WHEC 16 / 13-16 June 2006 – Lyon France

Economical Aspects of Sodium Borohydride for Hydrogen Storage

İ. Engin TÜRE, F. Öznur TABAKOĞLU, Gülbahar KURTULUŞ

UNIDO-ICHET, Sabri Ülker Sk. 38/4, Cevizlibag, Zeytinburnu, 34015 İstanbul

eture@unido-ichet.org; ftabakoglu@unido-ichet.org; gkurtulus@unido-ichet.org

ABSTRACT

Hydrogen is the best fuel among others, which can minimize the cause to global warming. Turkey has an
important location with respect to hydrogen energy applications. Moreover, Turkey has 72.2% of the
world’s total boron reserves. Sodium borohydride (NaBH4) which can be produced from borax has high
hydrogen storage capacity. Hence, it is important for Turkey to lead studies about sodium borohydride to
make it one of the most feasible hydrogen storage methods.

In this paper an approximate process cost analysis of a NaBH4-H2 system is given, starting with NaBH4
production till recycling of it. It is found that, the usage of NaBH4 as hydrogen storage material is relatively
an expensive method but after improving reactions and by-product removal in the system and reducing
the energy and reactant costs, sodium borohydride is one of the best candidates among hydrogen storage
technologies.

KEYWORDS: hydrogen storage, sodium borohydride, economic analysis

1. INTRODUCTION

The increasing energy demand since the industrial revolution has been mainly met by fossil fuels up to
now. However, utilization of fossil fuels has had many serious consequences such as global warming,
climate change, damage on ozone layer, acid rains and environmental pollution. Besides the negative
impact of environmental damage on people caused by fossil fuels, the finite reserves of oil and natural gas
made scientists search for alternative fuels and new energy resources. The main properties which an
ideal fuel should have are; environment friendly, renewable, light, having high calorific value, capable of
being produced, stored and used in a safe, clean and economic way. As a fuel, hydrogen meets almost all
these criteria and with further research and development can be expected to fulfill the remainder. In
addition, taking into account that the fossil fuel will be depleted completely in 40-50 years, there is not
another alternative. Hydrogen energy is also referred as “independence fuel” since it eliminates the
countries’ dependence on the importation of oil and natural gas. Hydrogen can be used in transportation,
spacecrafts, electricity generation, industry, houses and any other application where fossil fuels are
currently used.

2. HYDROGEN STORAGE METHODS

For widespread use of hydrogen energy it is necessary to develop hydrogen storage systems which are
safe, capable of storing large amounts in small volumes. Today, hydrogen can be stored in gaseous,
liquid or solid forms such as metal hydrides, chemical hydrides and carbon nanotubes. However, these
methods are still in development phase and it will take some time before they are economically feasible.
Although compressed hydrogen can be used in vehicle applications such as buses and cars, its use is not
appropriate in small portable device applications with power outputs less than 100 W. In such cases,
chemical hydrides, having high volumetric and gravimetric storage densities are being developed.

Direct methanol fuel cells have been developed as a solution to the portable liquid fuel usage (DMFC), but
their poor performance and the other problems caused by methanol have initiated scientists search for
better devices. Particularly, the liquid solutions of sodium borohydride (NaBH4) having both high energy
capacity and reliability, have been the subject of considerable interest in recent years [1]. However, the
 WHEC 16 / 13-16 June 2006 – Lyon France

high cost of chemical hydrides inherent to all chemical storage methods is also a disadvantage for sodium
borohydride. The selling prices of sodium borohydride produced via commercial production methods such as
Bayer, Rohm and Haas are US$ 55/kg for powder form and US$ 47/kg in a 12% NaOH solution [2].

3. BORAX AND ITS IMPORTANCE FOR TURKEY

Borax is boron mineral and is a compound used in sodium borohydride synthesis. Boron minerals contain
boron oxide (B2O3) in different ratios and the common ones found in Turkey are tincal (Na2B4O7.10H2O),
colemanite (Ca2B6O11.5H2O) and ulexite (NaCaB5O9.8H2O). The total boron reserves of Turkey are 851
million tons and constitute 72.2% of the world’s total estimated boron reserves. The boron reserves in the
world and in Turkey are shown in Table 1 and Figure-1.

Table 1: Boron Reserves in the World (thousand tonnes - B2O3) [3]

Country Proven Possible Total Share In

Economical Economical Reserve Total Reserve (%)
Reserve Reserve
Turkey 227 624 851 72.2
USA 40 40 80 6.8
Russia 40 60 100 8.5
China 27 9 36 3.1
Argentina 2 7 9 0.8
Bolivia 4 15 19 1.6
Chili 8 33 41 3.5
Peru 4 18 22 1.9
Kazakhstan 14 1 15 1.3
Serbia 3 0 3 0.3
Total 369 807 1,176,000 100,000

Figure 1: Distribution of Boron Reserves in Turkey [3]

Although Turkey has the highest share of proven and possible boron reserves in the world, USA has the
highest production. The boron products produced in Turkey are borax decahydrate, anhydrous borax,
borax pentahydrate, sodium perborate tetrahydrate, sodium perborate monohydrate and boric acid [4].
The boron reserves are in the state monopoly and are processed by the Eti Company. It is obvious that
Turkey having a 230-240 million US dollars boron export income does not have enough share in the boron
market based on the assumption that the boron trade value of the world is 1.25 billion US dollars [5]. The
 WHEC 16 / 13-16 June 2006 – Lyon France

boron compounds which constitute the raw material for more than 400 compounds in manufacturing
industry can be used in various applications such as detergents, space technologies, toothpaste and
engine oil. Therefore, boron mineral has a strategic importance similar to oil and natural gas [5].

Hydrogen storage technology is one of the application areas of borax and sodium borohydride can be
produced from borax decahydrate and anhydrous borax. These compounds are produced by processing
tincal mineral which is abundant in Turkey. As noted earlier the production cost of sodium borohydride
today is quite expensive, constituting a major obstacle to commercialization of sodium borohydride as a
hydrogen storage method. Nevertheless, it is expected that the cost will decrease to less than US$ 1/kg
within the next five years [6].

4. USAGE OF SODIUM BOROHYDRIDE AS HYDROGEN STORAGE MATERIAL

4.1. CHARACTERISTICS OF SODIUM BOROHYDRIDE

Sodium borohydride, NaBH4, is classified as a flammable solid, is available either as a white powder or as a
12% solution in caustic soda. It is stable to 300°C in dry air and in vacuum to 400°C with only partial
decomposition. In order to prolong the shelf life of sodium borohydride solutions, NaOH is added. Under
normal storage conditions, the loss of NaBH4 in 12% solution by decomposition is less than 0.1% NaBH4
per year [2].

NaBH4 is hygroscopic and when it absorbs water rapidly from moist air, it decomposes slowly to form
sodium metaborate and hydrogen. Hydrogen can be generated in a rapid and controlled manner by
adding an acidic compound or an appropriate metal such as nickel, cobalt, ruthenium or platinum.

Exothermic, catalytic hydrolysis reaction of sodium borohydride solution is shown in reaction (1). As a
result of the complete hydrolysis of NaBH4, 2.37 l H2/g NaBH4 is released [2]. Half of the hydrogen comes
from sodium borohydride and the half comes from water. Therefore, the hydrogen content of sodium
borohydride is quite high. The theoretical maximum hydrogen capacity of sodium borohydride is 10.8%.

NaBH4 + 2H2O → 4 H2 + NaBO2 + 300 kJ (1) ∆Gº (298) = -321 kJ/mol-NaBH4

NaBH4 has more hydrogen storage capacity than many complex hydrides, as shown in Figure 2.
Furthermore, the studies have shown that NaBH4 has more hydrogen storage capacity than compressed
hydrogen in a tank [7].

Figure-2. Comparison of chemical hydrides [8]

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Briefly, the advantages of hydrogen storage using NaBH4 can be summarized as follows:

• Sodium borohydride solutions are stable for long period of time,

• Sodium borohydride solutions are non-flammable,
• The volumetric and gravimetric hydrogen storage capacity of NaBH4 is high,
• The hydrogen release rate of NaBH4 can be controlled easily,
• The by-product NaBO2 can be recycled back to NaBH4 .

4.2. COSTS OF SYNTHESIS, HYDROLYSIS AND RECYCLING OF SODIUM BOROHYDRIDE

The Bayer process is one of the best known commercial sodium borohydride production methods. In this
process, a certain amount of anhydrous borax, sodium and quartz are heated together at 500°C under 3
atm hydrogen pressure [9]. After extraction of the products with ammonia and its evaporation, sodium
borohydride is obtained with high efficiency. As a secondary product sodium metasilicate is produced. The
reaction is given below:

1/4 Na2 B4O7 + 4Na + 2H2 + 7/4 SiO2 → NaBH4 + 7/4 Na2SiO3 (2)
∆Gº (298) = -411.3 kJ/mol-NaBH4 ; ∆Hº (298)=-541.348 kJ/mol NaBH4

The reaction enthalpy of the process is calculated and it is found that the energy cost of the process is
US$ 2/kg NaBH4. This assumes ideal conditions and that the energy cost of by-product removal is
excluded. On the other hand, in order to produce 1 kg NaBH4, approximately US$ 10 is spent for raw
materials. If sodium borohydride produced as described in section 4.1 is used in hydrolysis reaction, 4.73
kg of NaBH4 is needed to generate 1 kg hydrogen and the cost will be approximately US$ 50.

There is also a need for a catalyst in the hydrolysis reaction and depending on the catalyst type the cost
required to produce 1 kg H2 out of NaBH4 is estimated to be around US$ 80 kg/H2. It should be noted that,
if NaBH4 is not produced in the system and if it is purchased from industry at a price of around US$ 50/kg
NaBH4, the cost of this reaction would be around US$ 230/kg H2 and including the cost of catalyst, the
hydrolysis reaction cost would be approximately US$ 260/kg H2.

It is crucial to recycle NaBO2 back to NaBH4, which is generated via a hydrolysis reaction. It has been
shown that the recycling process can be realized by reacting NaBO2 with different chemicals such as
MgH2 [10] or Mg2Si [11]. In this study, the cost of recycling process using Mg2Si is calculated as at least
US$ 15/kg H2.

Finally, under the assumption of ideal conditions on, the total cost starting with NaBH4 production until
recycling amounts to around US$ 110/kg H2 and US$ 290/kg H2 if the sodium borohydride was purchased
directly from industry.

5. CONCLUSION

Fossil fuels are limited and it is foreseen that their amount will decrease considerably in the near future.
Hence, the best alternative fuel for the 21st century is hydrogen. Hydrogen production and storage
technologies are costly nowadays but in the future are expected to decrease.

Turkey has 72.2% of world’s boron minerals and utilization of boron ores could make an important
contribution to the Turkish economy drive. In particular, developing sodium borohydride for use as a
hydrogen storage material and being one of the leaders in this field will contribute to the Turkish economy and
its sustainable development. Although sodium borohydride is one of the best candidates to be used in
hydrogen storage, work is needed to improve the efficiency of the NaBH4-H2 system reactions and energy and
reactant costs must be decreased.
 WHEC 16 / 13-16 June 2006 – Lyon France

6. REFERENCES

1. Wee, J., A comparison of sodium borohydride as a fuel for proton exchange membrane fuel cells and
for direct borohydride fuel cells, Journal of Power Sources, 2006
2. Kirk-Othmer Encyclopedia of Chemical Technology, John Wiley & Sons, 2001
3. http://www.etimaden.gov.tr
4. Boron ores and the status in the world, http://science.ankara.edu.tr/~kavusan/
5 Alma,H., Acemioğlu, B., Boron Applications in Turkey, Science and Eng. J.,V.4, (2), 2001
6. http://merit.hydrogen.co.jp
7. Zeybek, O., Akın, S., “Hydrogen Storage Technology Using Sodium Borohyride”, Proceedings
International Hydrogen Energy Congress and Exhibition IHEC 2005, İstanbul.
8. Ying Wu, “Hydrogen Storage via Sodium Borohydride Current Status, Barriers, and R&D Roadmap”,
GCEP – Stanford University, April 14-15, 2003.
9. Schubert, F., Lang, K., Shabacher, W., Burger, A., US Patent Office, 3,077,376 (1963).
10. Z.P.Li,B.H.Liu, N. Morigasaki, S.Suda,Journal of Alloys Compounds 349 (1), 232-236, 2003.,
11. Kojima,Y., Haga, T., “Recycling process of sodium metaborate to sodium borohydride” International
Journal of Hydrogen Energy, 2002, 989-9932