ARTICLE IN PRESS

Water Research 39 (2005) 5055–5063

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Development of a reliable alkaline wastewater treatment

process: optimization of the pre-treatment step
M. Prisciandaroa, G. Mazziotti di Celsob, F. Vegliòa,
a
Department of Chemistry, Chemical Engineering and Materials, University of L’Aquila, Monteluco di Roio, L’Aquila, Italy
b
Department of Food Science, University of Teramo, Mosciano S. Angelo, Teramo, Italy
Received 15 February 2002; received in revised form 3 March 2004; accepted 21 December 2004

Abstract

Alkaline waters produced by caprolactam plants polymerizing the fibres of nylon-6 are characterized by a very high
alkalinity, salinity and COD values, in addition to the presence of recalcitrant organic molecules. These characteristics
make alkaline wastewaters very difficult to treat; so the development of the suitable sequence to carry out in a
depuration process appears of great interest.
The proposed general process consists of three main steps: first, pre-treatment for the acidification of the polluted
stream, second, a successive extraction of the bio-recalcitrant compound (noted as cycloexanecarboxysulphonic acid
(CECS)) and a final biological treatment. In particular, this paper deals with the pre-treatment step: it consists of an
acidification process by means of sulphuric acid with the concomitant precipitation of black slurries in the presence of
different substances, such as solvents, CaCl2, bentonite, several flocculants and coagulants.
The aim of this study is to set an experimental procedure, which could minimize fouling problems during sludge
filtration. The use of additives like bentonite seems to give the best results, because it allows good COD reductions and
a filterable precipitate, which avoids excessive fouling problems of the experimental apparatus.
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Keywords: Alkaline wastewaters; Bio-recalcitrant compounds; Mud precipitation; Pre-treatment

1. Introduction The detection of the appropriate treatment sequence

Industrial wastewater treatment has to be a suitable
arrangement of chemical, physical and biological
processes, to minimize the inhibitory, toxic or recalci-
trant effect of mineral and organic contaminants,
particularly on the microbiological agents of wastewater
treatment plant, in order to guarantee the role of
ultimate step to the biological stage (Donati et al., 1968;
Tempesti et al., 1976).
Corresponding author. Tel.: +39 862 434223;
fax: +39 862 434203.
E-mail address: veglio@ing.univaq.it (F. Vegliò).
plays a major role in those processes in which waste-
waters are particularly difficult to treat with a conven-
tional procedure, since they contain contaminants very
hard to neutralize (Hashim et al., 1992). This is the case of
alkaline wastewaters (AWW), like those produced by
caprolactam plants (Fantauzzi et al., 1998; Baccella et al.,
2000). On the other side, only effective solutions of
problems of increasing the profitability of petrochemical
plants makes it possible to produce competitive products.
A possible way is to raise the degree of processing of the
initial feedstock by recycling the byproducts, which may
create considerable problems for the environment, as in
the case of caprolactam plants (Semenov et al., 1997).

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doi:10.1016/j.watres.2004.12.025
 ARTICLE IN PRESS
M. Prisciandaro et al. / Water Research 39 (2005) 5055–5063 5061

Summarizing, results obtained during the II experi- 100

Precipitate weight (kg/m3)

mental series have showed that calcium chloride 90
addition during the acidification step reduces the
sticking characteristics of the black mud precipitated, 80
thus making the process reliable for an industrial 70
application.
60
3.3. III Series 50
40
Experiments belonging to the third series use a
different co-precipitator, chosen between those com-
monly utilized in the field of complex solid separa-

Sulphate (kg/m3 AWW)

114
tion, such as bentonite (Naseem et al., 2001). This
112
compound has been added to the solution in the range
from 10 to 30 kg/m3AWW and the results in terms of 110
precipitate amounts, filtrate sulphate concentration, 108
COD and cake-filter resistance have been reported in
106
Figs. 6i–iv.
Fig. 6i highlights that precipitate weight linearly 104
grows, increasing bentonite amount added in solution;
Fig. 6ii illustrates the behaviour of sulphates, which
initially decrease as increasing bentonite amount, then 288
grow, with a minimum concentration at 106 g/l for
COD (mg/l)

286
20 kg/m3AWW of bentonite added; Fig. 6iii reports
the linear decrease of COD from about 290 to 280 g/l, 284
corresponding to a 20% removal; finally, Fig. 6iv
concerns a parameter (b) directly linked to the cake- 282
filter resistance by means of Eq. (2); it appears that
280
b has a behaviour similar to that of sulphates, reaching
a minimum value for 25 kg/m3AWW of bentonite
added. The last two performances (Figs. 6iii and iv) 9 10–3
Slope b (g/cm8s) (Eq. 2)

could indicate that a massive precipitation of com- 8 10–3

pounds like NaHSO4 takes place, thus improving sludge
7 10–3
filterability.
Results obtained are very promising, most of all 6 10–3
because they show that black mud produced in the 5 10–3
presence of bentonite has a good filterability, greatly 4 10–3
reducing the problem of vessel wall fouling.
3 10–3
In order to improve bentonite performance, some
available commercial flocculants (Ecoclar Anionic 2 10–3
5 10 15 20 25 30 35
(8003), Cationic (8339) and Non-Ionic (8007)) and 3
Bentonite (kg/m AWW)
coagulants (Alpoclar and ferric chloride) in different
combinations have been tested. All experiments have Fig. 6. (i–iv) Behaviour of precipitate weight, sulphates, COD
been conducted for a fixed bentonite concentration, and cake-filter resistance as a function of bentonite added in
equal to 20 kg/m3, and a fixed amount of coagulants and solution.
flocculants, equal to 100 and 50 ppm, respectively.
Experimental runs have been performed, evaluating
the effects on precipitate weight, COD, total solids, filter resistance grows, too. Some of these results are
cake-filter resistance and sulphate concentration. Re- reported in Figs. 7 and 8, in particular, Fig. 7 shows
sults have been reported in Table 4, which shows that precipitate weight in the presence and in the absence of
the adding of flocculants and coagulants besides coagulants, with different flocculants utilized; while in
bentonite (runs 2–12) has almost always negative out- Fig. 8 the filtrate COD behaviour in the same conditions
comes with respect to the presence of bentonite alone has been reported.
(run 1). Finally, it can be concluded that to perform the best
Above all, while COD and total solid values are results, it is necessary to avoid adding coagulants and
slightly modified, precipitate weight increases, and cake- flocculants to bentonite.
 ARTICLE IN PRESS
5062 M. Prisciandaro et al. / Water Research 39 (2005) 5055–5063

Table 4
Experimental runs carried out with bentonite together with flocculants and coagulants

Run no. Coagulant Flocculant Precipitate weight Total solids b parameter pH Sulphates COD
(kg/m3) (g/l) Eq. (2) (g/cm8 s) (g/l) (g/l)

1 — — 63.1 372 0.0037 1.5 110.7 279.2

2 Alpoclar — 63.2 354 0.0029 1.6 117.9 260.8
3 Ferr. Clor. — 66.8 338 0.0034 1.6 110.1 273.6
4 — 8003 66.8 400 0.0010 1.6 92.7 309.6
5 Alpoclar 8003 63.5 396 0.0046 1.5 115.6 296.0
6 Ferr. Clor. 8003 67.4 334 0.0032 1.9 99.5 288.0
7 — 8007 62.8 372 0.0083 1.4 113.0 304.8
8 Alpoclar 8007 65.1 334 0.0071 1.8 109.6 293.6
9 Ferr. Clor. 8007 66.7 366 0.0059 1.7 108.7 288.0
10 — 8339 73.9 346 0.0062 1.6 101.0 296.0
11 Alpoclar 8339 67.0 376 0.0044 1.6 110.4 288.0
12 Ferr. Clor. 8339 77.3 384 0.0062 1.6 113.4 250.4

90 350

80
300
Precipitate weight (kg/m3)

70
no floc. no floc.
floc.1 250
60 floc.2 floc.1
floc.3
50 floc.2
COD (g/l)

200
floc.3
40

30 150

20
100
10

0 50
no coag. coag.1 coag.2
0
Fig. 7. Precipitate weight in the presence and in the absence of
no coag. coag.1 coag.2
coagulants for different flocculants.
Fig. 8. Filtrate COD behaviour in the presence and in the
absence of coagulants for different flocculants.
4. Conclusions

In the present work a pre-treatment study of AWW precipitable, which avoids excessive fouling of the
with high COD values (about 350 g/l) has been carried experimental apparatus.
out. The proposed process consists of three main steps, a
first pre-treatment to acidify the polluted stream, a
successive extraction of the bio-recalcitrant compound
(noted as CECS) and a final biological process. Acknowledgements
In particular this study has been focused to the first
step. During the acidification a black mud precipitated is Authors are grateful to Mrs. Lia Mosca and Mr.
formed and an optimization of this step is necessary to Marcello Centofanti for their precious assistance during
make it more treatable for the usual solid–liquid the execution of the experimental work.
separation units (i.e. filtration, centrifugation, etc.),
because of its serious fouling characteristics.
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