Ca₂Al₂SiO₇: 0～90
沼气组成/%(体积)	CH₄: 60, CO₂: 40
氧载体循环流率F_s/(kg?s^-1)	0.2~10.2
氧载体转化率变化ΔX_s	0.1~1.0
FR进口处水蒸气浓度 $x H 2 O$ /%（体积）	37.5~78.2
AR温度T_AR/K	1150~2500
FR温度T_FR/K	1150

图2 氧载体/沼气质量比(NiO+Ca2Al2SiO7)/biogas对FR出口处气体摩尔流率及ΔH的影响

Fig.2 Effects of (NiO+Ca2Al2SiO7)/biogas mass ratio on gas molar flow rate at FR exit and ΔH

图3 TAR对气体浓度及(NiO+Ca2Al2SiO7)/biogas比的影响

Fig.3 Effect of AR temperature TAR on gas concentration and (NiO+Ca2Al2SiO7)/biogas ratio

图4 采用不同NiO含量的氧载体时转化率ΔXs

Fig.4 Effect of ΔXs on H2 yield using various NiO loadings in oxygen carrier

图5 氧载体的质量流率Fs对H2产率、氧载体转化率变化ΔXs以及TAR的影响

Fig.5 Effect of Fs on H2 yield, ΔXs and TAR

图6 燃料反应器进口处H2O/biogas质量比对气体浓度及(NiO+Ca2Al2SiO7)/biogas的影响

Fig.6 Effect of H2O/biogas ratio at FR inlet on gas concentration and (NiO+Ca2Al2SiO7)/biogas ratio

图7 典型CLRa状态下系统的热量流动

Fig.7 Heat flow demonstration of a typical CLRa

表3 典型CLRa状态下吸热量和可回收热量分布

Table 3 Distribution of absorbed heat and recoverable heat during typical CLRa

热量符号	热量值/MW_th	描述	合计
Q₁	0.05	吸热
Q₂	0.12	吸热
Q₃	0.04	吸热	0.21
Q₄	0.07	放热
Q₅	0.13	放热
Q₆	0.06	放热	0.26

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基于NiO/Ca₂Al₂SiO₇的沼气自热化学链重整制氢热分析动力学模拟

Thermodynamics simulation of biogas fueled chemical looping reforming for H₂ generation using NiO/Ca₂Al₂SiO₇

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