NuRER 2012 – III.

International Conference on Nuclear & Renewable Energy Resources

İstanbul, TURKEY, 20-23 May 2012

HYDROLYSIS OF SYNTHETIC KBH4 BY CoI2 CATALYST

SUPPORTED ON ACTIVATED CARBON

Murat BİLEN*, Metin GURU**, Çetin ÇAKANYILDIRIM***

*Eti Mine Works, Head of Tech. Dev. Dep., Bahçekapı Mah. Fatih S. Mehmet Bul. No:179, Etimesgut/ANKARA
**Gazi University, Eng. Fac., Chemical Eng. Dep., Maltepe 06570, Ankara, Turkey
*** Hitit University, Eng. Fac., Chemical Eng. Dep., 19030, Çorum, Turkey

Abstract

Present study reports the production of KBH4 in the presence of KCl, B2O3 and MgH2 by means of mechanical
reaction. In order to obtain the maximum yield different values of reactant ratio and working time were studied.
Product was purified with ethylene diamine (EDA) and characterized by FT-IR and XRD analyses to figure out
the success of the process. 40(wt)% CoI2 supported on activated carbon (AC) catalyst was utilized to decompose
KBH4. It resulted in zero and first reaction order for low and high temperature regions whose activation energies
are 25.46 and 49.13 kJ/mol. Optimum time for mechano-chemical treatment and reactant ratio (MgH2/KCl) were
obtained as 1000 min and 1.0, respectively.

Key words: Hydrogen, KBH4, Ball milling, Catalyst

Introduction

Increasing energy demand of the modern lifestyle, forces scientists to find out new and environment friendly
solutions. Hydrogen is one of the most attractive alternatives for the conventional energy sources. Hydrogen
consuming systems are always clean and have high yield [1]. Thus, last decade has passed for the investigations
of chemical substances to produce hydrogen. NaBH4 was thought to be the best candidate to take the role. It is
very effective and secure storage mediums to keep hydrogen for long duration. NaBH 4 is widely used to reduce
reactions and to store hydrogen. It is also the best candidate to feed the fuel cells. However problems such as;
high price, waste problem and less energy percentage of designed systems has started to change the ideas of the
scientists [2].

Different borohydrides are in concern of scientists and KBH4 is one of the promising substances to meet the
expectations. It has been used as reducing agent to make hydrocortisone, prednisone, prednisolone, and
corticosteroids. It is also used in vitamin A synthesis [3]. KBH4 can be produced by the reaction of NaBH4 and
KOH as shown below [4].

Corresponding Author: mbilen@etimaden.gov.tr

1
 NuRER 2012 – III. International Conference on Nuclear & Renewable Energy Resources
İstanbul, TURKEY, 20-23 May 2012

NaBH4 + KOH NaBH4 + NaOH (1)

On the other hand, it is possible to produce KBH 4 by using dehydrated borate through ball-milling reaction [3].
Ball-millig reactors provide appreciate conditions at its three dimensional high speed. It makes the particles
collide to each other and creates nano-scale working conditions that make some chemical chances possible that
are otherwise not easy to achieve or to result limited yields. Additives doped on Al alloys such as Al-Hg and Al-
In in ball-millig can be used to hydrolyze water and liberate hydrogen. NaCl doped mixture can provide 971
mL/min.g cat. hydrogen generation rate in pure water [6]. Syntheses of MgB2 [5] ,LiBH4 and KBH4 are some of
the examples among many applications performed in ball-milling reactors [7, 3].

KBO2 + 2MgH2 KBH4 + 2MgO (2)

In this article, we report the production procedure of KBH 4 in the presence of KCl, B2O3 and MgH2. Reactions
take place at about 50 °C in ball milling reactor and purification process was applied. On the other hand,
hydrolysis reaction kinetic was determined with synthesized 40(wt)% CoI 2/AC catalyst.

Experimental

MgCl2 and KCl were provided by Merck and Carlo-Erba with 99.9% purity. Eti Mining Comp. supports B2O3
with 99% purity. CoI2 was purchased from Sigma Aldrich with 95% purity. KBH4 was synthesized according to
the Reaction 3, in Spex 8000M type ball-milling. XRD experiments were performed to control the phase
composition and crystalline state of the catalysts by Shimadzu powder diffractometer (CuKα radiation,
λ=1.5406Å). Jasco 480 model FT-IR was used simultaneously to determine the chemical chances during
mechano-chemical process.

Mechano-chemical reactor was fed with B2O3 and MgH2/KCl mixture whose mol ratios have arranged as 0.65, 1,
1.3. Glow-box was used to handle the reactants, load the reactor and take the product. Reactor working times
were set as 300, 600, 800 and 1000 min. In order to purify the reaction product (KBH4) ethylene diamine (EDA)
was utilized as solvent. Then, subsequent filtration and crystallization processes took place.

2
 NuRER 2012 – III. International Conference on Nuclear & Renewable Energy Resources
İstanbul, TURKEY, 20-23 May 2012

Catalyst Preparation and Kinetic Studies

CoI2 has supported on AC and pressed to give cylindrical shape (13 mm diameter and 3,6 mm high) for the
hydrolysis reaction of KBH4. Catalyst contents were mixed in ball-milling reactor for 60 min. Pellets were
pressed under 590 MPa and kept at 200 °C for 1 h to remove the stearic acid and create macro pores.

Eight distinct experiments (at 20, 30, 40, 50, 55, 60, 65 ve 70 °C) were performed with 40% CoI2 loaded
supported catalysts. Reaction rate order and activation energy of the decomposition was calculated by the data
obtained at these temperatures. During the experiments reactor was kept in water bath whose accuracy is 0.1 °C.

Results and Discussion

Investigation for the suitable route to produce KBH4, will bring down the production cost of this hydrogen
carrier material and increase its chance to feed the fuel cell systems. Thus, KCl was supposed to be one of the
promising reactant to synthesize KBH4 and meet the market’s expectations. In order to determine the optimum
conditions, working time and reactants ratio were chosen as two main parameters.

The thermodynamic values of this reaction were summarized in Table 1. Negative value of the Gibbs free energy
indicates the high yield possibility of the desired reaction.

2KCl + 4MgH2 + B2O3 2KBH4 + 3MgO + MgCl2 (3)

Table.1 Thermodynamic data of reaction (3).

ΔHf, kJ/mol -437.699

ΔSf, J/mol.K 57.130
ΔGf, kJ/mol -455.580
Kp 1.191
lnKp 0.175

FT-IR spectrums in Figure 1 indicate that the reaction results in higher yields if reaction happens for longer
durations. With respect to the whole experiments performed, it is evident that the duration enhances the results
without dependence to reactant ratios. Characteristic peaks between 2400-2200 cm-1 clearly prove the formation
of BH4- (Figure 1). MgO existence is evident by the peak appeared at about 1481 cm-1. That peak also proves the
success of the oxygen remove from B2O3 structure similar to the previous studies [1, 5, 8, 9, 10]. In Figure 2, FT-
IR determination of the KBH4 reaction is given for different MgH2/KCl ratios, each milled for 1000 min.

3
 NuRER 2012 – III. International Conference on Nuclear & Renewable Energy Resources
İstanbul, TURKEY, 20-23 May 2012

Especially MgH2 excess amount for the metal borohydride spent fuel (metal metaborate) recycle reactions is
very important because of the extreme surface behaviors of the Mg [8]. Furthermore, in order to clearly
understand the FT-IR spectrums Figure 3 was created by the integration of FT-IR peak’s areas. These
integrations depict to the positive effect of working time and optimum MgH2/KCl ratio for the experiments.

Figure 1. FT-IR analyses that show the effect of the working time (MgH2/KCl ratio is 1.0)

Figure 2. FT-IR spectrum for distinct MgH2/KCl ratios (Working time is 1000 min.)

XRD results of the studies performed at different MgH2/KCl are given in Figure 4. Results indicate that the
products are in crystalline phase and the some of the broad peaks indicate the existence of nano particles
according to the software of the device that makes calculation by Scherrer equation. Mechano-chemical devices

4
 NuRER 2012 – III. International Conference on Nuclear & Renewable Energy Resources
İstanbul, TURKEY, 20-23 May 2012

generally provide nano scale reactants and(or) product, which is necessary to obtain high yields. Amorphous
natures of the materials generally cause undetectable peak existence during the XRD studies. Thus, Figure 4 also
shows that the produced KBH4 is not in crystalline phase. Moreover, it is possible to realize the diffraction peaks
of the starting reactants (KCl and MgH2). That indicates uncompleted transaction. XRD spectrum also indicates
that the MgH2 peak at 28 2θ became weaker if the MgH2/KCl ratio is equal to 1.0, meanwhile for that ratio MgO
peak at 43 2θ is more visible, which shows the success of the desired reaction.

Figure 3. Stoichiometry and working time effect on FT-IR peak areas that indicates KBH4 existence.

Figure 4. XRD results for the reaction 3 at different MgH2/KCl ratios (Reaction time is 1000 min.)

5
 NuRER 2012 – III. International Conference on Nuclear & Renewable Energy Resources
İstanbul, TURKEY, 20-23 May 2012

Purification process is indispensible to obtain high product yield and remove the some side reaction products.
EDA is a suitable solvent to separate the KBH4. It does not decompose KBH4 or cause any reaction. A
comparison of commercial and synthesized KBH4, which was purified with EDA gives clearer FT-IR spectrums
as shown in Figure 5. Results depict that the two samples have similar peaks at 2400-2200 cm-1, however residue
EDA makes it hard to determine the peaks between 1700-900 cm-1, similar with our previous results.

Figure 5. FT-IR graphs of commercial and produced KBH4 1) Original KBH4 2) Synthesized KBH4 (1000 min,
MgH2/KCl ratio is 1.0)

Kinetic behaviors of the catalyst

In catalytic dehydrogenation, hydrogen containing substances need catalysts to release hydrogen inside.
Hydrogen atoms both come from both KBH4 and solvent water during hydrolysis. Oxygen of the water adheres
to potassium and boron to form KBO2. This compound is easy to recycle and that raise the feasible usage of
KBH4.

CoI2 supported on AC catalyst was synthesized and tested for different active material ratios. Optimum catalytic
conditions and hydrogen generation rates were obtained for 40(wt)% CoI2/AC catalyst. Therefore only that
catalyst composition was used to perform the kinetic tests of KBH4. Low solubility and blockage of the side
products and removal of Co particles during the process generally result in activation loose. In order to
compensate these effects water amount [11] and CoI2 ratio can be increased. However these cause decrease in
hydrogen density and physical strength of the catalyst. While the hydrolysis, first of all catalyst is reduced by
KBH4 and Co and(or) CoBx are created. Thus hydrogen generation rate is generally slower for the first attempts
[12, 13].

6
 NuRER 2012 – III. International Conference on Nuclear & Renewable Energy Resources
İstanbul, TURKEY, 20-23 May 2012

40(wt)% CoI2/AC catalyst was studied at eight different temperatures (20, 30, 40, 50, 55, 60, 65 and 70 °C) and
reaction rate order was investigated. Experimental data fit zero and first order kinetic for low and high
temperature regions (Figure 6, 7). That means at high temperature concentration of the reaction medium is an
important property. Activation energy computation results 25.46 and 49.13 kj/mol for low and high temperature
regions, respectively. This low activation energy values are advantageous if compared with the values given in
other studies.

Figure 6. Kinetic investigation of KBH4 decomposition at low temperature (between 20-40°C) a) Concentration
changes with time at different temperatures b) Changes of reaction rate constants with inverse of temperature.

7
 NuRER 2012 – III. International Conference on Nuclear & Renewable Energy Resources
İstanbul, TURKEY, 20-23 May 2012

Figure 7. Kinetic investigation of KBH4 decomposition at high temperature (between 50-70°C) a) Concentration
changes with time at different temperatures b) Changes of reaction rate constants with inverse of temperature.

Conclusion

Increasing energy consumptions and limited fossil fuel reservoirs force scientists to create permanent solutions.
This study discusses the production of KBH4 by means of KCl, MgH2, B2O3 and ball-milling. Results prove that
reaction duration has positive effect on the product yield. Furthermore, it was observed that the reaction occurs
very well if the MgH2/KCl ratio is kept at 1.0. Produced KBH4 needs to be purified to raise the yield of the
reaction. Synthesized catalyst obeys zero and first order kinetics depending on the temperature. Activation
energy calculations results 21.46 and 49.13 kJ/mol for low and high temperature regions. Aqueous solutions of
potassium borohydride at room temperature are very slowly hydrolized [14]. In future studies, it would be
beneficial to research for the catalyst systems that can decompose KBH4 rapidly.

Acknowlegments

We are indebted to the Eti Mining Works of Turkey for continuing support. Also this work was supported by the

Gazi University BAP Project No: 06/2010-57.

8
 NuRER 2012 – III. International Conference on Nuclear & Renewable Energy Resources
İstanbul, TURKEY, 20-23 May 2012

References

[1] Pişkin. M.B.. “Investigation of sodium borohydride prodııction process: Ulexite mineral as a boron source”,
Int. J. of Hydrogen Energy. 2009;34:4773-4779.

[2] Demirci UB, Akdim O, Miele P. Ten-year effort sand a no-go recommendation for sodium borohydride for
on-board automotive hydrogen storage. Int. J. of Hydrogen Energy. 2009;34(6):2638–2645.

[3] Li ZP, Liu BH, Morigasaki N, Suda S. Preparation of potassium borohydride by a mechano-chemical
reaction of saline hydrides with dehydratedborate through ball-milling. J. of Alloys Compd. 2003;354:243–247.

[4] M.D. Banus, R.W. Bragdon, US Patent 2,720,444, 1955.

[5] Akyüz Y, Gürü M, Tekeli S. Synthesis of MgB 2 from anhydrous B2O3 by ball-milling method and
determination of süper conductivity properties. KeyEng Mater. 2007;336-338:723–5.

[6] Fan M., Sun L., Xu F. Study of the controllable reactivity of aluminum alloys and their promising application
for hydrogen generation. Energy Conversion and Management. 2010;51(3):594-599.

[7] Çakanyıldırım, Ç, Gürü M. Processing of lithium borohydride from its elements by ball milling method.
Renewable Energy. 2008;33:2388–2392.

[8] Çakanyıldırım Ç, Gürü M. Production of NaBH4 and hydrogen release with catalyst. Renewable Energy.
2009;34(11):2362–2365.

[9] Kojima Y, Haga T. Recycling of sodium metaborate to sodium borohydride. Int. J. of Hydrogen Energy.
2003;28:989–993.

[10] Kantürk, A., Pişkin, S., Innovation in sodium borohydride production process from borosilicate glass with
sodium uııder hydrogen atmosphere: high pressure process. Int. J. of Hydrogen Energy. 2007;32:3981-3986.

[11] Çakanyıldırım Ç, Gürü M. Hydrogen cycle with sodium borohydride. Int. J. of Hydrogen Energy.
2008;33:4634-4639.

[12] Patel N., Fernandes R., Miotello A., Hydrogen generation by hydrolysis of NaBH 4 with efficient Co-P-B
catalyst: A kinetic study. J. of Power Sources, 188:411-420 (2008).

[13] Fernandes R., Patel N., Miotello A., Filippi M., Studies on catalytic behavior of Co-Ni-B in hydrogen
production by hydrolysis of NaBH4. J. of Molecular Catalysis A: Chemical, 298:1-6 (2009).

[14] Şahin Ö., Dolaş H., Özdemir M., The effect of various factors on the hydrogen generation by hydrolysis
reaction of potassium borohydride. Int. J. of Hydrogen Energy. 2007;32(13):2330-2336.