BULETINUL INSTITUTULUI POLITEHNIC DIN IAŞI

Publicat de
Universitatea Tehnică „Gheorghe Asachi” din Iaşi
Tomul LV (LIX), Fasc. 2, 2009
Secţia
CHIMIE ŞI INGINERIE CHIMICĂ

WASTEWATER TREATMENT BY ADSORPTION ON THE

MULTIPURPOSE CARBON MATERIALS
BY

CHIPURICI PETRE** GAVRILA ADINA IONUTA,** CALINESCU IOAN**,

PREDEANU GEORGETA*, BULEARCA ANCA MIHAELA**

Abstract.
The multipurpose carbon materials (MCM) are porous products resulted from the
carbonization and activation of the following materials used in our study: peach
and plum kernels, particleboard PAL and soybean hulls. The paper presents a
method for the removal of anionic surfactant (Dodecyl sulfate sodium salt) from
aqueous solutions by adsorption onto MCM using dynamic conditions. The
anionic surfactant has usually been determined by spectrophotometric methods,
using Methylene Blue. Experimental studies have been demonstrated the
possibility of surfactant removal by adsorption onto MCM. The breakthrough
point depends on the MCM parent type; the treated water volume increases with
the adsorbent column height and with the decreasing of the concentration and
supply flow
Key words: anionic surfactant, waste water treatment, adsorption, activated carbon

1.Introduction

Modern civilization development leads to an increase in the pollution to

all environmental systems: air, soil and especially water – which are the most
important natural reserves on the earth.
Water is an important element of the ecological equilibrium and its
pollution is the major problem which seriously affects the population.
Multipurpose carbon material (MCM) is the commercial name for some
adsorbents that involve different types of active charcoal. MCM is a porous
material, which can be obtained by carbonization and activation from different
carbon raw materials. These porous materials have a large internal surface (400-
1300 m2/g) and a high volume of pores (>30 cm3/100 g) [1].
 2 Chipurici P., Gavrila A.I., Calinescu I., Predeanu G., Bulearca A.M.

Diverse applications of MCM are based on the adsorption of organic

substances [2]. Some examples are: the separation of dissolved toxic solid
substances and of colloidal substances from solution (liquid discoloration and
clarifying the purification of drinkable waters), and chemical substances,
depollution of waste waters, in order to minimize the organic compounds
contents; separation by selective adsorption of gases from mixtures; catalysts
support.
The removal of water pollutants by adsorption is the most important
application of active charcoal. This is due to the following factors: the large
applicability of adsorption to different types of industrial waste water; new
residual products are not obtained; the adsorption is not dependent on toxic
residues; the adsorption plants require a minimal area.
In recent years, depollution of different organic pollutants, especially
phenol, in static and dynamic adsorption processes using activated carbon and
MCM have been intensively studied [3-9].
MCM can be obtained from various materials. In nowdays it is a trend
to obtain this materials from agricultural waste [10-13]. This fact has a double
reason: the conversion of these agricultural waste into valuble and useful
materials and the preparation of an efficient adsorbent for the removal of
organic pollutants from drinkable and residual waters.
Anionic surfactants are widely used in the production of many industrial
detergents, soaps, shampoos and toothpastes [14]. Anionic surfactants might
produce water pollution of rivers and lakes.
The adsorption of anionic surfactant (sodium dodecyl sulfate) in static
conditions, from aqueous solutions, on different activated carbons, has been
studied [15-17].
The purpose of this paper is to study the anionic surfactants removal from
water by adsorption onto MCM.

2. Experimental

MCM used in the present study has been prepared from agricultural
wastes (peach and plum kernels, soybean hulls) or from furniture industry
(particleboard PAL), by pirogenation at low temperature and activation. In the
first stage the initial raw materials were dried, preheated and transformed into
carbon material by carbonization at low temperatures 500-600 ºC (conditions:
heating rate of 7-9 ºC /min, reaction time of maximum 60 min and an
overpressure). The resulted material is activated at 1000 ºC using CO2 as an
activation agent.
 Bul. Inst. Polit. Iaşi, t. LIV (LVIII), f. 1, 2008 3

Adsorption and chemical-technical characteristics of commercial active carbon

(AC) and MCM obtained from previous materials are presented in table 1.

Table1. Adsorption and chemical-technical characteristics of MCM

Type MCM Adsorption characteristics Chemical-technical
characteristics
Surfa Micropores Iodine Volatile, Fixed Ash,
ce volumea, value, % Carbon, %
area, cm3/g mg/g %
SBET,
m2/g
AC 871.0 0.321 920.0 1.00 96.00 3.00
MCM- 123.0 0.050 438.6 15.70 66.50 17.8
soybean hulls
MCM-peach 880.4 0.267 912.9 1.55 96.22 2.23
kernels
MCM-plum 778.2 0.156 883.6 1.87 95.37 2.76
kernels
MCM- 889.7 0.230 910.3 3.13 91.40 5.47
particleboard
PAL
a
– Micropores average radius: 0.31-0.43

Sodium Dodecyl-sulfate (C12H25NaO4S) has been used as an anionic

surfactant. Aqueous solutions at different concentrations were prepared.
The characterization of the adsorption capacity of MCM in waste water
treatment was realized in dynamic conditions. Thus, different flows of the
pollutant have been passed through the adsorption column filled with the
material in fixed bed.
Adsorption column contains the adsorbent material (height 5-10 cm)
deposited in fixed bed between 2 layers of glass wool. The size of adsorbent
particles is 1 – 3 mm.
The pollutant flow was adjusted using a peristaltic pump and was varied
from 100 to 500 mL/h.
Determination of small amounts of anionic surfactants has been realized
using simplified spectrophotometric method, based on ions pair formation
between anionic surfactant – methylene blue [18]. This method presents some
advantages: small amount of chloroform needed for the ionic pair extraction,
small sample amount and short time for analysis.
The concentration of solution after passing through the adsorbent
material was followed and samples were collected at constant periods of time.
Analyses were realized using spectrophotometer UV-VIZ Shimadzu UV mini-
1240 type, and the wavelength was 650 nm.
 4 Chipurici P., Gavrila A.I., Calinescu I., Predeanu G., Bulearca A.M.

2. Results and discussion

In Romania, the normative which define the quality of waters are: Order no.
1146/2002; standards regarding effluents quality for improving receptor quality
(N.T.P.A. 001 - annexes 3.1., N.T.P.A. 002 and N.T.P.A. 011/2002 modified by H.G.
no.352/2005) and Law no. 458/2002 modified and completed by Law no. 311/2004
regarding the quality of drinkable water.
The maximum accepted concentration (CMA) for the treated water was the one
specified by the Romanian legislation (H.G. no.352/2005) for sewerage waters. Its value
is of 25 mg/L for biodegradable synthetic detergents.
In figure 1 is presented the variation of surfactant concentration function of the
adsorbent. It can be observed that MCM obtained from fruits kernels presents almost
identical adsorptive properties as AC. MCM from particleboard PAL has also
adsorptive properties similar to AC. Bad results were obtained for MCM soybean hulls.
All these results are in agreement with the chemical-technical and adsorptive
characteristics presented in table 1. The next experiments were realized using MCM
from peach kernels and AC because these materials lead to the best results.

Fig.1. Evolution of the effluent concentration after passing through the different MCM
(initial concentration of the surfactant 75 mg/L, column height 10 cm, volumetric flow
200 mL/h)
Another set of experiments were realized in order to determine the
influence of MCM layer height. Different column heights of adsorbent material
have been used (5 and 10 cm), initial concentration of surfactant was 75 mg/L
and the flow was 200 mL/h. When the column height was reduced to its half,
the treated water volume did not achieve half of its maximum accepted
concentration (CMA = 25 mg/L). It was reduced from 397 to 157 ml for peach
kernels and from 426 to 233 mL for AC.
 Bul. Inst. Polit. Iaşi, t. LIV (LVIII), f. 1, 2008 5

Fig.2. Evolution of the effluent concentration after passing through different column
heights (initial concentration of the surfactant 75 mg/L, volumetric flow 200 mL/h)

The next experiments were realized in order to study the influence of the
initial concentration on the surfactant (50, 75 and 100 mg/L). The height of the
adsorbent material was 10 cm and the effluent flow was maintained constant
(200 mL/h).

Fig.3. Evolution of the effluent concentration after passing through different surfactant
concentrations (column height 10 cm, volumetric flow 200 mL/h)
 6 Chipurici P., Gavrila A.I., Calinescu I., Predeanu G., Bulearca A.M.

From figure 3 it can be observed that the volume of treated water to CMA
increases with the decreasing of initial concentration of surfactant.
The next studied parameter was the influence of the feed flow on treated
water volume to CMA. Different flows have been used: 100, 200 and 500 mL/h,
the height of adsorbent material and the initial concentration of surfactant were
maintained constant (10 cm and 75 mg/L).

Fig.4. Evolution of the effluent concentration after passing it through different

volumetric flows (column height 10 cm, initial surfactant concentration 75 mg/L)
 Bul. Inst. Polit. Iaşi, t. LIV (LVIII), f. 1, 2008 7

Fig.5. Evolution of the treated water volume by adsorption onto MCM at the maximum
admissible concentration (CMA)
In figure 4 is presented the evolution of surfactant concentration in
effluent, based on the treated water volume. From this data, the treated water
volume at CMA had been calculated and represented in figure 5.
By analyzing the data from figures 4 and 5, it can be observed that by
decreasing the effluent flow, the treated water volume at CMA will increase.

3. Conclusion

1. Preparation of MCM using fruit kernels as raw materials is a

valuable method to transform the agricultural wastes which are pollutants for
the environment without commercial utilization into adsorbents for depollution
of waste waters.
2. Depollution of waters containing anionic surfactants (e.g. sodium
dodecyl sulfate) was studied. The comparative study was realized using MCM
obtained from agricultural waste (plum and peach kernels, soybean hulls),
industrial waste (particleboard PAL) and commercial active carbon.
3. MCM obtained from fruit kernels presented similar adsorptive
properties as the commercial active carbon.
4. The maximum accepted concentration specified by Romanian
legislation for sewerage waters is 25 mg/L. At this concentration, for a fixed
bed adsorbent layer, the treated water volume increases with:
 increasing of adsorbent layer height;
 decreasing of pollutant concentrations in effluent;
 decreasing of effluent feed flow.

*
Received: November, 05, 2009 Metallurgical Research Institute of Bucharest,
Departament of Raw Materials
**
“POLITEHNICA”University of Bucharest,
Faculty of Applied Chemistry and Material Science
e-mail: chipurici@gmail.com

REFERENCES

1. Predeanu G., Lambescu S., Slavescu V., Calinescu I., Avram R., Chipurici
P., Ciminian C., Antohe I., (2007), Manufacture and use of some Multipurpose Carbon
Materials, Proceedings International Conference on Materials Science and
Engineering, BRAMAT 2007, 22-24 february 2007, Brasov, Romania, 245-252
2. Dias J., Alvim-Ferraz M., Almeida M., Rivera-Utrila J., Sanchez-Polo M.,
Waste materials for activated carbon preparation and its use in aqueous-phase
 8 Chipurici P., Gavrila A.I., Calinescu I., Predeanu G., Bulearca A.M.

treatment: A review, Journal of Environmental.Mananagement, Elesevier Ltd., 85,(4)

833-846, (2007)
3. Mohan D., Singh K., Singh V., Wastewater treatment using low cost
activated carbons derivaded from agricultural byproducts – A case study, J. Hazard.
Mater., Elsevier B.V., 152,(3), 1045-1053, (2008)
4. Mukherjee S., Kumar S., Misra A., Fan M., Removal of phenols from water
environment by activated carbon bagase ash and wood charcoal, Chemical Engineering
Journal, Elsevier B.V. , 129, 133-142, (2007)
5. Hameed B.H., Rahman A.A., Removal of phenol from aqueous solutions by
adsorption onto activated carbon prepared from biomass material, J. Hazard. Mater.,
Elsevier B.V., 160,(2-3), 576-581, (2008)
6. Dabrowski A., Podkoscielny P., Hubicki Z., Barczak M., Adsorption of
phenolic compounds by activated carbon – a critical review, Chemosphere, 58, 1049-
1070, (2005)
7. Fierro V., Torne-Fernandez V., Montane D., Celzard A., Adsorption of
phenol onto activated carbons having different textural and surface properties,
Microporous and Mesoporous Materials, 111 (1-3), 276-284, (2008)
8. Predeanu G., Lambescu S., Slavescu V., Mihaescu D., Calinescu I.,
Chipurici P., Panaitescu C., Gavrila A.I., Wasterwater treatment by the use of some new
carbon based adsorbents, Chemical Engineering Transactions, AIDIC, 15, 23—338,
(2008)
9. Girods P. Dufor A., Firro V., Rogaume Y., Zoulalian A., Celzard A.,
Activated carbons prepared from wood particleboard wastes: Characterisation and
phenol adsorption capacities, J. Hazard. Mater., Elsevier B.V., 166, 491-501, (2009)
10. Ioannidou O., Zabaniotou A., Agricultural residues as precursors for
activated carbon production – A review, Renewable&Sustainable Energy Reviews,
Elsevier Ltd., 11, 1966-2005, (2007)
11. Aigun A., Yenisoy-Karakas S., Duman I., Production of granular activated
carbon from fruit stones and nutshells and evolution of their physical, chemical and
adsorption properties, Microporous and Mesoporous Materials, Elsevier Inc., 66, 189-
195, (2003)
12. Rengaraj S., Moon S.H., Sivabalan R., Arabindoo B., Murugesan V.,
Agricultural solid waste for the removal of organic: adsorption of phenol from water
and wastewater by palm seed coat activated carbon, Waste Management, Elsevier
Science Ltd., 22, 543-548, (2002)
13. Singh K., Malik A., Sinha S., Ojha P., Liquid-phase adsorption of phenols
using activated carbons derived from agricultural waste material, J. Hazard. Mater.,
Elsevier B.V., 150,(3), 626-641, (2008)
14. Zhang T., Oyama T., Horikoshi S., Zhao, J., Serpone N., Hidaka H.,
Photocatalytic decomposition of the sodium dodeylbenzene sulfonate surfactant in
aqueous titania suspensions exposed to highly concentred solar radiation and effects af
additives, Appl. Catal. B: Environ., Elsevier B.V., 42 (1), 13-24, (2003)
15. Gonzalez-Garcia C.M., Gonzalez-Martin M.L., Denoyel R., Gallardo-
Moreno A.M., Labajos-Broncano L., Bruque J.M., Ionic surfactant adsorption onto
activated carbons, J. Coll.Interf. Sci., Elsevier Inc., 278, 257-264, (2004)
 Bul. Inst. Polit. Iaşi, t. LIV (LVIII), f. 1, 2008 9

16. Ayranci E., Duman O., Removal of anionic surfactants from aqueous
solution by adsorption onto high area activated carbon cloth studied by in situ UV
spectroscopy, J. Hazard. Mater., Elsevier B.V., 148,(1-2), 75-82, (2007)
17. Basar C.A., Karagunduz A., Cakici A., Keskinler B., Removal surfactants
by powdered activated carbon and microfiltration, Water Research, Elsevier Ltd., 38,
2117-2124, (2004)
18. Koga M., Yamamichi Y., Nomoto Y., Irie M., Tanimura T., Yoshinaga T.,
Rapid Determination of Anionic Surfactants by Improved Spectrophotometric Method
Using Methylene Blue, Analytical Sciences, 15, 563- 568, (1999)

TRATAMENTUL APELOR REZIDUALE PRIN ADSORBTIE PE MATERIALE

CARBONICE MULTIFUNCTIONALE

(Rezumat)

Materialele carbonice multifunctionale (MCM) sunt produse poroase rezultate prin

carbonizarea si activarea diferitelor materiale: sâmburi de prună si piersică, PAL
melaminat si teci de soia. Lucrarea prezintă o metodă de îndepărtare a surfactantilor
anionici (dodecilsulfat de sodiu) din solutiile apoase prin adsorbtie pe materialele
carbonice multifunctionale în conditii dinamice. Concentratia surfactantului anionic a
fost determinată spectrofotometric utilizând albastru de metilen. Studiile experimentale
au demonstrat posibilitatea îndepărtării surfactantului prin adsorptia pe MCM. Punctul
de străpungere depinde de tipul de material carbonic folosit; volumul de apă tratată
creste cu înăltimea coloanei cu material adsorbant si cu micsorarea concentratiei
surfactantului si cu scăderea debitului de alimentare.