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Activated carbon obtained by pyrolysis of potato peel for the removal of heavy
metal copper (II) from aqueous solutions
J.C. Moreno-Piraján a,∗ , L. Giraldo b
a
Departamento de Química, Facultad de Ciencias, Universidad de Los Andes, Grupo de Investigación en Sólidos Porosos y Calorimetría, Bogotá, Colombia
b
Departamento de Química, Universidad Nacional de Colombia, Bogotá, Colombia
a r t i c l e i n f o a b s t r a c t
Article history: Activated carbons (ACs) were prepared by pyrolysis of potato peel in presence of zinc chloride (chemi-
Received 17 January 2010 cal activities). Potato peel from Colombian cultives were impregnated with aqueous solutions of ZnCl2
Accepted 18 October 2010 following a variant of the incipient wetness method. Different concentrations were used to produce
Available online 23 October 2010
impregnation ratios of 40, 70, 110 and 160 wt.%. Activation was carried out under argon flow by heating
to 823 K with 4 h soaking time. The porous texture of the obtained ACs was characterized by physical
Keywords:
adsorptions of N2 at 77 K and CO2 at 273 K. The impregnation ratio had a strong influence on the pore
Peel potato
structure of these ACs, which could be easily controlled by simply varying the proportion of ZnCl2 used in
Adsorption
Surface area
the activation. Thus, low impregnation ratio led to essentially microporous ACs. At intermediate impreg-
Activated carbon nation ratios, ACs with wider pore size distribution (from micropores to mesopores) were obtained.
Langmuir Finally, high impregnation ratios yielded essentially mesoporous carbons with high surface area and
Prausnitz–Radke pore volume. The four best-fit three-parameter isotherms Sips, Toth, Radke–Prausnitz and Vieth–Sladek
suggest that the sorption capacity of activated carbon of potato peel to uptake copper ions to be 74 mg/g.
1. Introduction primary foods in our country and usually used for traditional food,
cake, etc. Various agricultural products are widely used as basis
Activated carbons are materials having complex porous Colombia food such as cassava, maize, onion, rice, sugar and spe-
structures with associated energetic as well as chemical inhomo- cially potato. The potato production in Colombia is very huge and
geneities. Their structural heterogeneity is a result of existence only small amounts are utilized by traditional food industries, and
of micropores, mesopores and macropores of different sizes and the rest are used as the raw material for cassava starch industries.
shapes. Activated carbon is one of the most important adsorbents Potato starch making operation produces a large amount of solid
from an industrial view of point. The main application of this adsor- wastes (potato peel), and direct discharge of this solid wastes will
bent is for separation and purification of gaseous and liquid phase cause the environmental problems. Here we report on the porous
mixtures [1–7]. texture characteristics of ACs prepared by ZnCl2 activation of potato
There are two processes for preparation of activated carbon: peel, i.e. the shells covering potato. These constitute a by-product
chemical activation and physical activation. Chemical activation is from potato processing following harvest with few practical appli-
known as a single step method of preparation of activated carbon in cations and whose uncontrolled spill (e.g. in rivers) causes some
the presence of chemical agents. Physical activation involves car- environmental concern. In fact, applications of potato peel are lim-
bonization of a carbonaceous materials followed by activation of ited to use as fuel or as feedstock to obtain food for animal.
the resulting char in the presence of activating agents such as CO2 The other hand solid and liquid wastes are generated in large
or steam. The chemical activation usually takes place at a temper- amounts in the wastewater of several industries such as metal
ature lower than that used in physical activation, therefore it can cleaning and plating baths, refineries, paper and pulp, fertilizers
improve the pore development in the carbon structure because of and wood preservatives which are being dumped or released into
the effect of chemicals. The carbon yields of chemical activation the water causing detrimental effects not only on humans but also
are higher than physical one [6,8–30]. Potato is the most impor- upon environment, therefore it has become imperative to develop
tant foods in Colombia, an agricultural country. Potato is one of the methods for treating such wastes. Studies have proved that heavy
metals such as lead, zinc, cadmium, chromium and copper are very
toxic elements [8,9]. The excessive intake of copper by man leads
∗ Corresponding author. Tel.: +57 1 3394949; fax: +57 1 3324366. to severe headaches, hair loss, hypoglycemia, increased heart rate,
E-mail address: jumoreno@uniandes.edu.co (J.C. Moreno-Piraján). nausea, damage of kidney, and liver. It may also cause psychological
0165-2370/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.jaap.2010.10.004
J.C. Moreno-Piraján, L. Giraldo / Journal of Analytical and Applied Pyrolysis 90 (2011) 42–47 43
Fig. 1. Furnace vertical for obtain of activated carbon from cassava peel.
problems, such as brain dysfunction, depression, and schizophrenia 2.3. Pore structure characterization
[9–36].
We will show that carbon adsorbents with high surface areas The porous texture of ACs was characterized by physical
and pore volumes can be obtained from this material, and that adsorption of nitrogen at 77 K (using an automatic volumet-
development of the porous structure can be modulated by changing ric adsorption apparatus, AUTOSORB 3B from Quantachrome
the relative proportions of feedstock and ZnCl2 . instruments) and carbon dioxide at 273 K (using a automatic
volumetric adsorption apparatus, AUTOSORB 3B from Quan-
2. Experimental tachrome instruments). In either case the samples were degassed
overnight at 573 K before every adsorption measurement. Gases
2.1. Reagents used had minimum purities of 99.999% (N2 ) and 99.98% (CO2 ).
N2 adsorption data were analyzed by means of the BET and
All chemicals were of reagents grade, purchased Merck and Dubinin–Radushkevich (DR) equations, the ␣S method (using
potato peel were obtained from cultives Colombian. Spheron-6 carbon black as reference material) and the density func-
tional theory (DFT). CO2 adsorption data were analyzed by the
2.2. Treatment and preparation of sample Dubinin–Radushkevich–Kaganer (DRK) equation.
Prior to the use, the potato peel was repeatedly washed with dis-
tilled water in order to remove dust and other inorganic impurities,
then oven-dried for 24 h at 393 K to reduce the moisture content. 2.4. Study of pH and determination of isotherms of adsorption
Peel from Colombian potato were impregnated with aqueous solu- from aqueous solution
tions of chloride zinc following a variant of the incipient wetness
method; similar cases have been described in literature [11–14]. Batch adsorption experiments were carried out in a series of
This consists of adding dropwise (while stirring the solid, to facil- stopper reagent bottles. 100 mL of CuSO4 solution with prede-
itate homogeneous absorption of liquid) the amount of aqueous termined initial concentration of 10, 20, 30, 40, 50 to 100 mg/L
solution (2.0 mL g−1 potato peel) necessary to produce swelling was put inside the 30 mL stopper reagent bottles, which contained
until incipient wetness. Different concentrations of ZnCl2 in aque- 0.5 g using the activated carbon of mayor area (ACPP160). Prior to
ous solution were used to vary the content of impregnation agent, that, the pH solution was adjusted to the desired values by adding
which will be expressed as impregnation ratio (Xp , wt.%), defined HNO3 or NaOH. The reagent bottles with activated carbon–CuSO4
as (gram ZnCl2 per g potato peel) × 100. Impregnation ratios of 40, mixture were shaken using an orbital incubator shaker, which
70, 110 and 160 wt.% were used. After impregnation, the samples operated at 100 rpm and 298 K (±1 K) for 8 h to attain the equi-
were dried for 8 h at 383 K in air. Pyrolysis treatments (activations) librium condition. Blank solutions were treated similarly without
were carried out in a vertical tubular reactor made of quartz in fur- the adsorbent, and the recorded concentrations at the end of each
nace CarboliteTM , (Fig. 1) using in all cases 25 g of impregnated and operation were taken as the initial. The final concentrations of the
dried material. solution were then determined from a calibration curve. The solu-
All treatments were done at a constant heating rate of tions were continuously agitated for at least 8 days, which is the
10 K min−1 and with an argon (99.999% pure) flow of 30 maximum contact time to reach equilibrium with this sorbent and
STP cm3 min−1 , which was kept during heating and cooling. An acti- particle size (according to previous studies with many other met-
vation temperature of 823 K and a soaking time of 4 h were used. als). Blank samples were also processed in the absence of sorbent to
After cooling the solid pyrolysis residue to room temperature it check for sorption on the experimental equipment (flasks, filtration
was washed with milli-Q distilled water until lowering the con- units, etc.) and the absence of precipitation phenomena. Samples
ductivity of the washing liquids to <5 s cm−1 (measured with a were finally collected and filtered using 1.2 m pore size filter
pH/conductivity meter HP, model MARK 602). The resulting ACs membranes. Metal content in the filtrate was measured by atomic
was dried at 383 K for 24 h in a vacuum furnace. The activated car- emission spectrometry (AES) (Perkin Elmer AAnalyst 300, US). The
bon were labeled here as: ACPP40, ACPP70, ACPP110 and ACPP160, mass balance equation was used to calculate the amount of copper
of according to their impregnation ratios with ZnCl2 . at equilibrium. Therefore, the sorption capacity q (mg Cu g−1 ) was
44 J.C. Moreno-Piraján, L. Giraldo / Journal of Analytical and Applied Pyrolysis 90 (2011) 42–47
200
ume corresponding to pores of width <0.7 nm) follows the opposite
3
175 trend. Let us examine now the variation of the micropore volume
as a function of Xp . Parameters such as Vmicrop. (DRK, CO2 )] and
150
ads
2,5 80
70
2
60
1,5 50
qe,mg/g
qe,mg/g
40
1
30
0,5 20
10
0
0 2 4 6 8 10 12 0
pH 0 20 40 60 80 100 120
Ce, mg/L
Fig. 3. Effect of pH on adsorption capacity of copper ions on activated carbon CP160.
Fig. 4. Adsorption of copper for ACPP160. Model Langmuir conditions: pH: 7.0,
Temp: 298 K.
itively charged such that the attraction between biomass and metal
cations is reduced.
In contrast, as the pH increases, more negatively charged sur- Experiments were performed at controlled pH using sodium
face becomes available thus facilitating greater copper removal. It hydroxide and sulfuric. The pH of the solutions was regularly
is commonly agreed that the sorption of metal cations increases checked and the pH was controlled when the variation was ±0.1.
with increasing pH as the metal ionic species become less stable We have followed the same treatment for our adsorption data from
in the solution. However, at higher pH values (pH 9, pH 10, pH 11 aqueous solution suggested in [13,17]. For non-linear method, a
and pH 12) there is a decrease in the adsorption capacity. This is trial and error procedure, which is applicable to computer oper-
due to the occurrence of copper precipitation. At pH 6 there are ation is developed using solver add-in, Microsoft spreadsheet,
three species present in solution as suggested by Elliot and Huang Microsoft Excel [17] shows the calculated isotherm parameters and
[4], Cu2+ in very small quantities and Cu(OH)+ and Cu(OH)2 in large their corresponding coefficient of determination, r2 , values were
quantities. Three species are adsorbed at the surface of adsorbent shown in Table 3. From this table, it was observed that the higher r2
by ion exchange mechanism with the functional groups present values for the three-parameter Sips, Redlich–Peterson and the two-
in adsorbent or by hydrogen bonding. This behavior agrees with parameter Langmuir isotherms suggests the applicability of these
results found by our research group [12,13]. models to represent the equilibrium sorption of copper ions by acti-
vated carbon of potato peel particles. In addition to Sips, Langmuir
and Redlich–Peterson isotherm the equilibrium copper ions uptake
3.3. Adsorption isotherm of copper from aqueous solution
by activated carbon of potato peel particles was reasonably well
represented by Toth, Radke–Prausnitz and Vieth–Sladek isotherms
The capacity of the adsorption isotherm is fundamental, and
with r2 values of 0.978. The value of Sips isotherm constant mS
plays an important role in the determination of the maximum
and the Redlich–Peterson isotherm constant g equal to unity sug-
capacity of adsorption. It also provides a panorama of the course
gests that the isotherm is approaching the Langmuir isotherm and
taken by the system under study in a concise form, indicating
not Freundlich isotherm. The lower r2 values for Freundlich and
how efficiently a carbon will adsorb and allows an estimate of
the economic viability of the carbons commercial applications for
the specified solute. In order to adapt for the considered system, Table 3
Isotherm parameters for copper ions onto activated carbon ACPP from cassava
an adequate model that can reproduce the experimental results
potato obtained by non-linear method at 298 K.
obtained, equations of Langmuir, Freundlich, Redlich–Peterson,
Toth, Vieth–Sladek, Fritz–Schluender, Radke–Prausnitz and Temkin Langmuir Freundlich
have been considered. Thus, the non-linearized forms of the dif- qm (mg/g) = 62.76464521 KF = 7.654389
ferent isotherm models were shown in Table 2. Fig. 4 shows the KL = 0.087392543 1/nF = 0.482726
adsorption of ions copper adjusted of Langmuir model. r2 = 0.989875464 r2 = 0.958191
Table 4 Table 5
Sorption capacities of several adsorbents for the uptake of ions copper from its Thermodynamic parameters for the adsorption of Cu(II) onto ACPP160.
aqueous.
Temperature (K) G◦ (kJ/mol) H◦ (kJ/mol) S◦ (kJ/mol)
Sorbent Sorption capacity Reference
303 −18.89
Bark pine pulp 45.2 [27] 313 −15.87
Manganese nodule power 40.0 mg/g [28] 323 −13.45
−37.838 −0.08490
Tourmaline 30.0 mg/g [29] 333 −11.45
Bamboo 15.0 mg/g [30] 343 −10.23
Humic acids from Fluka AG and Aldrich 51.47 mg/g [31] 353 −9.76
Activated charcoal 10.20 mg/g [32]
Zeolite 5.0 mg/g [33]
Fungal mycelium pellets of Aspergillus niger 4.5 mg/g [34] and hence resulting in lesser adsorption capacity at higher tem-
Alumina 15.0 mg/g [35]
peratures. The value of H◦ is negative, indicating that adsorption
Clay 18.0 mg/g [36]
Activated carbon of cassava peel 52 mg/g [12,13] process is exothermic in nature. The negative value of S◦ indi-
Activated carbon of potato peel 62 mg/g This study cates the stability of sorption process with no structural change at
solid–liquid interface.
The effect of temperature, a major factor, influencing the adsorp- The authors would like to thank the Departments of Chemistry
tion was studied in the range of 303–343 K. The thermodynamic of the Universidad Nacional de Colombia and of the Universidad
parameters, such as enthalpy (H◦ ), entropy (S◦ ) and Gibb’s free de Los Andes (Colombia) and the Master Agreement established
energy (G◦ ) were estimated using the following relation: between these two institutions. Special gratitude the Fondo Espe-
cial de Investigaciones de la Facultad de Ciencias de la Universidad
Ca de Los Andes (Colombia) for its partial financing of these research.
Kc = (2)
Ce
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