CIESC Journal ›› 2019, Vol. 70 ›› Issue (S1): 193-201.doi: 10.11949/j.issn.0438-1157.20181282

• Energy and environmental engineering • Previous Articles     Next Articles

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

Daofeng MEI1,2(),Haibo ZHAO3,Shuiping YAN1,2()   

  1. 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:2019-04-26
  • Contact: Shuiping YAN;


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 yNiO, oxygen carrier circulation rate Fs, oxygen carrier conversion variation ΔXs, steam concentration xH2O and air reactor temperature TAR. 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 TAR and ΔXs can lead to the decrease of H2 yield, while rising of Fs 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), TAR close to 1150 K, ΔXs lower than 0.25, Fs higher than 2 kg?s-1 and xH2O 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

CLC Number: 

  • TK 16

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"


h0i /


ai /


bi /


ci /



Table 2

Main parameters and values used for simulations"



NiO: 10~100,

Ca2Al2SiO7: 0~90

沼气组成/%(体积)CH4: 60, CO2: 40


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


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


Effect of ΔXs on H2 yield using various NiO loadings in oxygen carrier"


Effect of Fs on H2 yield, ΔXs and TAR"


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


Heat flow demonstration of a typical CLRa"

Table 3

Distribution of absorbed heat and recoverable heat during typical CLRa"

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