Thermodynamic analysis of steam reforming of glycerol for hydrogen production at atmospheric pressure

doi:10.1007/s11705-020-1975-0

Front. Chem. Sci. Eng.

2021, Vol. 15

Issue (1) : 60-71 https://doi.org/10.1007/s11705-020-1975-0

RESEARCH ARTICLE

Thermodynamic analysis of steam reforming of glycerol for hydrogen production at atmospheric pressure

Ammaru Ismaila¹, Xueli Chen², Xin Gao^1,³(

), Xiaolei Fan¹(

)

¹. Department of Chemical Engineering and Analytical Science, School of Engineering, The University of Manchester, Manchester M13 9PL, UK
². Institute of Clean Coal Technology, East China University of Science and Technology, Shanghai 200237, China
³. School of Chemical Engineering and Technology, National Engineering Research Center of Distillation Technology, Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin University, Tianjin 300072, China

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Abstract

Thermodynamic chemical equilibrium analysis of steam reforming of glycerol (SRG) for selective hydrogen production was performed based on the Gibbs free energy minimisation method. The ideal SRG reaction (C₃H₈O₃+3H₂O→3CO₂+7H₂) and a comprehensive set of side reactions during SRG are considered for the formation of a wide range of products. Specifically, this work focused on the analysis of formation of H_2, CO₂, CO and CH₄ in the gas phase and determination of the carbon free region in SRG under the conditions at atmospheric pressure, 600 K–1100 K and 1.013 × 10⁵–1.013 × 10⁶ Pa with the steam-to-glycerol feed ratios (SGFR) of 1:5–10. The reaction conditions which favoured SRG for H₂ production with minimum coke formation were identifies as: atmospheric pressure, temperatures of 900 K–1050 K and SGFR of 10:1. The influence of using the inert carrier gas (i.e., N₂) in SRG was studied as well at atmospheric pressure. Although the presence of N₂ in the stream decreased the partial pressure of reactants, it was beneficial to improve the equilibrium yield of H₂. Under both conditions of SRG (with/without inert gas), the CH₄ production is minimised, and carbon formation was thermodynamically unfavoured at steam rich conditions of SGFR>5:1.

Keywords steam reforming of glycerol H₂ N₂ carbon deposition thermodynamic analysis Gibbs free energy minimisation

Corresponding Author(s): Xin Gao,Xiaolei Fan

Just Accepted Date: 25 August 2020 Online First Date: 29 October 2020 Issue Date: 12 January 2021

Cite this article:

Ammaru Ismaila,Xueli Chen,Xin Gao, et al. Thermodynamic analysis of steam reforming of glycerol for hydrogen production at atmospheric pressure[J]. Front. Chem. Sci. Eng., 2021, 15(1): 60-71.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-020-1975-0
https://academic.hep.com.cn/fcse/EN/Y2021/V15/I1/60

Parameter	Formula
Glycerol conversion	$X g l y c e r o l (%) = F g l y c e r o l i n − F g l y c e r o l o u t F g l y c e r o l i n × 100$
Hydrogen yield	$Y H 2 (%) = F H 2 o u t 7 × F g l y c e r o l i n × 100$
Yield of C-containing product i	$Y i (%) = ♯ c F i o u t 3 × F g l y c e r o l i n × 100$
Molar fraction	$M F = n i o u t n t o t a l o u t$
Product selectivity	$S i (%) = F i o u t ∑ j F j o u t × 100$
CO₂ ratio	$CO 2 CO x = F CO 2 o u t F CO 2 o u t + F CO o u t$

Tab.1 Definition of various parameters used in the analysis of SRG

Fig.1 Equilibrium constants of reactions occurred in SRG as a function of the process temperature as described by (a) Eqs. (1) and (5) and (b) Eqs. (2-12).

Fig.2 Thermodynamic equilibrium analysis of SRG at atmospheric pressure: effect of temperature and SGFR on (a) molar fraction of H₂; (b) H₂ yield; (c) selectivity to H₂.

Fig.3 Thermodynamic equilibrium analysis of SRG at atmospheric pressure: effect of temperature and SGFR on (a) molar fraction of CH₄ and (b) CH₄ yield.

Fig.4 Thermodynamic equilibrium analysis of SRG at atmospheric pressure: effect of temperature and SGFR on (a) molar fraction of CO; (b) molar fraction of CO₂; (c) CO yield; (d) CO₂ yield.

Fig.5 Effect of temperature and SGFR on the distribution of CO₂/CO_x in SRG at atmospheric pressure.

Fig.6 Thermodynamic equilibrium analysis of SRG at atmospheric pressure: effect of temperature and SGFR on (a) molar fraction of carbon and (b) carbon yield.

Fig.7 Product distribution from SRG as a fucntions of reaction temperatures (at atmospheric pressure, SGFR= 10:1).

Fig.8 Effect of N₂ dilution of the feed on (a) H₂ yield and (b) CH₄ yield as a function of reaction temperature at equilibrium.

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