Fuel 96 (2012) 250–256

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Fuel
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A novel desulphurization process of coal water slurry via sodium metaborate

electroreduction in the alkaline system
Yafei Shen, Tonghua Sun ⇑, Jinping Jia
School of Environmental Science and Engineering, Shanghai Jiaotong University, Dongchuan Road 800, Shanghai 200240, People’s Republic of China

a r t i c l e i n f o a b s t r a c t

Article history: The present work investigated an alternative desulfurization process for coal water slurry (CWS) using
Received 9 June 2011 sodium metaborate (NaBO2) electroreduction under the ambient conditions. Desulfurization efficiency
Received in revised form 2 January 2012 improved with the increases of NaBO2 concentration, electrolytic time, and electrolytic voltage, while
Accepted 4 January 2012
with the decreases of coal particle size and CWS concentration. Up to 50% desulfurization efficiency
Available online 16 January 2012
was obtained in the 6109 lm (140 mesh) coal under the optimized conditions of CWS (50 g/L), NaBO2
(13.2 g/L), NaOH (1 g/L), electrolytic voltage (3.5 V), and electrolytic time (4 h). Furthermore, the possible
Keywords:
reaction mechanism of electrochemical desulfurization (ED) was that NaBO2 was converted into NaBH4
Coal water slurry (CWS)
Electrochemical desulphurization (ED)
by means of the electrochemical reduction (ER) on the cathode, which induced transformation of pyritic
Sodium borohydride (NaBH4) sulfur (PS) and organic sulfur (OS) in the coal into H2S and S2!, and S2! in the solution was further oxi-
Sodium metaborate (NaBO2) dated into SO2!
4 (SS) on the anode.
! 2012 Elsevier Ltd. All rights reserved.

1. Introduction
Sulfur dioxide (SO2) emission from coal-fired power plants and
refinery operations has been implicated as a cause of acid rain and
other air pollution related problems [1]. The Ministry of Environ-
mental Protection of China issued a new public announcement that
SO2 emission cut down by 6.18 million tons in 2015 (‘‘Emission
standard of air pollutants for fire power plants’’) on September 21,
2011. However, SO2 is one of the significant air pollutants, result-
ing in the further requirements of coal desulfurization. Clean coal
technology is being applied and popularized at an unprecedented
rate in China [2]. CWS, a coal-based liquid fuel, is made of low
ash and low sulfur coals. Deep desulfurization of CWS prior to
combustion can reduce amounts of costs of the follow-up flue
gas desulfurization (FGD) [3]. The search for efficient, economical
and clean desulfurization methods has drawn wide attention
[4–11].
As a clean, efficient and environmental friendly method, the
electrochemical desulfurization (ED) is being given more and more
importance [12–17]. At first, Coughlin and Farooque proposed a
new electrochemical desulfurization of CWS, which generates pure
streams of hydrogen at the cathode [14–16]. Lalvani [13,17] sug-
gested the electrochemical oxidation (EO) for coal desulfurization,
and inorganic sulfur in coal removed by 70–100%, such as pyrite,
but organic sulfur only removed by 40–70%. It can easy to find
excellent oxidizers and get high desulfurization efficiency. After
⇑ Corresponding author.
E-mail address: sunth@sjtu.edu.cn (T. Sun).
that, EO has become the prevailing ED methods in the world, while
electroreductive desulfurization (ER) is rarely reported. During the
process the coal structure is usually destroyed to an appreciable
and significant extent due to oxidation in the anode [18–20]. ER
methods can utilize cathodic reduction to change some chemical
compounds into strong reducing agents which convert S into H2S
and S2!, thus releasing S from coals. Meanwhile, ER can proceed
under mild conditions, as well as producing more high-purity
hydrogen. Thus, this method has a prospective future for coal
desulfurization and hydrogenation, if outstanding reductants are
found.
In the previous work, sodium borohydride (NaBH4), which
showed incomparable advantages: mild conditions, short reaction
time, and high efficiency, was researched for reductive desulfuriza-
tion [3,21]. However, it is confronted with the disadvantages of
expensive, incomplete reaction and excessive waste. Sodium meta-
borate (NaBO2) [22], the end product of the hydrolysis and electro-
oxidation of NaBH4 [31], is much cheaper and stable. It is of great
importance to reconvert NaBO2 into NaBH4. So far, the methods of
recycling NaBH4 from NaBO2 included chemical reduction [23],
mechanical and chemical combination [23–25] and electrochemi-
cal reduction [26–29]. Electrochemical method can realize boron
recycling only by the process of discharge and recharge Eqs. (1)
and (2) [30]. If electric work is provided, the following reactions
[31] may be happened:
Cathode reaction : BO!2 þ 6H2 O þ 8e! ! BH!4 þ 8OH! E0c ¼ !1:24 V
ð1Þ

0016-2361/$ - see front matter ! 2012 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2012.01.003
 Y. Shen et al. / Fuel 96 (2012) 250–256 251

Table 1 110 "C in an oven, the solid residue of CWS was ground and passed
The plus voltage values with different ionic activity rate (PO2 = 1000 Pa). through different sizes of sieve. The analytical results of original
a [NaBO2]/a 1:1 1:2 1:3 1:4 1:5 1:6 1:7 CWS sample are given in Table 3. NaBO2)4H2O (>99%, AR) and
[NaBH4] NaOH (>96%, AR) were purchased from Sinopharm Chemical Re-
DE0 (V) 2.469 2.447 2.434 2.424 2.417 2.395 2.321 agent Co. Ltd., China. All chemicals were used for experiments
without any further purification. And the experimental solutions
were prepared in the deionized water.
Anode reaction : 4H2 O ! 8e! ! 2O2 þ 8Hþ E0a ¼ 1:229 V ð2Þ
2.2. Experimental apparatus and procedure
DG ¼ !ZFðEa ! Ec Þ ð3Þ
The experimental set-up (volume: 400 ml) is shown in Fig. 1a. It
Ec ¼ Ec;e ! gc ð4Þ
mainly consists of five parts: magnetic stirring apparatus, electro-
Ea ¼ Ea;e þ ga ð5Þ lytic cell, electrodes (anode/cathode), power supply, and adsorp-
Substituting Eqs. (4), (5) into Eq. (3), and assumption tion bottle of tail gas (H2O2, aq.). The cathode and anode were
DE0 ¼ ga ¼ gc , it can get the Nernst Eq. (6) [32]. Table 1 shows the prepared by acid washing of lead (Pb) and graphite (C) plates
plus voltage values with different ionic activity rate. When the respectively, which are both 5 * 5 cm2 of their effective areas.
external voltage (DE0 ) is greater than 2.469 V, possibly DG0m < 0. It
is suggested that B recycling can be realized by electrochemistry. 2.2.1. General procedure (Fig. 1b)
Our aim is to convert NaBO2 into NaBH4 by means of electroreduc- 200 ml the blended electrolyte of NaBO2 (13.2 g/L) and NaOH
tion. By NaBH4 reduction, sulfides in coal can be translated into H2S (1 g/L) were added in the electrolytic cell, and then mixed with
and S2! on the cathode, and S2! in the solution is further oxidated the prepared CWS powder (10 g) at the speed of 300 rpm in one
into SO2!
4 on the anode. minute. After the DC was turned on, the reaction occurred sponta-
(" # ) neously, and the stirring speed was adjusted to 100 rpm. The stir-
RT a½NaBO2 ' ring was not suspended until the electrolysis completed (5 h). At
DG ¼ !ZF ðE0a ! E0c Þ ! ln ! D E 0
ð6Þ
ZF a½NaBH4 ' ( ½Po2 =P h '2 last, clean CWS powder could be obtained by filtering, leaching
and drying.
2. Experimental section
2.3. Analysis methods
2.1. Materials
The proximate analysis of the solid CWS sample followed the
A CWS sample used in the investigation was collected from Chinese standard methods (GB/T 212-2001). Total sulfur (TS) was
Dongli Fuels Co. Ltd. (Shanghai, China). After being dried at determined using the elemental analyzer (Elementar Vario EL III).

Fig. 1. Schematic of experimental set-up and general procedure of the ED process.

252 Y. Shen et al. / Fuel 96 (2012) 250–256

The sulfate sulfur (SS) was analyzed gravimetrically using the Esc-
hka Method. Pyritic sulfur (PS) was analyzed by measuring the
amount of iron contained in the pyritic state (GB/T 215-2003). Or-
ganic sulfur (OS) was estimated by the difference. Concentration of
NaBH4 was measured by iodometric titration [33,34]. The concen-
tration of SO2!4 in the filtrate was determined by the Ion Chroma-
tography (830 IC Metrohm), and S in the adsorption bottle was
determined by the Inductively Coupled Plasma analysis (‘‘ICP’’, Iris
Advantage 1000, Thermo king-cord Co.) Analyses of coal calorific va-
lue and ignition temperature were accorded to the Chinese Stan-
dards of GB/T 213-2003 and GB/T 18511-2001, respectively. The
OS structures were analyzed by the Fourier Transform Infrared
(‘‘FTIR’’, EQUINOX 55, Bruker). And the minerals in coal were ana-
lyzed by X-ray Diffractometer (‘‘XRD’’, D8 ADVANCE, Bruker). The
data was presented as the average of two replicates (data error
<5%) in each treatment. Desulfurization efficiency was calculated
by the following formula, where TS1 is sulfur content in the original
Fig. 2. Effect of electrolytic time. Process conditions: CWS (25 g/L, 6109 lm),
CWS sample, and TS2 is sulfur content in the treated CWS sample.
electrolytic time (4 h), NaBO2 (20 g/L), NaOH (3 g/L), electrolytic voltage (4 V).

TS1 ! TS2
Desulfurization Efficiency ðwt%Þ ¼ * 100%
TS1

3. Results and discussions

3.1. Effect of electrolytic time

Desulfurization efficiency increased before 4 h, after which, the

growth trend decreased (Fig. 2). Given a certain current density,
increasing the electrolytic time would increase the electric quan-
tity on electrode, conducing to improve desulfurization efficiency.
Furthermore, NaBH4 was generated during the desulfurization pro-
cess and its concentration increased with increasing of electrolytic
time in accordance with the empirical curve below (red1 dotted
line in Fig. 2). It is suggested that electrolytic time is of great impor-
tance to the CWS desulfurization and NaBH4 production. Possibly
the generation rate is faster than the hydrolysis rate of NaBH4 due Fig. 3. Effect of CWS concentration. Process conditions: electrolytic time (4 h),
to the alkaline condition. However, longer electrolytic time can re- NaBO2 (20 g/L), NaOH (3 g/L), electrolytic voltage (4 V).
duce the economical efficiency, so 4 h is considered as the appropri-
ate processing time.
3.3. Effect of NaBO2 concentration
Empirical equation: C = –6.38 exp (–t/10.54) + 6.40 (R2 = 0.99845),
where C is the concentration of NaBH4 (mM), and t (0–5 h) is the
NaBO2 concentration is a key factor of producing NaBH4, so it is
electrolytic time (h).
significant to the present ED as well. Desulfurization efficiency in-
creased with the increase of NaBO2 concentration. In absence of
NaBO2 (0 g/L), the desulfurization efficiency was only 15%. When
3.2. Effect of CWS concentration
NaBO2 concentration increased from 6.6 to 13.2 g/L, the desulfur-
ization efficiency increased rapidly (Fig. 4). At the NaBO2 concentra-
CWS concentration has effect on the mass transfer, and the
tion of more than 13.2 g/L, the growth tendency of desulfurization
probability of contact with the electrode surface [20]. Low CWS
efficiency was slow down. It can conclude that NaBO2 indeed
concentration was benefit for mass transfer, but it decreased the
contributes to improve the desulfurization efficiency. Meanwhile,
contact frequency of electrodes and coal particles, to some extent,
NaBO2 concentration will not be of great importance to deep desul-
resulting in the efficiency reduction of electrochemical reaction;
furization, when it reaches to a certain value (13.2 g/L). And the pro-
while high CWS concentration inhibited mass transfer, accordingly
duction of NaBH4 and desulfurization efficiency may depend on
with the decrease of desulfurization efficiency. As shown in Fig. 3,
other important factors, such as electrolytic voltage.
the desulfurization efficiency was little affected when the CWS
concentration was below 50 g/L, beyond that, the desulfurization
efficiency dramatically decreased with the increase of CWS con- 3.4. Effect of electrolytic voltage
centration. The maximum value of desulfurization efficiency was
observed at the CWS concentration of 50 g/L, where the total sulfur Desulfurization efficiency can be improved by increasing elec-
removal was about 300 mg/L {Total Sulfur Removal (mg/L) = Total trolytic voltage. After 4 h, the growth tendency of desulfurization
Sulfur Content (%) ⁄ Desulfurization Efficiency (%) ⁄ CWS Concentra- efficiency reduced, when the electrolytic voltage was greater than
tion (g/L)⁄ 103 (mg/g)}. 3.5 V (Fig. 5). Increasing the voltage could profoundly enhance the
electrolysis and desulfurization rates, but it was not the prerequi-
1
For interpretation of color in Fig. 2, the reader is referred to the web version of site to further improve the desulfurization efficiency. Additionally,
this article. high voltage (HV) can destroy the coal quality and increase the pro-
 Y. Shen et al. / Fuel 96 (2012) 250–256
Fig. 4. Effect of NaBO2 concentration. Process conditions: CWS (50 g/L, 6109 lm),
electrolytic time (4 h), NaOH (3 g/L), electrolytic voltage (4 V).
Fig. 5. Effect of electrolytic voltage. Process conditions: CWS (50 g/L, 6109 lm),
electrolytic time (4 h), NaBO2 (13.2 g/L), NaOH (3 g/L).
cessing expense. Thus, 3.5 V was chosen for optimum electrolytic
voltage.
3.5. Effect of sodium hydroxide (NaOH) concentration
It is well known that NaBH4 hydrolyzes spontaneously when
stored as aqueous solution. NaBH4 has strong reducibility, but its
aqueous solution is unstable. This hydrolysis reaction can be
greatly inhibited by addition of NaOH. Rong [35] indicated the
introduction of sodium hydroxide could inhibit the hydrolysis of
NaBH4. At room temperature and pH < 9, NaBH4 can hydrolyze
spontaneously in the solution. For example, when pH value is 8,
more than 50% of NaBH4 can hydrolyze off within 30 s. However,
the half-life of NaBH4 is 430 days when pH value is 14. This means
that NaBH4 can be stable in the strong alkaline solutions. There are
two contradictory effects by increasing NaOH concentration. On
one hand, it helps create O2 and other active oxygen free radicals
()OH, O2), and O)) on the anode to promote the indirect oxidation;
On the other hand, it can alleviate NaBH4 hydrolysis in the alkaline
medium, reducing desulfurization efficiency. So it is necessary to
investigate a reasonable NaOH concentration for the ED. As shown
in Fig. 6, the desulfurization efficiency increased initially, and then
decreased with the increase of NaOH concentration. The maximum
value of desulfurization efficiency (46%) was obtained when NaOH
253
Fig. 6. Effect of NaOH concentration. Process conditions: CWS (50 g/L, 6109 lm),
electrolytic time (4 h), NaBO2 (13.2 g/L), electrolytic voltage (4 V).
Fig. 7. Effect of coal particle size. Process conditions: CWS (50 g/L), electrolytic time
(4 h), NaBO2 (13.2 g/L), NaOH (1 g/L), electrolytic voltage (4 V).
concentration was about 2 g/L, corresponding to pH = 13 or so. Be-
sides, high concentration of NaOH can increase the ash content and
destroy the coal quality severely. Experimentally, NaOH concentra-
tion is controlled at 1–2 g/L, at which the desulfurization efficiency
can reach more than 45%.
3.6. Effect of coal particle size
Polarization potential generated by the constant voltage
electrolysis presents the slot voltage decreasing with the decrease
of coal particle size. The reason is that small particle size has higher
mass transfer efficiency in favorable of dispersion. Thus, desulfur-
ization efficiency also increased with the decrease of coal particle
size. Significantly, the desulfurization efficiency got greatly im-
proved, when the coal particle size was 6120 lm. As shown in
Fig. 7, coal particle size 6109 lm was used in the following
experiments.
3.7. Electrode
Compared with the couple electrodes of Ti/Pb and C/Cu, C/Zn,
Pb/Pb and C/Pb exhibited higher desulfurization efficiency
(Fig. 8). Zn has excellent catalytic activity as cathode material,
but some weak reductive metal ions, e.g. Fe2+ can be reduced into
254 Y. Shen et al. / Fuel 96 (2012) 250–256

Table 3
Analytical results of coal physicochemical and combustion characteristics.

Parameters Original coal Treated coal

Ultimate analysis (wt.%, as received)
C 73.66 71.48
H 9.48 8.75
N 1.56 1.42
S 1.30 0.66
O(diff.) 14.00 17.69
Multiform sulfurs content (wt.%, db)
TS 1.30 0.64
PS 0.52 0
SS 0.33 0.40
OS(diff.) 0.45 0.24
Combustion characteristic
Calorific value (J/g) 31,790 31,418
Ignition temperature ("C) 348 343
Proximate analysis (wt.%, db)
Ash 12.6 11.4
Volatile matter 23.9 21.3
Fig. 8. Effect of electrode. Process conditions: CWS (50 g/L, 6109 lm), electrolytic Moisturea 3.2 1.8
time (4 h), NaBO2 (13.2 g/L), NaOH (1 g/L), electrolytic voltage (4 V). Fixed carbon 63.5 67.3

0
Fe which is absorbed on the Zn electrode surface. Anodic electrode
(Pb), oxidated into PbO2, is easy to wear down and produce the
additional Pb pollution. Graphite (C) as anodic material has lots
of advantages [36,37]: (a) easy to process and model by electro-
discharge machining; (b) high desulfurization efficiency; (c) low
wastage and price; (d) fine thermostability and conductivity; (e)
anti-corrosion. Thus, C was selected as the optimum anodic elec-
trode here. After the treatment, small amounts of powders (quali-
tative determined as Fe and S) adsorbed in the cathode (Pb)
surface. Above all, negative electrode had almost no loss (Fig. 8).
Electrode materials are various, and reasonable electrodes should
be investigated in all respects. So it will be a big challenge to find
superior electrodes of improving the desulfurization efficiency and
hydrogen production in this ED system.
Processing condition was 50 g/L of CWS (6109 lm), 13.2 g/L of NaBO2, 1 g/L of
NaOH, 3.5 V of electrolytic voltage, and 4 h of electrolytic time.
a
Atmospheric condition, db (dry basis), particle size 6109 lm.
tion (C, mg/L) ( electrolyte volume (V, L). If desulfurization efficiency
was calculated by 50%, 66.5 mg S was removed from the original
coal (133 mg S). So the estimated value (62.19 mg) of TS removal
was approach to the experimental value (66.5 mg). These results
indicated some S in coal was converted into the highest valence
of SO2!
4 in the solution because of anodic oxidation. The others
(51.1% of TS removal) escaped from the reactor in the form of
H2S due to reductive reaction in the cathode.
3.9. Reaction mechanism

3.8. Sulfur balance Dibenzothiophene (DBT, ) is a typical OS widely

After the treatment, SO2! (without S2!) and PO3! concentra- existing in coals. Compared with the spectrum of original coal,
4 4
tions in the electrolyte increased from 32.2 to 488 mg/L (elevated the adsorption peaks of DBT at 432 cm!1 were lost after the treat-
by 15 times) and 0 to 20.4 mg/L, respectively (Table 2). It can con-
clude phosphorus (P) and S were released from coal in the forms of ment, while the adsorption peaks indicating diphenyl and thiazide
PO3! 2!
4 and SO4 . Calculating the solution concentration (C) and vol-
sulphone (DTS, ) appeared at 798 cm!1 (Fig. 9A). It
ume (V) in the following formula (M = C ( V), the mass (M) of SO2! 4
increased by 91.17 mg, correspondingly TS in the electrolyte indicated the DBT was oxidated into DTS, probably with concur-
increasing by 30.39 mg. And S in the adsorption bottle was
31.8 mg. Thus, the estimated value of TS reduction (mg) = S1 (S in rence of inorganic SO2!4 . Moreover, the strength of CAH stretching
the electrolyte, mg) + S2 (S in the adsorption bottle, mg) = 30.39 + vibration became weak at 2850 cm!1 and 2925 cm!1 resulting in
31.8 = 66.5 mg. The experimental value of TS reduction (M, the increase of C/H ratio. In addition, hydroxyl (AOH) adsorption
mg) = desulfurization efficiency (%) ( TS content (%) ( CWS concentra- peak at 3200 cm!1 was enhanced probably due to the oxidation
and hydrolysis (not shown in the diagram). Electrolysis in alkaline
systems allowed OH! lose charges on the anode surface and create
Table 2 active oxygen free radicals (H2O), O), H2O2), O2), etc.). These active
Analytical results of the filtrates.
free radicals attack OS in coals, which is oxidated into polysulfide.
Ions Before ED (mg/L) After ED (mg/L) Furthermore, the polysulfide is oxidated into sulfoxide
IC analysis Electrolyte (200 ml, aq.) (RAS@OAR¢) and sulphone (RAO@S@OAR¢). Then sulphone is
F! 9.85 8.65 converted into sulfonic compounds or SO2! 4 by hydrolysis. Reduc-
Cl! 57.4 61.4 tive electrode basically removes OS of the mercaptan (RASH) and
PO3! 0 20.4
4 the thioether (RASAR¢). And oxidizing electrode removes fat sulfur
NO! 78.1 70.8
3
and thiophenic sulfur. The participation of anodic oxidation is ben-
SO2! 32.2 488
4
efit for OS reduction. Significantly, the adsorption peak of CAS
ICP analysis Adsorption liquid (100 ml, aq.) (696 cm!1) disappeared after the treatment, which may be caused
S 0 318
by S reduction.
The condition is 50 g/L of CWS (6109 lm), 13.2 g/L of NaBO2, 1 g/L of NaOH, 3.5 V of The possible sulfur removal mechanism of the ED is proposed as
electrolytic voltage, and 4 h of electrolytic time. follows (Eqs. (1), (7)–(19) and Fig. 10).
 Y. Shen et al. / Fuel 96 (2012) 250–256 255

Fig. 9. FT-IR (A), XRD (B) analysis of the solid CWS samples. Process conditions: CWS (50 g/L, 6109 lm), electrolytic time (4 h), NaBO2 (13.2 g/L), NaOH (1 g/L), and
electrolytic voltage (4 V).

Fig. 10. Schematic diagram of the ED process in the alkaline sodium metaborate system.

Cathode : BO!2 þ 6H2 O þ 8e! ! BH!4 þ 8OH! ðas aboveÞ ð1Þ

+ [O]
BO!4 þ 2H2 O ! BO!2 þ 8H( ðactiv e hydrogen atomÞ ð7Þ S S ð17Þ

O
ð1Þ PS removal : FeS2 þ 2H( ! Fe þ S þ H2 S " ½3; 21' ð8Þ

ð2Þ Fat-sulfur removal : 2H( þ R ! SH ! R ! H þ H2 S " ð9Þ + [O]

S ð18Þ
S
4H þ R ! S ! R! ! R ! H þ R! ! H þ H2 S "
( ( (
ð10Þ O O
O
H2 S þ H2 O2 ! S # þ2H2 O ð11Þ
OH
Anode : 4H2 O ! 8e! ! 2O2 ½O'ðactiv e oxygen free radicalsÞ þ 8Hþ
+ 4 H 2O + H2SO4
ð12Þ S
O O OH

ð3Þ Fat-sulfur removal : 2R ¼ SH þ ½O' ð19Þ

! R ! S ! S ! R þ H2 O
½O' þ R ! S ! S ! R ! R ! S ! SðOÞR!
4½O' þ R ! S ! S ! R ! R ! SðO2 Þ ! SðO2 ÞR!
R ! SðO2 Þ ! SðO2 ÞR! þ 6H2 O ! R ! OH þ R! ! OH þ 10Hþ þ 2SO2!
4 ken and part of the carbon is washed away [38]. However, calorific
(4) DBT sulfur removal (special example)
ð13Þ
3.10. Coal characterization
ð14Þ
Ignition temperature and calorific value are two most important
ð15Þ coal combustion characteristics. Oxidative desulfurization of coal
tends to decrease its calorific value since some CAC bonds are bro-
ð16Þ value of coal can also increase after oxidation, because oxidation
can lead to its demineralization [39]. Thus, the change in calorific
value after desulfurization may depend on the decarbonitation/
demineralization ratio. In the present work, the calorific value
256 Y. Shen et al. / Fuel 96 (2012) 250–256
and ignition temperature of coal samples reduced from 31,790 to
31,418 J/g and 348 to 343 "C, respectively. Meanwhile, the ratios
of decarbonitation and deashing were 3.0% and 9.5%, respectively.
(Table 3) It indicates this ED method can not only remove S but
also decrease the ash content in CWS. Compared with some
conventional methods, it is relatively moderate. The coal calorific
value reduction may be caused by decarbonitation, owing to the
electrochemical oxidation. Minerals in coal can be qualitative and
quantitative analysis by X-ray diffraction (XRD). According to the
PDF card of standard diffraction datum and previous research re-
sults [40–42], the used of coal samples mainly contain the minerals
of kaolinite, quartz, illite, pyrite and the others, which are common
minerals in the coals of China [43]. After the treatment, the diffrac-
tion characteristic peaks (DCP) of pyrite disappeared in accordance
with the PS removal. Meanwhile, the DCP of other minerals
became weak or disappeared after the ED (Fig. 9B). To some extent,
demineralization contributes to the improvement of coal combus-
tion characteristics. It may be the decarbonitation is greater than
the demineralization resulting in the slight decrease of the coal
calorific value.
4. Conclusions
In summary, the ED process for CWS in alkaline sodium meta-
borate system is convenient, effective, and moderate. Under the
ambient conditions of CWS 50 g/L, coal particle size 6109 lm,
NaBO2 13.2 g/L, NaOH 1 g/L, electrolytic voltage 3.5 V, and electro-
lytic time 4 h, the desulfurization efficiency can reach about 50%.
Among different type sulfur species, PS and OS were most effi-
ciently removed, with the reduction of 100% and 46.7%, respec-
tively. These observations indicate this ED method is effective in
removing PS and OS of CWS. The increase of SS (highest valence
S) caused by anodic oxidation, could be easily removed by filtering
and leaching. Namely, the S releasing from coal particles is mainly
in the forms of H2S (volatilization) and SS (filtration), so only the
residues of OS in the treated coal may produce SO2 during the pro-
cess of CWS combustion. Moreover, the produced H2S could easily
be collected by the alkaline liquors. The ED process described here
is an environmental friendly method, since it only uses electricity
to realize B recycling. Particularly, the filtrate recycling and the
hydrogen releasing will be further helpful in cost reduction in
the future work.
Acknowledgements
This work is financially supported by the National High Technol-
ogy Research and Development Program (‘‘863’’ program, Grant No.
2009AA062603). The assisted measurement works were provided
by Dr. Zhang Li from Instrumental Analysis Center of Shanghai Jiao-
tong University. And the insightful comments and suggestions pro-
vided by reviewers and editor are greatly appreciated.
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