international journal of hydrogen energy 35 (2010) 11810–11815

Available at www.sciencedirect.com

journal homepage: www.elsevier.com/locate/he

Hydrogen production from lignite via supercritical water

in flow-type reactor

Rong Zhang*, Wei Jiang, Leming Cheng, Bingjie Sun, Dongkai Sun, Jicheng Bi
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, No. 27 South Taoyuan Road,
Taiyuan 030001, China

article info abstract

Article history: A supercritical water reactor with throughput of 10 kg/h was set up, which was operated
Received 29 September 2009 with continuous feeding of coal water slurry. The effects of reaction temperature (500–
Received in revised form 650  C), pressure (20.0–30.0 MPa), Ca/C molar ratio (0–0.45) and O/C molar ratio (0–0.35) on
7 January 2010 the hydrogen generation characteristics were investigated. It is found that there is
Accepted 9 January 2010 a notable increase in the hydrogen content and yield with the increase of reaction
Available online 29 March 2010 temperature. The hydrogen yield increases from 24.67 ml/g to 135.73 ml/g when the
temperature increases from 500  C to 650  C. The contents of CO2 in gas product decrease,
Keywords: while that of hydrogen increases with the increase of Ca/C molar ratio. At Ca/C molar ratio
Supercritical water of 0.45, nearly all CO2 is fixed. Correspondingly, the content of hydrogen in gas is 73.29%,
Lignite and the yield of hydrogen is 348.30 ml/g compared to 135.42 ml/g in the absent of CaO.
Hydrogen Moreover, both of CaO and KOH catalyze gasification and water-shift reaction. The
Catalyst formation of hydrogen and the carbon gasification efficiency are improved by the added
Partial oxidation H2O2 when O/C ratio is less than 0.3.
ª 2010 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved.

1. Introduction directly converted to hydrogen, hydrocarbons and fuels in

supercritical water. Because of the high water excess,
Hydrogen is an environmentally clean energy source since it hydrogen and carbon dioxide are generated at temperatures
generates no pollutants. It is well known that reserves of solid of 600  C or higher instead of the synthesis gas produced
fossil fuels give a much bigger energy independence during classical gasification processes. In this way, one
compared with liquid and gaseous fossil fuels (oil and natural process step of classical hydrogen generation would no longer
gas). Coal is likely to play a key role for large scale hydrogen be required, namely, the conversion of CO with water into H2
production, as required for the development of the hydrogen and CO2.
economy. Thermochemical process, such as steam gasifica- Previous studies using batch reactor showed that water,
tion, is currently being industrialization to obtain gases from calcium oxide and potassium hydroxide are reliable cata-
coal [1]. Since the specific objective is to produce a maximum lysts for the gasification of biomass and low-rank coal [5–7].
of hydrogen, further improvement must be made to convert For the supercritical water gasification process to become
the coal feedstock to a gas rich in hydrogen. Recently, low- a practical technology as soon as possible, experiments
rank coal treatment in supercritical water (SCW) has attrac- using a larger-scale continuous flow reaction system are
ted much attention [2–4]. Low-rank coal without drying can be needed. Moreover, it is difficult to complete gasification of

* Corresponding author. Tel.: þ86 351 4151519; fax: þ86 351 4072379.
E-mail address: [email protected] (R. Zhang).
0360-3199/$ – see front matter ª 2010 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2010.01.029
 international journal of hydrogen energy 35 (2010) 11810–11815 11811

coal at rather low temperature. Increase the temperature to 250  C. Water was supplied with a plunger pump with
enhance gasification efficiency is a drawback to supercrit- maximum feed rate of 7 l/h to a preheater set at 700  C. The
ical water gasification process. Yield stress of metals feed slurry and preheated water with flow rate ratio of 1:3
decreases as temperature increases, leading to thicker wall were mixed at the reactor inlet with a mixing tee to rapidly
and thus larger amount of materials needed for reactor heat incoming coal slurry. The tubular reactor is 1000 mm
fabrication [8]. To achieve high gasification efficiency, long, 50 mm id, and 15 mm wall thickness. Following
partial oxidation has been employed. Preliminary study has depressurization, the effluent was phase separated in a low
been conducted by General Atomics [9] and Matsumura pressure gas–liquid separator. Reaction gases were sampled
et al. [8]. In this paper, a flow-type reaction process has and analyzed by gas chromatography. The oil product was
been developed, in which coal and supercritical water can extracted with tetrahydrofuran. In the runs with CaO, solid
be continuously introduced and the gas and solid reaction sample was dissolved by an excess amount of hydrochloric
products continuously removed. The effects of reaction acid solution. According to the volume of CO2 released, the
conditions, calcium oxide, potassium hydroxide, and partial content of carbon as carbonate was determined. Calibration of
oxidation on the conversion and product yields were this determination was conducted with a pure CaCO3 regent.
discussed. Carbon gasification efficiency and main gas yields were
calculated as follows:

Carbon gasification efficiencyð%Þ ¼ ðcarbon in gaseous products=carbon in coal feedÞ100

molar fraction  volume of gas product
gas yield ðml=g; dafÞ ¼
coal feed; daf

Lignite from Yunnan Province of China was used in this

2. Experimental
study. The properties of coal sample are shown in Table 1.

A schematic diagram of flow-type apparatus with throughput

of 10 kg/h is shown in Fig. 1. The apparatus mainly consists of 3. Results and discussions
coal slurry and water supply system, preheater, reactor, back-
pressure regulator and gas–liquid separator. The coal sample 3.1. Influence of feed dry meter content
was crushed and grounded in a ball mill and then sieved to
less than 200 mesh. The test slurries were made by mixing The dependence of gasification efficiency on the dry matter
coal powder with water and additives. The ratio in weight of content or carbon input is of special interest. The more
additive to coal powder was 1%. The pressurized slurry was hydrogen that can be produced from 1 kg coal, the lower the
fed to the preheater where it is preheated to a temperature of production price of hydrogen will be. Product yields at 600  C,

6
7

2 8
5
1

9 10
4

12
3
11

Fig. 1 – Flow diagram of flow-type reaction system 1.water feeder I; 2.water preheater; 3.water feeder II; 4.coal water slurry
feeder; 5.coal water slurry preheater; 6.furnace; 7.reactor; 8.back-pressure valve; 9.separator; 10.sampling tank; 11.overfall
tank; 12. flowmeter.
11812 international journal of hydrogen energy 35 (2010) 11810–11815

Table 1 – The proximate and ultimate analyses of coal 500

sample. C2-C4 CH4 H2 CO CO2
Proximate analysis/ Ultimate analysis/
wt%, air dry base wt%, daf 400

M A V C H N S Oa

Yield (ml/g,daf)
14.75 10.89 40.96 67.86 5.46 1.41 2.64 22.63 300

a By difference

200
25 MPa with various coal slurry concentrations are shown in
Table 2. The increase of slurry concentration leads to
a decrease in gasification efficiency, which conformed what 100
was found by Antal et al. [10] and Kruse et al. [11] with biomass
model compounds in a tubular reactor. Fig. 2 shows the yields
0
of gaseous products. The yields of H2 and CO2 decrease by 25%
20 30 40 50
while that of CH4 increases by 50% with an increase of the coal
Slurry Concentration(wt.%)
slurry concentration from 20% to 50%. It suggests that part of
CH4 is formed by reaction of char and hydrogen. More CH4 is Fig. 2 – Yields of gas products at various slurry
formed under high slurry concentration might due to the high concentrations (Conditions: 600 8C, 25 MPa).
partial pressure of hydrogen under these conditions.
The water/carbon ratio decreases with the increase of
slurry concentration, which is unfavorable to the gasification CH3, and –O–R by direct hydrolysis. Since a significant fraction
reaction. In addition it has been proposed that water and of low-rank coal fragments are linked by carbon–oxygen
hydrogen molecules are adsorbed competitively onto the bonds, a higher conversion can be obtained due to the ability
same active sites [12]. The powerful inhibiting effect of of water to participate in the hydrolysis reaction. Adschiri
hydrogen on the rate of gasification has been observed [13–15]. et al. [2] reported that hydrolysis rate increased with the
Carbon gasification rate decreased linearly as the partial increase of water density. This is also supported by many
pressure of hydrogen increased. studies of model compounds [16–18]. Therefore, an increase in
water pressure enhances coal conversion in SCW.
3.2. Effect of temperature and pressure The importance of methane generation during carbon
gasification at elevated pressures has been pointed out by
A comparison of the results obtained under different condi- previous researchers. Most of them detected an increase in
tion shows that temperature has a considerable effect on the the rate of methane generation with increasing water vapor
yields and composition of the products. The yields of gas pressure. Goring et al. [19] and Zielke and Gorin [15] revealed
products at different temperature are shown in Fig. 3. A two- a strong dependence of the methane formation rate on steam
fold increase is observed when temperature increasing from pressures up to 3.0 MPa at 870  C, indicating the participation
500  C to 650  C. At lower temperatures pyrolysis of coal is the of water in the methane generation reaction. The proportional
main reaction. The reaction between coal and SCW and tar generation of methane with respect to the steam vapor pres-
reforming reaction might occur at temperatures higher then sure was observed in the temperature range of 750–830  C at
600  C. As a result the yield of hydrogen increases from
24.67 ml/g to 135.73 ml/g.
Fig. 4 shows gas yields under different pressure at 600  C.
The yields of H2, CH4 and CO2 increase with the increase of
pressure, while those of other compounds change slightly.
The density and solubility parameter of water increase with
the increase of pressure, therefore, enhancing the extraction
of products from the lignite matrix. Moreover, SCW reacts
with the low-energy linkage in lignite structure, such as –O–

Table 2 – Carbon gasification efficiency and product yields

at various slurry concentrations.
Concentration (wt%) 20 30 40 50

Carbon gasification 23.26 23.14 23.00 21.26

efficiency (%)
Gas (wt%)) 31.37 30.93 28.13 26.07
Oil (wt%) 10.26 7.54 7.36 5.81
Fig. 3 – Yields of gas products at various temperatures
Char (wt%) 48.13 53.89 56.04 64.84
(Conditions: 25 MPa, coal slurry concentration 40 wt%).
 international journal of hydrogen energy 35 (2010) 11810–11815 11813

CH4 C2-C4 H2 CO CO2

100

Gas composition (mol%)

80

60

40

20

0
0 0.1 0.15 0.35 0.45
Ca/C molar ratio

Fig. 4 – Yields of gas products at various pressures Fig. 5 – Composition of gas products at various Ca/C ratios
(Conditions: 600 8C, coal slurry concentration 40 wt%). (Conditions: 600 8C, 25 MPa, coal slurry concentration
20 wt%).

steam pressures as high as 4.7 MPa [20]. van Heek et al. [21]
combustible gases produced are H2, CO and CH4 with little
conducted a nonisothermal kinetic study of coal gasification
amount of C2–C4 hydrocarbons. As the Ca/C ratio increases,
in steam at pressures up to 7.1 MPa, and found two mecha-
CO2 diminishes in the gaseous product with an increase in the
nisms of methane generation: pyrolysis of coal observed at
amount of carbonate, indicating CO2 capture by CaO. With the
lower temperatures (less than 700  C), and reaction between
fixation of CO2, trace CO was observed, while the fraction of H2
steam and coal at higher temperatures (higher than 600  C).
increases remarkably. It suggests that CO convert to CO2 and
Methane formation by pyrolysis was not intensified by pres-
H2 via water–gas shift reaction. At Ca/C molar ratio of 0.45,
sure, but the rate of reaction between steam and char clearly
nearly all CO2 is fixed. Correspondingly, the content of
increased with pressure.
hydrogen in gas is 73.29%, and the yield of hydrogen is
3.3. Effect of Ca/C molar ratio 348.30 ml/g compared to 135.42 ml/g in the absent of CaO.
It is noteworthy that at a Ca/C ratio of 0.45, CO2 sorption is
Coal gasification in supercritical water in the presence of near 100%, while seventy percent of the calcium is utilized as
calcium oxide can obtain gas abundant in hydrogen without CaCO3. The XRD pattern for the residue suggests the forma-
the emission of CO2. Table 3 lists the conversions and yields tion of complex inorganic compounds, such as mayenite
obtained at temperatures around 600  C and pressures around (Ca12Al14O33), calcium silicate (Ca2SiO4) and yoshiokaite
25 MPa as function of Ca/C molar ratio. At a Ca/C ratio of 0.45, (Ca(Al,Si)2O4). It indicates that calcium oxide tend to undergo
the carbon gasification efficiency increases from 23.00% to a solid–solid reaction with coal-derived ash components such
47.22%. Correspondingly, the yield of gas increases from as silicon (Si) and aluminum (Al).
29.61% to 63.33% compared with in the absence of CaO. The An increase in the gasification efficiency tends to be
yield of oil product decreases slightly with the increase of Ca/C remarkable with the increase of Ca/C ratio, indicating that
molar ratio. CaO promotes the depolymerization and gasification of lignite
As shown in Fig. 5, in the absence of CaO, CO2 is the major in supercritical water. Moreover, the oil yield decreases while
component in gaseous product. Near 50% of the gas formed is
CO2, indicating the high carboxylic content of lignite. The

Table 3 – Carbon gasification efficiency and product yields

at various Ca/C ratios.
Ca/C molar ratio 0 0.15 0.35 0.45

Carbon gasified (%) 23.00 33.32 43.64 47.22

Gas (wt%)) 29.61 45.02 60.24 63.33
Oil (wt%) 5.79 3.07 2.99 2.96
Char (wt%) 57.91 40.38 22.27 20.88
Main gas yield
(ml/g,daf)
H2 135.42 253.10 281.04 348.30
CO2 211.67 106.13 88.96 5.07
CO 19.58 0 0 0
CH4 40.42 64.08 101.89 93.93
Fig. 6 – Effect of KOH on gas products yields (Conditions:
C2–C4 12.08 29.05 20.35 27.96
600 8C, 25 MPa, coal slurry concentration 20 wt%).
11814 international journal of hydrogen energy 35 (2010) 11810–11815

Fig. 7 – Effect of O/C ratio on temperature profiles Fig. 9 – Effect of O/C ratio on gas products yields
(Conditions: 600 8C, 25 MPa, coal slurry concentration (Conditions: 600 8C, 25 MPa, coal slurry concentration
20 wt%). 20 wt%).

those of H2 and CO2 increase. It suggests that CaO may cata- hydroxide on product yields at 600  C and 25 MPa. An increase
lyze the steam reforming of hydrocarbons to hydrogen. As of the KOH amount from 0 to 4.1% leads to a diminution of oil
mentioned above, trace CO was detected with the fixation of yield and a corresponding increase in hydrogen and carbon
CO2. Elliott et al. [22] proposed a cyclic system with three dioxide yield. The yields of hydrogen and CO2 increase by
intermediate anions for catalysis of the water–gas shift reac- 103.48 ml/g and 78.31 ml/g, respectively. However, the yield of
tion by basic aqueous solutions under subcritical state. They CO decreases by 70% due to the catalytic activity of potassium
suggested that a carbonate ion reacts with water to form for the water–gas shift reaction.
hydroxide and carbon dioxide. The hydroxide ion reacts with KOH is likely to promote lignite conversion by the attack of
carbon monoxide to generate formate ion. The formate an alkali ion against the oxygen atom and thus accelerates the
decomposes to carbonate and formaldehyde which in turn cleavage of the macromolecular structure of lignite into small
generates hydrogen by decomposition. Any basic catalyst molecules [7]. The study of the reactions occurring during
precursor which generates one of the three catalytic species activation of an anthracite by KOH or NaOH [23] has shown
can promote the water-shift reaction. Therefore, the catalytic that chemical activation consists of a reaction between the
role of CaO is considered to be three effects, one on the gasi- carbon and the hydroxide. The reaction products are the
fication of carbon, one on the steam reforming of hydrocar- metal carbonate, hydrogen and some metallic compound.
bons, and the other on water-shift reaction.
6KOH þ 2C / 2K þ 3H2 þ 2K2CO3 (1)
3.4. Effect of KOH
McKee [24] proposed sequences of cyclic redox processes
A pronounced effect of the addition of KOH has been involving reaction of the salt with the carbon substrate and
observed. Carbon gasification efficiency increases from 23.82% subsequent reoxidation by reaction with water vapor to
to 31.53% with the increase of the amount of KOH added. Fig. 6 explain the catalytic effects of the carbonate of potassium.
shows the influence of different amount of potassium
K2CO3 þ 2C / 2K þ 3CO (2)

2K þ 2H2O / 2KOH þ H2 (3)

3.5. Effect of partial oxidation

It is known that the formation of high molecular weight

hydrocarbons (tar) is a function of feed heat-up time [25], with
longer heat-up times yielding higher amounts of these prod-
ucts. In the presence of sub stoichiometric quantities of an
oxidant, the molecular dispersion of the organic and oxidant
reactants within a single phase, in conjunction with the high
diffusivity, low viscosity, and relatively dense SCW reaction
medium, is conducive to rapid oxidation reactions. Therefore,
Fig. 8 – Product yields at various O/C ratios (Conditions: a high feedstock heating rate could achieve by heat released
600 8C, 25 MPa, coal slurry concentration 20 wt%). by partial oxidation.
 international journal of hydrogen energy 35 (2010) 11810–11815 11815

Temperature along the length of the reactor is shown in a continuous flowing system. Int J Hydrogen Energy 2010;
Fig. 7. Compared with water flow, the temperature at the 35(13):7151–60.
reactor inlet falls by about 40  C after the mixing of coal slurry [4] Lin SY, Suzuki Y, Hatano H, Harada M. Hydrogen production
from hydrocarbon by integration of water-carbon reaction
and SCW, due to pyrolysis and gasification of coal. The
and carbon dioxide removal (HyPr-ring method). Energy
temperature at the reactor inlet increases and the gradient of Fuels 2001;15:339–43.
temperature along the reactor is reduced with the increase of [5] Lin SY, Harada M, Suzuki Y, Hatano H. CO2 separation during
O/C ratio. It is clearly observed that heat released by oxidation hydrocarbon gasification. Energy 2005;30:2186–93.
of reactive molecule raise the temperature rapidly. [6] Schmieder H, Abeln J, Boukis N, Dinjus E, Kruse A, Kluth M,
Figs. 8 and 9 show the effect of O/C molar ratio on the et al. Hydrothermal gasification of biomass and organic
products yields at 600  C. The carbon gasification efficiency wastes. J Supercrit Fluids 2000;17:145–53.
[7] Wang J, Takarada T. Role of calcium hydroxide in
increases, while the yield of oil decreases with the increase of
supercritical water gasification of low-rank coal. Energy
O/C molar ratio. By partial oxidation, the yield of carbon dioxide Fuels 2001;15:356–62.
increases, while yields of CO and hydrocarbons decrease. The [8] Matsumura Y, Harada M, Li DY, Komiyama H, Yoshida Y,
yield of hydrogen reaches a maximum of 248.49 ml/g at an O/C Ishitani H. Biomass gasification in supewrcritical water with
ratio of 0.30. Increase in O/C ratio from 0.30 to 0.35 does not partial oxidation. J Jpn Inst Energy 2003;82:919–25.
affect total gas yield so much. However, the yield of hydrogen [9] Hong GT, Spritzer MH. Supercritical water partial oxidation.
Proceedings of the 2002 U.S. DOE Hydrogen program review.
decreases. It suggests that the addition of large amount of
NREL/CP-610–32405.
oxidant results in further oxidation of product gas.
[10] Antal Jr MJ, Allen SG, Schulman D, Xu XD. Biomass gasification
Coal contains phenolic structures and phenols are difficult in supercritical water. Ind Eng Chem Res 2000;39:4040–53.
to be gasified and are referred to the ‘last hurdle’ to get over for [11] Kruse A, Henningsen T, Sinağ A, Pfeiffer J. Biomass
complete gasification [3]. Hydrogen peroxide is usually used as gasification in supercritical water: influence of the dry
a source of free radicals to help decompose the phenolic matter content and the formation of phenols. Ind Eng Chem
compound. So the gasification efficiency in the present of Res 2003;42:3711–7.
[12] Matsumura Y, Xu X, Antal Jr MJ. Gasification characteristics
oxidant is relatively higher. Meanwhile the oxidant reacts
of an activated carbon in supercritical water. Carbon 1997;35:
with the combustible gaseous product. Therefore, there exists 819–24.
proper amount of oxygen to be added. [13] Lussier MG, Zhang Z, Miller DJ. Characterizing rate inhibition
in steam/hydrogen gasification via analysis of adsorbed
hydrogen. Carbon 1998;36:1361–9.
4. Conclusions [14] Matsumoto S, Walker Jr PL. Char gasification in steam at
1123K catalyzed by K, Na, Ca and Fe-effect of H2, H2S and
A supercritical water reactor with continuous feeding of coal COS. Carbon 1986;24:277–85.
water slurry was set up. The decrease in coal slurry concen- [15] Zielke CW, Gorin E. Kinetics of carbon gasification. Ind Eng
Chem 1957;49:396–403.
tration and the increase in temperature lead to an intense
[16] Penninger JML, Kersten RJA, Baur HCL. Reactions of
increase in hydrogen formation. The pressure dependence of
diphenylether in supercritical water-mechanism and
the gas yields is slight. In the presence of calcium oxide gas kinetics. J Supercrit Fluids 1999;16:119–32.
abundant in hydrogen was produced without CO2 emission. It [17] Townsend SH, Klein ST. Dibenzyl ether as a probe into the
was found that both of CaO and KOH could catalyze the supercritical fluid solvent extraction of volatiles from coal
gasification reaction, hydrocarbon reforming reaction, and the with water. Fuel 1985;64:635–8.
water-shift reaction. Moreover, the use of partial oxidation in [18] Townsend SH, Abraham MA, Huppert GL, Klein MT,
Paspekt SC. Solvent effects during reactions in supercritical
situ to rapidly heat the gasification medium, resulting in less
water. Ind Eng Chem Res 1988;27:143–9.
char formation and improved hydrogen yield. [19] Goring GE, Curran GP, Tarbox RP, Gorin E. Kinetics of carbon
gasification by steam–effect of pressure and carbon burn-off
on rate of interaction of low temperature char with steam–
Acknowledgment hydrogen mixtures at 1600 F. Ind Eng Chem 1952;44:1057–65.
[20] Blackwood JD, McGrory F. The carbon-steam reaction at high
pressure. Aust J Chem 1958;11:16–33.
This study was supported by the National Basic Research
[21] van Heek KH, Juntgen H, Peters W. Fundamental studies on
Program of China under grant 2006CB705800. coal gasification in utilization of thermal energy from
nuclear high-temperature reactors. J Inst Fuel 1973;46:
249–58.
references [22] Elliott DC, Hallen RT, Sealock Jr LJ. Aqueous catalyst system
for the water–gas shift reaction. 2. Mechanism of basic
catalysis. Ind Eng Chem Prod Res Dev 1983;22:431–5.
[1] Cormos CC. Assessment of hydrogen and electricity co- [23] Lillo-Rodenas MA, Cazorla-Amoros D, Linares-Solano A.
production schemes based on gasification process with Understanding chemical reactions between carbons and
carbon capture and storage. Int J Hydrogen Energy 2009;34: NaOH and KOH An insight into the chemical activation
6065–77. mechanism. Carbon 2003;41:267–75.
[2] Adschiri T, Sato T, Shibuichi H, Fang Z, Okazaki S, Arai K. [24] McKee DW. Mechanisms of the alkali metal catalysed
Extraction of Taiheiyo coal with supercritical water–HCOOH gasification of carbon. Fuel 1983;62:170–5.
mixture. Fuel 2000;79:243–8. [25] Xu XD, Matsumura Y, Stenberg J, Antal Jr MJ. Carbon-
[3] Li YL, Guo LJ, Zhang XM, Jin H, Lu YJ. Hydrogen production catalyzed gasification of organic feedstocks in supercritical
from coal gasification in supercritical water with water. Ind Eng Chem Res 1996;35:2522–30.