international journal of hydrogen energy 34 (2009) 4773–4779

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Investigation of sodium borohydride production process:

‘‘Ulexite mineral as a boron source’’

Mehmet Burcin Piskin*

Department of Bioengineering, Yildiz Technical University, 34210 Istanbul, Turkey

article info abstract

Article history: Currently, the energy requirements of the entire world are mostly provided by hydro-
Received 7 February 2009 carbon-based fossil fuels, such as coal, fuel oil, or natural gas. Because of environmental
Received in revised form pollution, decrease in energy sources, and difficulties in storing electricity, more attention
23 March 2009 is dedicated to new sources of energy, such as hydrogen. Presently, sodium borohydride
Accepted 25 March 2009 (NaBH4) appears to be an excellent hydrogen-storage medium due to its high theoretical
Available online 28 April 2009 hydrogen yield by weight, 10.6%. The main aim of the present study is to investigate NaBH4
production from ulexite mineral (NaCaB5O9$8H2O). The experimental investigation
Keywords: consists of four steps, such as (1) Characterization of NaCaB5O9$8H2O by X-ray diffraction,
Hydrogen energy differential thermal and thermogravimetric analysis, scanning electron microscopy, and
Storage attenuated total reflectance of Fourier-transform infrared spectroscopy; (2) Preparation of
Sodium borohydride ulexite–borosilicate glass (NaCaB5O9$SiO2); (3) Synthesis of NaBH4 from ulexite–borosilicate
Ulexite mineral glass; and (4) Separation of NaBH4 from the reaction mixture. NaBH4 can thus be produced
by heating ulexite mineral form of borosilicate glass with metallic sodium under 3-atm.
hydrogen pressure at 450–500  C for 4 h.
ª 2009 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights
reserved.

1. Introduction environment. It is the oldest, simplest, and most common

Hydrocarbon-based fossil fuels (coal, fuel oil, and natural gas)
are used as primary energy sources that provide the energy
requirements of the entire world. The burning of fossil fuels is
the largest sources of CO2 emissions, which is one of the
greenhouse gases that allow radioactive forcing and contrib-
utes to global warming. Furthermore, fossil fuel amounts have
decreased steadily since 1980, mainly caused by the reduced
consumption of coal. Because of environmental pollution,
decrease in energy sources, and difficulties in storing elec-
tricity, increasing attention is paid toward developing a new
energy carrier.
Hydrogen has been recognized for a long time as an energy
carrier in industrial applications and is used as a fuel for vehicles.
Hydrogen is one of the basic chemical elements in our
element in the universe and is only found in nature combined
with other elements. Furthermore, hydrogen can be produced
from many sources using solar, hydro and wind power. One of the
most important features of hydrogen is that it can easily be
stored.
Pure hydrogen can be stored in the gaseous and liquid form
in tanks, physically in carbon nanotubes, and chemically as
hydrides. Traditional hydrogen-storage technology has been
inadequate because of the dangers in storage and trans-
portation, in addition to the fact that hydrogen is a light gas
and occupies much more space. These difficulties comprise
the main problems of using hydrogen for vehicular applica-
tions. The term ‘‘chemical hydrogen storage’’ is used to
describe storage technologies in which hydrogen is generated
through a hydrolysis reaction, and they involve the hydrolysis

* Tel.: þ90 212 383 46 55; fax: þ90 212 482 80 71.
E-mail address: mpiskin@yildiz.edu.tr
0360-3199/$ – see front matter ª 2009 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2009.03.043
4774 international journal of hydrogen energy 34 (2009) 4773–4779
reaction of chemical hydrides with water to produce hydrogen
[1–5].
NaBH4, also known as sodium tetrahydroborate, has
attracted more attention as a hydrogen-storage medium
because of its high hydrogen-storage capacity, 10.6 wt.%,
which is more than that of the other hydrogen-storage alloys.
It is a selective reducing agent used in the manufacture of
pharmaceuticals and other organic compounds.
NaBH4 can generate hydrogen gas according to the
following hydrolysis reaction (Eq. (1)).
NaBH4 þ 2H2O / 4H2 þ NaBO2 þ Q (217 kJ). (1)
The reaction can be controlled in an aqueous medium
through pH and the use of a catalyst [6,7]. Many catalysts for
the reaction have been developed, and Ru-based catalysts are
the most effective for generating H2 [8]. Moreover, Zhang et al.
[9] have measured the enthalpy of the reaction, 53 kJ/mol H2;
this value is compared with that of NaBH4 hydrolysis. Fer-
nandes et al. [10] have studied the catalytic efficiency of
amorphous Co–Ni–P–B catalyst powders in the hydrogen-
generation process of hydrolysis of NaBH4 in alkaline solution.
They have compared the efficiency with previously published
catalytic activity of Co–B, Co–Ni–B, and Co–P–B catalyst
powders. These catalyst powders are synthesized by chemical
reduction of cobalt and nickel salts at room temperature. They
have concluded that the Co–Ni–P–B catalyst shows the highest
efficiency among all the catalysts studied.
In accordance with several publications, NaBH4 can be
produced by several methods. Schlesinger et al. [11] have
described that 1 mol of methyl borate reacted with 4 mol of
sodium hydride (NaH) to produce NaBH4. In the following
process, the reaction occurs at 225–275  C.
4NaH þ B(OCH3)3 / NaBH4 þ 3NaOCH3 (2)
Hale and Sharifian [12] describe the preparation of NaBH4
in an electrolytic cell, which comprises an anode compart-
ment containing a solution of aqueous sulfuric acid and
a cathode compartment with 25% solution of tetra-
methlyammonium borate. The anode and cathode compart-
ments are separated by a cationic membrane, Nafion 427.
NaBH4 can be produced by the reaction of diborane (B2H6)
with sodium amalgam in the presence with diethyl ether
during 24 h as following reaction [13].
2Na þ B2H6 / NaBH4 þ NaB3H8 (3)
In addition to this, boron halogenure can be used for NaBH4
production. NaBH4 is produced by atomization of metallic Na
into hydrogen and boron trifluoride (BF3) [14].
4Na þ 2H2 þ BF3 / NaBH4 þ 3NaF (4)
Boron phosphate (BPO4) is reacted with NaH to produce
NaBH4 through the following reaction [13].
4NaH þ BPO4 / NaBH4 þ Na3PO4 (5)
NaBH4 has been reported to be formed by the reaction of
NaBO2 with Mg and hydrogen (or MgH2) through the following
reaction at around 450  C. Furthermore, sodium metaborate
(NaBO2) is recycled back to NaBH4 using coke or methane by
the overall equation provided below [15].
NaBO2 þ 2Mg þ 2H2 / NaBH4 þ 2MgO (6)
NaBO2 þ 2C þ 2H2O / NaBH4 þ 2CO2 (7)
In addition, Hsueh et al. [16] have reported the high-energy
ball-milling process that was used to regenerate spent NaBH4,
i.e., the NaBO2 was converted back to NaBH4 by reaction with
magnesium hydride (MgH2).
The effects of hydrogen pressure, reaction temperature,
and addition of transition metal on NaBH4 synthesis by the
reaction of NaBO2 with Mg and H2 have been investigated, and
higher H2 pressure has been proved beneficial to NaBH4
formation. The activation energy of NaBH4 formation from
Mg, NaBO2, and H2 was estimated to be 156.3 kJ/mol NaBH4,
according to the Ozawa analysis [17].
In addition to these methods, borax has been used as boron
sources for the thermochemical reactions under hydrogen
atmosphere to synthesize NaBH4. It was reported a high-
pressure process (HPP) for producing NaBH4, which is based
on the conversion reaction of borosilicate glass at temperature
at 475  C under 22 atm. hydrogen pressure [18].
The largest world reserves of borates occur in an L-shaped
area in western Turkey. Especially, ulexite reserves are found at
different borate deposits in the Marmara Region, Central Ana-
tolia Region, and Aegean Region. The deposits have average ore
grades of 29% B2O3 for the ulexite and appear to have been
formed from a larger basin [19]. In addition to this, primary and
secondary ulexite deposits are always found in association with
reserves of borax (Na2[B4O5(OH)4]$8H2O) and colemanite
(CaB3O4(OH)3$H2O). Ulexite is a structurally complex mineral,
with a basic structure containing chains of sodium, water, and
hydroxide octahedra. Because of these reasons, it is very
important and necessary to elucidate NaBH4 formation from
ulexite mineral (Na–Ca borate) as a boron source.
In this study, the authors focus on the synthesis of NaBH4
from ulexite mineral. The experimental procedure is based on
four steps, such as detailed characterization of ulexite mineral
(NaCaB5O9$8H2O) by X-ray diffraction (XRD), differential
thermal and thermogravimetric analysis (DTA–TG), scanning
electron microscopy (SEM), and attenuated total reflectance of
Fourier-transform infrared spectroscopy (FT-IR/ATR) tech-
niques, preparation of ulexite–borosilicate glass (NaCaB5O9–
SiO2), synthesis of NaBH4 from NaCaB5O9–SiO2, and separation
of NaBH4 from the reaction mixture.
2. Experimental
The experimental investigation of NaBH4 production based on
the following equation consists of four steps [20].
NaCaB5O9–SiO2 þ 20Na þ 10H2 / 5NaBH4 þ 8Na2SiO3 þ CaO (8)
 international journal of hydrogen energy 34 (2009) 4773–4779 4775

The present method is investigated for producing NaBH4

Table 1 – The chemical and physical properties of ulexite
which includes only one conversion reaction of NaCaB5O9–
mineral.
SiO2, which is prepared from readily available minerals:
Empirical formula B5CaH16NaO17
ulexite and quartz. The authors described all the details of the
ICSD name Sodium calcium
manufacture process in which ulexite mineral used as boron borate hydroxide hydrate
source, that is specified in our research article. In addition to, Composition %
the characteristic-optimum reaction parameters are declared B 2O 3 42.97
such as reaction time and yield, temperature range and Na2O 7.65
working pressure values to produce NaBH4 from ulexite CaO 13.83
H2O 35.55
mineral.
Hardness 2.5 Mohs
Specific gravity 1.955 g/cm3
2.1. Characterization of NaCaB5O9$8H2O by XRD, Colour and transparency White, colorless, silky, transparent
DTA–TG, SEM and FT-IR/ATR techniques

NaCaB5O9$8H2O used as a boron source in NaBH4 production The microstructure was determined by SEM (JEOL JSM-
was provided by Eti Mine Works, Turkey (Fig. 1). The chemical 5910LV). Low- and high-magnification SEM images of NaCa-
and physical properties of NaCaB5O9$8H2O are shown in B5O9$8H2O are provided in Fig. 4a, b. The corresponding
Table 1. After cleaning the mineral of visible impurities, it images showing nonuniform particles.
was ground and sieved to a particle size below 150 mm by To characterize chemical bonds in the ulexite structure,
standard sieves (as determined by the American Society for the technique of FT-IR/ATR spectroscopy (Perkin Elmer Spec-
Testing and Materials). The sample was characterized using trum One) was used. Before the analysis, the crystal area was
XRD, DTA–TG, SEM, and FT-IR/ATR techniques. cleaned, and the background corrected; the solid material was
XRD analysis was used to determine the crystalline struc- placed over the small crystal area on a Universal diamond ATR
ture of NaCaB5O9$8H2O. The analysis was carried out at top-plate. The FT-IR spectrum was obtained after force was
ambient temperature in a range of diffraction angles from applied to the sample, pushing it onto the diamond surface.
0 to 50 (45 kV and 40 mA). Data were collected on a Philips The IR spectrum was recorded in the spectral range of 4000–
Panalytical X’Pert-Pro diffractometer with CuKa radiation 650 cm1 at a resolution of 8 cm1 and is shown in Fig. 5.
(l ¼ 1.54178 Å). Sample was ground in agate mortar and settled
in an aluminum sample holder. Then the sample was
2.2. Preparation of NaCaB5O9–SiO2
compressed to have an even surface to prevent X-ray scat-
tering. Phase identification was carried out using the available
NaCaB5O9$8H2O was calcined at 527  C (determined according
data from an inorganic crystal structure database (ICSD), and
to the DTA–TG data), for 3 h to remove the 8 mol of water.
the XRD pattern of NaCaB5O9$8H2O is shown in Fig. 2.
Subsequently, the dehydrated ulexite (NaCaB5O9) was mixed
Thermal decomposition of NaCaB5O9$8H2O was conducted
with quartz (SiO2) and glass powder was prepared to produce
with a Perkin Elmer Diamond DTA–TG instrument. Analysis
NaCaB5O9–SiO2. The Seger formula (empirical ceramic
was carried out under N2 atmosphere at a constant flow rate of
formula) of this prepared glass mixture is provided in Table 2.
100 ml/min in the temperature range of 30–900  C, with
After mixing for 30 min in a mortar grinder, the mixture was
a heating rate of 10  C/min. DTA–TG instrument which was
introduced into a refractory pot in a furnace, where it was
calibrated by means of the melting points of indium
sintered at 1060  C. NaCaB5O9–SiO2 was obtained and ground
(Tm ¼ 156.6  C) and tin (Tm ¼ 231.9  C) under the same condi-
tions with the sample. Samples were ground in agate mortar
and stored under inert atmosphere before the analyses. The
DTA–TG curve of NaCaB5O9$8H2O is provided in Fig. 3.

Fig. 1 – Ulexite mineral used as a boron source. Fig. 2 – XRD pattern of ulexite mineral.
4776 international journal of hydrogen energy 34 (2009) 4773–4779

Fig. 3 – DTA–TG curve of ulexite mineral.

to obtain a particle size below 150 mm; it is ready for use as autoclave to generate a hydrogen atmosphere at a constant
starting material in NaBH4 production. pressure of 3 atm. Hydrogen gas was fed until absorption was
complete and subsequently, the pressure of the hydrogen in
the autoclave was stable, implying that NaBH4 was
2.3. Synthesis of NaBH4
synthesized.
The reaction mixture was allowed to cool under hydrogen
The synthesis was carried out in a stainless-steel autoclave
atmosphere to the ambient temperature after the heating
equipped with a mechanical stirrer and a serpentine that
system of the autoclave was shut down. The reaction mixture
allows water-cooling. It can be pressurized with hydrogen gas,
was analyzed by XRD for qualitative identification of the
ranging from atmospheric pressure to 50 atm., and the
NaBH4 formation, and the XRD pattern is shown in Fig. 6. The
components can be heated until 500  C under these pressures.
characteristic peaks of NaBH4 indicated by ‘‘ ’’ are indexed
NaCaB5O9–SiO2 and metallic sodium (Na, Riedel de Haën-
using the NaBH4 structure, which has a cubic crystal system
13401, 99%) were introduced into a stainless-steel autoclave
with a, b, c ¼ 6.1635 Å [PDF Number: 01-074-1891, space group
according to the stoichiometric proportion of Eq. (8) and
Fm-3m (225)]; the (200) diffraction peak corresponding to
heated under a hydrogen pressure of 3 atm. until 400–500  C in
28.95 diffraction angle had the maximum intensity (100%),
the absence of air and moisture. Pure hydrogen gas was
matching with the characteristic peaks of NaBH4. In addition,
continuously fed from a hydrogen generator, in which
Na2SiO3 is defined with 29.47 and 37.28 diffraction angles in
hydrogen gas is produced by the electrolysis of water, into the

Fig. 4 – SEM images of ulexite mineral. (a) Low magnification and (b) high magnification.
 international journal of hydrogen energy 34 (2009) 4773–4779
Fig. 5 – FT-IR spectrum of ulexite mineral.
the mixture. Na2SiO3 has an orthorhombic crystal system (a, b,
c ¼ 10.48, 6.07, 4.82 Å) with Cmc21 space group and, space
group number of 36 (PDF Number: 01-072-0079).
2.4. Separation of NaBH4 from the reaction mixture
The reaction mixture, which contains NaBH4 and the by-
product Na2SiO3, was extracted with suitable solvent to
separate NaBH4; the latter was obtained as a white solid
powder after evaporating the extraction solution in a rotary
dryer under vacuum. The main product was analyzed using
XRD for qualitative identification, and the XRD pattern is
represented in Fig. 7.
3. Results and discussion
The experimental investigation of NaBH4 production from
ulexite mineral has been studied, and all the investigation
steps are analyzed and discussed in detail.
Fig. 2 shows the XRD pattern of ulexite mineral, which was
recorded in a range of diffraction angle from 0 to 50 . In the
sample, the representive of (0 1 0) diffraction peak, corre-
sponding to 12.35719 Å peak at 7.1538 , had the maximum
(100%) intensity. This identified the NaCaB5O9$8H2O in the
anorthic crystal system with P-1 space group and, space group
number of 2. NaCaB5O9$8H2O has a unit cell structure of a, b,
c ¼ 8.8160 Å, 12.8700 Å, 6.6780 Å, according to references (PDF
number: 01-083-2421).
Table 2 – Seger formula of powder-glass material
(NaCaB5O9–SiO2 mixture).
Na2O ¼ 0.33 B2O3 ¼ 1.69 SiO2 ¼ 5.35
CaO ¼ 0.67
4777
The process of thermal decomposition of ulexite occurs in
six stages, as can be observed in the DTA–TG curve (Fig. 3). The
first three steps showed weight loss of 4.063%, 8.921% and
17.501%, respectively, observed in the temperature ranges of
70–280  C, attributed to removal of the crystal water. Weight
loss of 2.884% corresponded to the release of OH groups in
the temperature range of 350–527  C. It is concluded that
NaCaB5O9$8H2O releases 8 mol of water in the temperature
range of 70–527  C, and it is converted to the NaCaB5O9 form.
After further heating, one exothermic peak occurred at 645  C
corresponding to the recrystallization of amorphous
NaCaB5O9 to CaB2O4. Residual NaB3O5 is melted at 862  C and
transformed to the amorphous structure through an endo-
thermic reaction.
The FT-IR spectra of the ulexite mineral showed the
following infrared absorption bands, as depicted in Fig. 5. The
bands at 3415.49 cm1 represent the stretching mode of O–H.
The band at 1625.84 cm1 is assigned to free H2O band. The band
at 1408.50 cm1 is assigned to the asymmetric stretching mode
of B–O in BO3. The bands at 1352.80, 1315.79, and 1209.20 cm1
are assigned to the in-plane bending band of (OH)1. The bands
at 1050.86, 975.58, and 856.24 cm1 are assigned to the asym-
metric stretching of B–O in BO4. The bands at 746.06 and
712.42 cm1 are assigned to the out-of-plane bending of (OH)1
and symmetric stretching band of B–O in BO4 [21].
Fig. 6 shows the XRD pattern of the reaction mixture after
heating the ulexite–borosilicate glass with metallic sodium
under hydrogen atmosphere. The diffraction peaks show the
existence of NaBH4 and Na2SiO3. The characteristic peaks of
NaBH4 are observed at the diffraction angles of 28.96 and
41.40 . However, the diffraction peak positions of 29.34 and
37.27 belong to Na2SiO3. This result proves that NaBH4 can be
synthesized from the ulexite mineral form of borosilicate glass.
Fig. 7 shows the XRD pattern of the main product after the
extraction, filtration, and evaporation steps of the reaction
mixture. All the diffraction peaks are mainly associated with
4778 international journal of hydrogen energy 34 (2009) 4773–4779

Fig. 6 – XRD pattern of reaction mixture (NaBH4 and Na2SiO3).

Fig. 7 – XRD pattern of main product (NaBH4).

NaBH4, and they clearly show the existence of NaBH4. The
characteristic peaks of NaBH4 occur at 28.95 and 41.39
diffraction angles. In addition, the XRD result proves the
nonexistence of the Na2SiO3 phase in the sample. Further-
more, it should be noted that Na2SiO3 can be reused as a raw
material in the glass industry.
 NaBH4 can be produced by heating ulexite–borosilicate glass
with metallic sodium between the temperature ranges of
400–500  C under 3-atm. hydrogen pressure, for 4 h with
a 94% reaction yield.
Acknowledgements

4. Conclusion
In the present study, the experimental investigation proce-
dure of NaBH4 production is presented. The following results
are obtained from this study:
 The NaBH4 production process consists of four steps such as
characterization of the ulexite mineral (NaCaB5O9$8H2O) by
XRD, DTA–TG, SEM, and FT-IR/ATR analysis techniques,
preparation of ulexite–borosilicate glass (NaCaB5O9–SiO2),
synthesis of NaBH4, and separation of NaBH4 from the
reaction mixture.
 It is suggested that ulexite mineral, a type of ulexite–boro-
silicate glass, can be used as a boron source or starting
material in the synthesis of NaBH4.
The authors would like to thank the Turkish State Planning
Organization (Project No: 98-DPT-07-01-02) for its financial
support.
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