Hydrogen Production From Water by Using Hydrogen Sulfide As Reducing Agent in Hydrothermal Reactions
Hydrogen Production From Water by Using Hydrogen Sulfide As Reducing Agent in Hydrothermal Reactions
Hydrogen Production From Water by Using Hydrogen Sulfide As Reducing Agent in Hydrothermal Reactions
Cuixiang Ma1, Fangming Jin1*, Guangyi Zhang1, Xu Zeng1, Jianglin Cao1, Takeo Mogi2, Atsushi Kishita2 and Heiji Enomoto2
1
State Key Laboratory of Pollution Control and Resources Reuse, College of Environmental Science and Engineering,
Tongji University, Shanghai, China
2
Graduate School of Environmental Studies, Tohoku University, Sendai, Japan
fmjin@mail.tongji.edu.cn*
Keywords: Hydrogen; Hydrogen sulfide; Hydrothermal power covers only a rough 0.5% of the total primary energy
reaction; Geothermal energy supply. However, its potential is nearly inexhaustible.
Expert calculations suggest that theoretically more than ten
ABSTRACT times the global energy demand of today could be
generated by geothermal power every year (Yorozu and
The aim of this work is to investigate the hydrogen
Hirano (1987), Young (1989)).
generation from water using H2S as a reducer in
hydrothermal reactions. The effects of reaction temperature, Therefore, hydrogen from water might be generated with
reaction time and initial pH values of reaction solution on H2S acting as a reducer by utilizing low environmental
the production of hydrogen from water were studied. The burden heat source such as geothermal energy for the
experimental results showed that hydrogen could be hydrothermal reaction. The aim of this work is to
produced from water only when the reaction temperature investigate that hydrogen generates from water using H2S
was beyond 200 oC. Moreover, the hydrogen production as reducer in hydrothermal reaction.
strongly depended on the initial pH values of the solution.
Under strong alkaline conditions the hydrogen production
from water was much higher than that under acidity or 2. EXPERIMENT SECTION
weak alkaline conditions. The possible mechanism of 2.1 Experiment Materials
hydrogen production was discussed.
Due to the toxicity of H2S, Na2S·9H2O was selected as test
material to replace H2S. Na2S·9H2O (99.99%) were
1. INTRODUCTION purchasing from Sigma-Aldrich company. Hydrochloric
Our current energy infrastructure is dominated by fossil acid and sodium hydroxide (AR) were used to adjust the
fuels which are being depleted. Considerable efforts are initial pH values of the Na2S aqueous solution.
always under way to search for an alternative to fossil fuels. Hydrochloric acid and sodium hydroxide were obtained
Hydrogen is considered as a nonpolluting, efficient, from Sino-pharm Chemical Reagent Co., Ltd.
inexhaustible energy carrier to alternate fossil fuels for the
future. When hydrogen combines with oxygen, only water 2.2 Experiment Procedure
is formed as the reaction product. Recently, the hydrogen
The experiments were conducted using a batch reactor
production from water has attracted much more attention
made of Hastelloy C-276 with an internal volume of 42 ml.
than that from the other primary sources, such as natural
The batch reactor was connected with the gas-collection
gas, heavy oil, methanol, biomass, wastes and coal, etc
equipment. The typical procedure was as follows: the
(Manuela and Michele (2003), Chang and Laia (2008), Guo
desired amount of Na2S·9H2O and water were added to the
and Lu (2007), Yukihiro and Ki (2008) ).
batch reactor and then sealed. The reactor was put into an
High-temperature water (HTW) is a promising new induced heating furnace and then heated to a desired
medium due to its environmentally benign nature and temperature with an increasing rate of 40 oC / min. The
feasibility in the adjustment of solvent characters (Naoko induced heating furnace was swayed with a frequency of 20
and Phillip (2002)). The hydrogen bonding in water times / min during experiments. After a desired reaction
becomes weaker and less persistent with increasing time, the reactor was removed from the induced heating
temperature and decreasing density in HTW. Furthermore, furnace and cooled by the electric fan. All experiments
HTW exhibits an increasing solubility toward organic were performed with degassed water and the reactor was
compounds. Individual water molecules can actively purged with nitrogen. The reaction time was defined as the
participate in the reaction as reactants and/or as catalysts. time during that reactor was kept at the desired temperature.
Experimental conditions for producing hydrogen are as
It is well known that H2S is a strong reducer. Moreover follows: reaction temperature 200-330 oC, reaction time
dissolved sulfide was detected in hot spring waters (Xu and 0.5-8 h, and water fill 36 %.
Schoonen (1998)). Our past studies on hydrothermal
treatment of sulfur-containing rubber showed that H2S and 2.3 Sample Analysis
hydrogen could be produced. However, the conversion After reaction, liquid and gas samples were collected for
mechanism of hydrogen production in hydrothermal analyses. The gas samples were analyzed by an Angilent
reaction is not yet fully understood. It is mostly likely that 6890 gas chromatographs with thermal conductivity
hydrogen is produced from HTW because H2S acts as a detection (GC-TCD) equipped with molecular sieve 5A
reducer in HTW due to its strong reduction property. The columns. The liquid samples were filtered using a syringe
enormous heat inside the earth can be used continuously for filter with 0.45-µm filter film. The separation of sulfur
heating and electricity generation. Worldwide, geothermal anions in aqueous solution were analyzed by an Agilent
1
Ma et al
Capillary Electrophoresis (CE) system equipped with a UV- examine the other effect on the production of hydrogen
Vis absorbance diode array detector (DAD). The separation from water.
of sulfur species were achieved with indirect UV detection
at two different wavelengths: 214 nm with reference at 372 3.2 Effect of the Initial pH of the Solution on the
nm. Production of Hydrogen from Water
Hydrogen sulfide is a weak diprotic acid and there can exist
3. RESULTS AND DISCUSSION
in three chemical forms in solution, H2S, HS-, and S2- ions.
3.1 Effects of Reaction Temperature and Reaction Time The solution pH determines the distribution of these
on Hydrogen Production from Water reduced sulfur species and is the predominant solution
variable.
To examine the production of hydrogen from water with
H2S as a reducer, hydrothermal experiments were It is generally known that the ionizations of H2S in water
performed with 3 mmol Na2S·9H2O (0.2 mol/L) by varying are carried out by the follow two equilibriums:
the reaction temperature and reaction time. Fig. 1 gives the
production of hydrogen at varying temperatures from 200 (1)
o H 2 S − ←⎯→ H + + HS −
HS − ←⎯→ H + + S 2− (2)
k2
8
7 the ionization constants (pKa) for eq. (1) and eq. (2) are
7.02 and 14, respectively, at ambient temperature. The
6
distribution of dissociation species of H2S at ambient
5 temperature is shown in Fig. 2.
H2 (mmol)
4 0
200 C
0
3 250 C
0 100
280 C
2 0 H2S. HS . S distribution rate (%)
300 C
0
1 330 C 80
H2S
0 -
0 1 2 3 4 5 6 7 8 60 HS
2-
S
Reaction time (h)
40
2-
2
Ma et al
4. CONCLUSIONS
0 Hydrogen could be produced from water only when the
0 1 2 3 4 5 6 reaction temperature was beyond 200 oC. The production of
The amount of Na2S (mmol) hydrogen in strong alkaline conditions was favored than in
the acidity or weak alkaline conditions. The possible
mechanism of hydrogen production was proposed that
hydrogen sulfide were oxidized into S2O32-, SO32- and SO42-
Figure 4: Effect of the amount of Na2S on the ions, meanwhile, hydrogen was produced from water in
production of hydrogen from water (Na2S 1, 2, 3, hydrothermal reaction.
6 mmol, temp. 300 oC, time 4 h, 15 ml solution).
3
Ma et al
Guo,L.J., Lu,Y.J., Zhang, X.M., Ji,C.M. , Guan, Y. and Pe,i Yukihiro, I., Ki, C. P., Tomoo, Y., Hiroshi, T., Bungo, G.
A.X. Catalysis today, 129, (2007), 275-286. and Yasuhiko, F. Progress in Nuclear Energ, 50,
(2008), 438- 442.
Manuela, S., Michele, A. L., Christopher L. M. and
Richard, D. Energy Fuels. 17 (3), (2003), 705 -713. Y. Yorozu, M. Hirano, K. Oka, and Y. Tagawa: Electron
spectroscopy studies on magneto-optical media and
M. Young, The Technical Writer's Handbook. Mill Valley, plastic substrate interface, Proceedings, IEEE Transl.
University Science, CA(1989). J. Magn. Japan, 1987.
Naoko, A. and Phillip, E. S. Chemical Review, 102, (2002).
2725-2750.