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

doi:10.11949/j.issn.0438-1157.20181282

Abstract

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

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

CLC Number:

TK 16

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.

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.

Figures/Tables 10

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

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

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

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

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

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

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

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

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

Fig.7 Heat flow demonstration of a typical CLRa

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

基于NiO/Ca₂Al₂SiO₇的沼气自热化学链重整制氢热分析动力学模拟

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