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A comparative thermodynamic analysis and experimental studies on hydrogen synthesis by supercritical water gasification of glucose

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Abstract

A thermodynamic equilibrium analysis of hydrogen (H2) production from supercritical water gasification (SCWG) of glucose was explored based on Gibbs free energy minimization using Soave–Redlich–Kwong equation of state with Boston Mathias alpha function (SRK-BM) property method. The effects of experimental conditions [i.e., glucose concentration (0.1–1.2 M), temperature (773–1073 K), and pressure (22–35 MPa)] on the equilibrium gas product yields and gasification performance were investigated. The temperature of about 923 K, pressure of 23–28 MPa, and glucose concentration being 0.1–0.2 M are justified to provide H2 yield in the order of its stoichiometric value (12 mol) with negligible amounts of CO and CH4. The simulated product yields, gasification efficiency (GE), cold gas efficiency (CGEP), cold gas efficiency of H2 (CGEH2), and calculated heat duty in this study were compared with their respective experimental data taken from the literature. The aforementioned operating conditions correspond to minimum heat duty of 60–107 MW and significant values of CGEP, CGEH2, and GE of 121.1–118.4, 118.4–105.4, and 158.3–151.6 %, respectively. The dissimilarity between the experimental product distributions reported in the literature is related to the reactor material and residence time as well as catalyst type. The current study provided thermodynamic parameters for optimizing the operational condition of glucose SCWG, which may be extended to other biomass supercritical water gasification systems.

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Abbreviations

a ik :

Number of atoms of the kth element present in each molecule of species i

a i :

Attractive parameter of SRK equation

a 1 :

Asymmetric (polar) term in alpha function

A k :

Total moles of kth element in the feed (mol/min)

b i :

Covolume parameter

C i (and d i ):

Constants for Boston–Mathias

F :

Steam flow rate (mol/min)

\(\hat{f}_{i}^{\text{g}}\) :

Fugacity of species i in gas system

\(\hat{f}_{i}^{\text{l}}\) :

Fugacity of species i in the liquid phase

\(\hat{f}_{i}^{\text{s}}\) :

Fugacity of species i in the solid phase

\(\hat{f}_{\text{C}}^{\text{s}}\) :

Fugacity of solid carbon at the operational pressure

\(\hat{f}_{\text{C}}^{\text{v}}\) :

Fugacity of solid carbon at its vapor pressure

\(f_{i}^{{ \circ {\text{g}}}}\) :

Standard state of fugacity of pure component i in the gas phase

\(f_{i}^{{ \circ {\text{l}}}}\) :

Standard state of fugacity of pure component i in the liquid phase

\(f_{i}^{{ \circ {\text{s}}}}\) :

Standard state of fugacity of pure component i in the solid phase

\(f_{i}^{{ * , {\text{l }}}}\) :

Liquid fugacity of pure species i at mixture temperature

\(\overline{G}_{i}\) :

Partial molar Gibbs free energy of each component i in each phase (kJ/mol)

\(G_{i,e}^{ \circ }\) :

Standard Gibbs free energy of element i (kJ/mol)

\(G_{i}^{{ \circ {\text{g}}}}\) :

Standard Gibbs free energy of species i in the gas phase (kJ/mol)

\(G_{i}^{{ \circ {\text{l}}}}\) :

Standard Gibbs free energy of species i in the liquid phase (kJ/mol)

\(G_{i}^{{ \circ {\text{s}}}}\) :

Standard Gibbs free energy of species i in the solid phase (kJ/mol)

\(G_{\text{C}}^{{ \circ {\text{s}}}}\) :

Standard Gibbs free energy of pure solid carbon (kJ/mol)

\(G_{{ ( {\text{T,P)}}}}^{\text{t}}\) :

Total Gibbs free energy of three phases (kJ)

\(\Delta G_{\text{fi }}^{ \circ }\) :

Standard Gibbs free energy of formation for species i (kJ/mol)

\(\Delta G_{\text{fi}}^{{ \circ {\text{g}}}}\) :

Standard Gibbs free energy of formation for species i in the gas phase (kJ/mol)

\(\Delta G_{\text{r}}^{ \circ }\) :

Gibbs free energy change of reaction (kJ/mol)

H i :

Henry’s constant

\(l_{ij} \; ( {\text{and}}\;k_{ij} )\) :

Interaction parameters

m i :

Acentric function

\(n_{i }\) :

Molar flow rate of species i (mol/min)

N :

Number of species in a reaction system

N P :

Number of phases

P :

Pressure of the reaction system (atm)

p :

Polar parameter in Boston–Mathis alpha function

\(P^{ \circ }\) :

Standard-state pressure (1 atm)

\(P_{\text{ci}}\) :

Critical pressure of species i (atm)

\(P_{\text{C}}^{\text{sat}}\) :

Vapor pressure of pure solid carbon at the operational temperature

R :

Molar gas constant (kJ/mol. K)

T :

Temperature of the reaction system (K)

Tci :

Critical temperature of species i (K)

T ri :

Reduced temperature of species i (K)

V m :

Molar volume (m3/mol)

x i (and x j ):

Mole fraction of species i (or j)

y i :

Mole fraction of species i in gas phase

α i :

Alpha function of species i

\(v_{i}\) :

Stoichiometric coefficient of species i

\(\hat{\phi }_{i}^{\text{g}}\) :

Fugacity coefficient of species i in the gas phase

\(\hat{\phi }_{i}^{\text{l}}\) :

Fugacity coefficient of species i in the liquid phase

γ i :

Activity coefficient of the supercritical species

γ *i :

Normalized activity coefficient for the dissolved gases in the liquid phase

γ ∞ i :

Infinite dilution activity coefficient of species i in the mixture

γ l i :

Liquid activity coefficient of species i

ω i :

Acentric factor

g:

Gas phase

l:

Liquid phase

s:

Solid phase

t:

Total

i (and j):

Component in the mixture

k :

Element in each molecule

SCWG:

Supercritical water gasification

SCW:

Supercritical water

WGS:

Water gas shift

AC:

Activated carbon

MDR:

CH4 dry reforming

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Acknowledgments

Our gratitude goes to Prof. Zainuddin Manan (Director of PROSPECT) for providing Aspen Plus software at the Simulation Lab, Department of chemical engineering in University Technology Malaysia, Assoc. Prof. Sharifah Rafidah Wan Alwi, and Dr. Tohid Nejad ghaffar Borhani for their kind advice during the manuscript revision.

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Authors and Affiliations

  1. Chemical Reaction Engineering Group (CREG), Department of Chemical Engineering, Universiti Teknologi Malaysia (UTM), 81310, Skudai, Johor, Malaysia

    Maryam Khoshtinat Nikoo

  2. School of Chemical Engineering, Amirkabir University of Technology (Tehran Polytechnic), No. 424, Hafez Avenue, 15914, Tehran, Iran

    Samrand Saeidi

  3. Department of Chemical Engineering, Faculty of Engineering, Ryerson University, Toronto, ON, M5B 2K3, Canada

    Ali Lohi

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  1. Maryam Khoshtinat Nikoo
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Nikoo, M.K., Saeidi, S. & Lohi, A. A comparative thermodynamic analysis and experimental studies on hydrogen synthesis by supercritical water gasification of glucose. Clean Techn Environ Policy 17, 2267–2288 (2015). https://doi.org/10.1007/s10098-015-0965-2

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