Hydrodechlorination of 4-Chlorophenol using Ni-Al Pillared Clays as

Catalysts

C.B. Molina*, A. H. Pizarro, J.A. Casas, J.J. Rodrguez
Chemical Engineering Area. School of Sciencies. University Autnoma of Madrid. 28049.
Madrid. Spain. Tel.: 34-914973516; Fax: 34-914973516; *carmenbelen.molina@uam.es

Introduction

Chlorophenols are synthetic organic compounds obtained on large industrial and commercial
scales and extensively used as pesticides, herbicides, dyes, etc. They are highly toxic and
hardly biodegradable and different methods have been tested to remove them from water.
Hydrodechlorination (HDC) is one of the more promising, yielding phenol and/or more
hydrogenated products as cyclohexanone. Different supported metal catalysts have been used
for this reaction, mainly noble metals on activated carbon [1], Al
2
O
3
[2] or zeolites [3]. In this
work, a low-cost metal as nickel has been used as active phase supported on Al-pillared clays
as catalysts for HDC of 4-chlorophenol (4-CPhOH) using hydrogen as reducing agent at mild
conditions.

Experimental

Ni-Al pillared clays were synthesized by impregnation of Al pillared clay (Al-PILC)
calcinated at 350C with a solution of NiCl
2
, NiNO
3
or nickel acetate (0.5 ml solution/g clay).
After impregnation, the Ni-Al pillared clays were calcinated at 500 C. The Ni loads tested
were 1, 2.5, 5 and 10 wt % of Ni in the final catalyst. The HDC experiments were performed
in a batch stirred glass jacketed reactor at 50C in most cases and atmospheric pressure. 100
mL of 4-CPhOH solution (100 mg/L) were placed in the reactor with 1 g/L of catalyst. H
2
was
introduced in the reactor by bubbling in the liquid phase. The HDC process was followed
from the evolution of the concentration of 4-CPhOH, phenol (measured by HPLC) and more
hydrogenated products as cyclohexanone or cyclohexanol which were measured by FID/CG.

Results and discussion

The Ni-Al pillared clays prepared showed basal spacing values around 1.9 nm and surface
area around 180 m
2
/g, indicating a successful pillaring process. The effect of the nickel
precursor was studied using NiCl
2
, NiNO
3
and nickel acetate (10 wt % of Ni in all cases) and
a reaction temperature of 50C. As can be seen in Fig. 1, NiNO
3
gave rise to the catalyst with
the highest 4-CPhOH removal and phenol production. Thus, this salt was chosen as precursor
of Ni for the synthesis of the rest of Ni-Al pillared clays. Next, the effect of Ni load was
tested. Al-pillared clays with 1, 2.5, 5 and 10 wt % of Ni were prepared and they were used as
catalysts in the HDC reaction at 50C (Fig. 2). As can be seen, the catalysts with 1 or 2.5 wt
% of Ni gave rise to a low 4-CPhOH removal whereas the ones with the highest Ni content, 5
and 10 wt %, yielded a high catalytic activity very similar between them. A 5 wt % of Ni was
selected for next studies. Likewise, the effect of reaction temperature was checked in the
range of 25-70 C and the results are shown in Fig. 3. When the reaction was performed at 25
C a very low 4-CPhOH removal was achieved, while higher temperatures as 50 and 70C
yielded a dramatic increase in the 4-CPhOH conversion, with very similar values in the
phenol production in these last cases. Finally, the effect of the catalyst concentration was
tested, increasing it up to 2 and 4 g/L at 50C. As can be seen in Fig. 4, a significant increase
in the 4-CPhOH removal was achieved at higher catalyst concentration in the reaction media,
a)
being the experiment with 4 g/L of catalyst the only one where cyclohexanone was also
detected as by-product. A fairly stable fixation of nickel was achieved since this metal was
found in very low amount in the reaction media.



























Conclusions

An active, stable and low-cost catalyst has been prepared, based on Ni-Al pillared clays,
which allows reaching a high 4-CPhOH removal which is converted to much less toxic phenol.
Although a high catalyst concentration is needed to obtain the complete removal of the 4-
CPhOH (4 g/L) at the working temperature (50C), this is compensated by the fact that the
active phase used, nickel, is much more economical than the noble metals usually employed
for HDC of chlorophenolic compounds.

Acknowledgments

The authors would like to thank the financial support from the Spanish MEC through the
project CTQ2005-02284/PPQ.

References
[1] Calvo, L., Mohedano, A.F., Casas, J.A., Gilarranz, M.A., Rodrguez, J.J., Hydrodechlorination of 4-
chlorophenol in aqueous phase using Pd/AC catalysts prepared with modified active carbon supports, Applied
Catalysis B: Environmental, 67(1-2) (2006), 68-76
[2] Keane, M.A., A review of catalytic approaches to waste minimization: Case study - liquid-phase catalytic
treatment of Chlorophenols, Journal of Chemical Technolology and Biotechnology, 80(11) (2005), 1211-1222
[3] Howe, R.F., Zeolite catalysts for dehalogenation processes, Applied Catalysis A, 271 (2004), 311
Figure 2. Effect of Ni load at 50C
a)
b)
b)
Figure 3. Effect of reaction
temperature using NiAl-IMP-5

Figure 1. Effect of the Ni precursor at
50C
Figure 4. Effect of catalyst
concentration using NiAl-IMP-5