You are on page 1of 13

Resources, Conservation and Recycling 49 (2007) 436448

Conversion of leather wastes to useful products


Onur Ylmaz a , I. Cem Kantarli b , Mithat Yuksel c ,
Mehmet Saglam c , Jale Yanik b,
a

Department of Leather Engineering, Faculty of Engineering, Ege University,


35100 Izmir, Turkey
Department of Chemistry, Faculty of Science, Ege University, 35100 Izmir, Turkey
c Department of Chemical Engineering, Faculty of Engineering, Ege University,
35100 Izmir, Turkey

Received 7 October 2005; received in revised form 18 April 2006; accepted 24 May 2006
Available online 7 July 2006

Abstract
The main objective of the present study is to investigate the production of useful materials from
different kinds of leather waste. Three different types of tannery wastes (chromium- and vegetabletanned shavings, and buffing dust) were pyrolyzed in a fixed bed reactor at temperatures of 450 and
600 C under N2 atmosphere. Gas, oil, ammonium carbonate and carboneous residue were obtained by
pyrolysis. The effect of temperature and type of leather waste on product distribution of pyrolysis was
investigated. Buffing dust gave the highest yield of oil (ca. 23%), while other wastes recorded yields
of ca. 9%. Results of elemental analysis and column chromatography showed that pyrolysis oils could
be used as fuel or chemical feedstock after re-treatment. The yields of carboneous residue (chars) were
between 37.5% and 48.5% and their calorific value was between 4300 and 6000 kcal kg1 , suitable
for use as solid fuel. In addition, these chars were activated by CO2 to obtain the activated carbon.
The activated carbon having highest surface area (799.5 m2 g1 ) was obtained from chromium-tanned
shavings. Activated carbons prepared from chromium-tanned leather were presented as an adsorbant
for the adsorption of dyes from aqueous solution.
2006 Elsevier B.V. All rights reserved.
Keywords: Leather wastes; Biomass; Pyrolysis; Activated carbon

Corresponding author. Tel.: +90 232 3884000x2386; fax: +90 232 3888264.
E-mail address: jale.yanik@ege.edu.tr (J. Yanik).

0921-3449/$ see front matter 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.resconrec.2006.05.006

O. Ylmaz et al. / Resources, Conservation and Recycling 49 (2007) 436448

437

1. Introduction
Leather industry is the one of the wide spread industries of Turkey. But, environmental
pollution is the main problem for leather industry. The leather making process generates
substantial quantities of solid and liquid wastes (hides and skins, fats, shaving and trimmings,
buffing dust, process effluents, sludge). The most common way to manage solid wastes is
by disposing of them on land sites.
It is reported that the tanned wastes of 0.22 kg/kg of wet salted hides/skins is generated
per year in Turkey. Since the chromium metal is the most important tanning agent, the
solid wastes from chromium-tanned leather requires special attention because of the large
amount produced and because of the legislative restrictions. In literature, there are many
studies on the treatment of tannery wastes. Most of these studies concerns the extraction
of chromium from wastes to re-use in the tanning process (Cassano et al., 1997; Imai and
Okamura, 1991; Petruzelli et al., 1995; Sivaparvathi et al., 1986a, 1986b) and isolation of
protein fractions (Mu et al., 2003; Cabeza et al., 1996, 1997, 1998).
On the other hand, pyrolysis may be one of the alternative route for treatment of solid
wastes from tannery wastes. Pyrolysis have being widely applied to organic wastes, such as
agricultural wastes, scrap tyres, sewage sludges and plastic wastes. The pyrolysis process
involves heating the carboneous material in an inert atmosphere. The products of pyrolysis
are gas, oil and carbonaceous residue. The gas can be used as fuel and the oil can either
be used as fuel or as raw material for chemicals. The carbonaceous residue can be burnt as
fuel or safely disposed ofsince the heavy metals are fixed in the carbonaceous matrix. In
addition, this residue is also suitable for production of activated carbon.
Activated carbons can be produced from carbonaceous materials by chemical (Girgis
and Ishak, 1999; Jagtoyen and Derbyshire, 1998; Namasivayan and Kadirvelu, 1997; Philip
and Girgis, 1996) and physical activation (Gonzalez et al., 1997; Lua et al., 2002; Miguel
et al., 2003; Namasivayan and Kadirvelu, 1997). The physical activation method involves
pyrolysis of the raw material and the subsequent activation at high temperature in a carbon
dioxide or steam atmosphere. The chemical activation method involves the pyrolysis of the
raw material previously impregnated with a chemical agent such as zinc chloride, phosphoric
acid, potassium hydroxide, etc. A large number of agricultural by products such as coconut
shells, palm-kernel shells wood chips, sawdust, corn cobs, seeds, etc., have been successfully
converted into activated carbons. The qualities and characteristics of activated carbons
depend on the properties of the starting materials as well as the activation methods and
processes.
In literature, there are few studies related to pyrolysis of tannery wastes. Caballero et al.
(1998) carried out a kinetic analysis of the global thermal decomposition of leather. The
pyrolysis of chromium-tanned leather was modeled assuming that it was formed by two
different fractions which decompose by two independent reactions. They also studied on
the pyrolytic products evolved from the thermal degradation of chromium tannery wastes
by two stages pyrolysis (Font et al., 1999). They concluded that the formation of pyrolytic
products was influenced by the operation conditions (temperature, heating rate). They also
detected significant levels of ammonia, hydrogen cyanide and sulfur dioxide.
On the other hand Martinez-Sanchez et al. (1989a, 1989b) and Martin-Martinez et al.
(1989) prepared the activated carbons by carbonization in nitrogen at 900 C followed by

438

O. Ylmaz et al. / Resources, Conservation and Recycling 49 (2007) 436448

activation at 825 C in carbon dioxide of chromium-tanned leather. The porous texture of


carbons has been characterized by adsorption of N2 , CO2 and iso-butane. To investigate
the effect of Cr2 O3 , they used also both pickled leather (without chromium) and extracted
leather (after chromium extraction) as carbon precursors (Martinez-Sanchez et al., 1989b).
The micropore volume (corresponding N2 at 196 C) of activated carbon from chromiumtanned leather was 0.30 cm3 g1 where as activated carbon from pickled leather had a very
low adsorption capacity. They concluded that tanning process favors the formation of the
basic structure needed to form a proper activated carbon. On the other hand, activated carbon
from extracted leather exhibited a very high adsorption capacity. It was mentioned that the
Cr2 O3 particles were partially blocking micropores in carbons and the adsorption capacity of
carbons could be increased by elimination of chromium via previous extraction of the leather.
Taking the above considerations into account, the aim of this work was to investigate
the production of useful materials from different kinds of leather wastes by pyrolysis. A
primary focus of the paper is on the production of activated carbon and investigation of its
aqueous adsorption characteristics.

2. Materials and methods


2.1. Materials
The tannery wastes chromium- and vegetable-tanned shavings and buffing dust were
supplied by Sepiciler Co., Izmir, Turkey. The chromium- and vegetable-tanned shavings
(CTS and VTS) were shredded into the rectangular pieces (1 cm 0.5 cm). Buffing dusts
(BD) was used as received. Some properties of wastes are given in Table 1.
2.2. Pyrolysis procedure
Pyrolysis experiments were carried out under nitrogen atmosphere at the temperatures
of 450 and 600 C. The pyrolysis experiments were performed in a fixed bed design and
Table 1
The properties of tanned shavings and buffing dust
Chromium-tanned

Vegetable-tanned

Buffing dust

Proximate analysis (wt.%)


Moisture
Volatile matter
Ash

7.1
67.0
9.6

5.9
59.0
3.9

5.2
67.7
6.7

Ultimate analysis (dry, wt.%)


C
H
N
S
Oa

44.3
3.1
14.2
1.8
36.6

52.4
0.9
6.6
1.1
39.0

42.8
6.1
11.0
2.1
38.0

From difference.

O. Ylmaz et al. / Resources, Conservation and Recycling 49 (2007) 436448

439

stainless steel reactor (L, 210 mm; 60 mm) under atmospheric pressure using a semi-batch
operation. The reactor was purged before experiments by nitrogen gas flow of 25 ml/min
for 10 min to remove air inside. In a typical pyrolysis experiment, a quantity of 5060 g of
leather wastes was loaded and then the reactor temperature was increased by a heating rate
of 5 C/min up to pyrolysis temperature and hold for 2 h at the desired temperature. The
nitrogen gas swept the volatile products from the reactor into the condensation unit where
the crystals of ammonium carbonates were accumulated on the wall of connection glass
line and traps and the liquid products were condensed in the traps. The non-condensable
volatiles (gases) were vented to the atmosphere.
The liquid product contained the aqueous and organic phase. The aqueous phase in liquid
product was separated from the organic phase (oil) by centrifugation. In each experiment;
char, oil, (NH4 )2 CO3 and aqueous fraction yields were determined by weighting the amount
of each obtained and calculating the corresponding percentage. Gas yield was calculated
by the difference.
2.3. Demineralization and activation of char
The char obtained from the pyrolysis was demineralized to decrease its inorganic content.
Thus, char was treated with HCl solution (10 wt.%) at 100 C for 2 h and then it was
washed with distillated water until no chlorine ions could be detected and dried at 100 C
for 24 h.
Activated carbons were prepared from chars by physical activation method. Activation
process was carried out in the pyrolysis reactor by carbon dioxide. In activation process, nondemineralized and demineralized char was heated up to 900 C under a flowing (25 ml/min)
nitrogen atmosphere. When 900 C was reached, the inert atmosphere was rapidly substituted by flowing carbon dioxide (350 ml/min). The tested activation times were 4, 6, 8 and
10 h. At the end of desired the activation time, reactor was cooled to room temperature under
nitrogen atmosphere. The resulting carbons (activated carbon) from activation process were
weighted to calculate the burn-off value.
2.4. Analysis
Elemental analysis (C, H, and N) of wastes used and oils was determined with an elemental analyzer (Carlo Erba 1106). Sulfur amount in oil was determined by using Ultraviolet
Fluorescence according to ASTM D5453. The asphaltenes of the oil were precipitated with
n-hexane and soluble in n-hexane portions were fractioned by column chromatography into
aliphatic, aromatic and polar fractions by using hexane, toluene and methanol, respectively
(Yanik et al., 1995).
The BET surface area of the activated carbons was calculated from the adsorption
isotherms by using BrunauerEmmettTeller equation. The BET (BrunauerEmmett
Teller) surface area measurements were obtained from nitrogen adsorption isotherms at
77 K using a Micrometrics FlowSorb II-2300 surface area analyzer. The scanning electron
microscopy (SEM) analyses were performed on some of activated carbons using JEOL-FEG
with EDS detector. The ash content and calorie values of activated carbons were determined
by using the following standard methods: ASTM D3172, ASTM D 5865.

440

O. Ylmaz et al. / Resources, Conservation and Recycling 49 (2007) 436448

2.5. Aqueous adsorption characteristics


The methylene blue and phenol adsorption isotherms were carried out using a batch
equilibration technique in a 250 ml conical flask at room temperature. Each flask was filled
with 100 ml of methylene blue (MB) or phenol at a known concentration (ranging between
100 and 400 mg l1 for MB and 25200 mg l1 for phenol) and 0.1 g of activated carbon.
The flask was then shaken for a determined equilibrium time (24 and 4 h for MB and
phenol, respectively) and filtered through Whatman No.1 filter-papers. The filtrate was
analyzed for adsorbate concentration using the UV spectrophotometer at max (665 nm).
Selected activated carbon was investigated for their aqueous adsorption characteristics using
phenol and MB. Residual concentrations were determined using Perkin-Elmer UVvis
spectrophotometer at 665 nm (MB) and 269 nm (phenol).

3. Results and discussion


3.1. Pyrolysis yields
The product distributions from pyrolysis of leather wastes at different temperatures are
presented in Table 2. It can be seen that the effect of temperature on product yield varied
depending on the waste type. In the case of the pyrolysis of chromium-tanned shaving (CTS)
and buffing dust (BD), high temperature led to an increase in gas yields but a decrease in
char yields. However, in the case of vegetable-tanned shaving (VTS), the gas yield did not
significantly changed when the temperature increased from 450 to 600 C.
Table 2
Product yields from the pyrolysis of leather wastes (wt.%)
Waste type
Temperature = 450 C
Gasa

Chromium-tanned

Vegetable-tanned

Buffing dust

17.8

22.4

16.8

Liquid
Aqueous
Oil

21.1
10.9

21.5
7.7

14.7
22.2

Char
(NH4 )2 CO3

44.5
5.7

48.5
Nil

40.1
6.2

23.6

23.6

20.0

Liquid
Aqueous
Oil

19.5
9.4

23.5
8.9

15.1
23.5

Char
(NH4 )2 CO3

38.1
9.3

43.8
0.3

37.5
3.9

Temperature = 600 C
Gasa

Calculated from mass balance.

O. Ylmaz et al. / Resources, Conservation and Recycling 49 (2007) 436448

441

It must be noted that the formation of (NH4 )2 CO3 was mainly observed in the pyrolysis
of CTS and BD. It may be assumed that (NH4 )2 CO3 is formed via reaction between NH3
and CO2 in the cold zone (connection lines and the wall of traps). As known NH3 is
formed from the degradation of polypeptides and the carbon dioxide is formed from the
decarboxylation of carboxylates. The fact that the formation of (NH4 )2 CO3 from chromiumtanned wastes rather than from vegetable-tanned wastes may be explained as follows. Since
the decarboxylation can be more easily occurred in presence of chromium, the evolution of
NH3 and CO2 might take place at the same time. Therefore, they can be reacted with each
other. But, in degradation of vegetable-tanned wastes, decarboxylation might be delayed. For
this reason, the formed NH3 at first was condensed in aqueous phase, without any reaction.
In pyrolysis of CTS at 600 C, the amount of (NH4 )2 CO3 was higher than that of at
450 C. This shows that high temperature improves the decarboxylation. The increment in
temperature decreased the formation of (NH4 )2 CO3 in the case of BD. This difference can
be mainly due to the particle size. It is known that particle size is one of the parameters
that influence the formation of pyrolytic products, for example mass transfer restrictions to
the volatile evolution and escape of the evolved volatiles from the inside of particle. Due
to the high reactivity of small particles, evolved NH3 can easily further react with other
decomposition products at high temperatures.
The particle size also affected the oil yields obtained from pyrolysis. For two temperatures
(450 and 600 C), the maximum oil yields were obtained from pyrolysis of BD.
3.2. Oil properties
Pyrolysis liquids can be separated into water soluble and organic phases, of which latter,
named as oil, consists of mainly a brown tar containing the high molecular weight compounds, while the water-soluble fraction contains the lower molecular weight substances.
Elemental composition of oils obtained from pyrolysis of leather wastes is shown in
Table 3. The oils from pyrolysis of chromium-tanned shaving and buffing dust were denoted
as CTSO and BDO, respectively.
The biomass-derived oils is consistent of very complex mixture. To characterize the
pyrolysis oil, the oil was fractionated as asphaltenes, aliphatics, aromatics and polars. The
composition of oils obtained from BD is shown in Table 4.
Table 3
Elemental composition of oils obtained from leather wastes pyrolysis (wt.%)
Pyrolytic oil type
CTSO

C
H
N
S
Oa
a

From difference.

BDO

450 C

600 C

450 C

600 C

63.1
1.0
14.2
0.3
21.4

59.3
6.8
15.0
0.4
18.5

65.9
3.7
8.5
0.5
21.4

68.4
6.3
7.2
0.5
17.6

442

O. Ylmaz et al. / Resources, Conservation and Recycling 49 (2007) 436448

Table 4
Composition of oils obtained from pyrolysis of buffing dust at 450 and 600 C (wt.%)

Asphaltene
Aliphatics
Aromatics
Polars

450 C

600 C

54.8
11.9
7.0
26.3

59.7
11.5
4.5
22.2

As seen from Table 4, oil contained large amount asphaltenes and the pyrolysis temperature had no considerable effect on the composition of oil. The amount of aromatic and
polar fractions slightly decreased as temperature increased. This may be due to the repolymerization of aromatics and polars to asphaltenic compounds. The unchanged amount of
aliphatic compounds shows that these compounds are resistant in the pyrolysis conditions.
The high asphaltene and polar contents of oil affect the quality of pyrolysis oil and its
use. For this, the oil obtained from leather waste can be used as fuel or chemical feedstock
after re-treatment, such as, steam cracking, hydrogenation, FisherTropsch synthesis, etc.
3.3. Char properties
Pyrolysis of leather wastes gave the char yields of about 4048%. The char consisted of
carboneous material generated during the leather thermal decomposition, polymerization
and polycondensation reactions occurring in the pyrolysis reactor and almost all of the
inorganic compounds originally present in leather wastes.
In principle, three methods can be used for the disposal of char obtained from pyrolysis
of any carboneous material, such as waste sludges, agricultural wastes, etc. (Inguanzo et
al., 2002). The char can be used as fuel, alone or mixed with other fuels. It can be used as a
cheap adsorbent. As third option, it could be safely disposed of by landfill, since the heavy
metals present in char are relatively resistant to natural lixiviation (Caballero et al., 1997).
The resulting carbonaceous residue of wastes (both CTS and VTS) was in solid block,
which was easily disintegrable into small particles. However, the char from BD was a fine
dispersed material. The main fractions were 15 mm and their share was about 49 wt.% of
the total char mass.
The calorific value and ash content of chars are given in Table 5. Because of the low ash
content, the char derived from VTS had the highest calorific value, which is comparable
to those of lignite. It could be used alone as solid fuel; the others could be incinerated by
mixing with coal.
3.4. Demineralization and activation of chars
One of the aims of this study was to produce activated carbon from solid residue of leather
wastes pyrolysis. In contrast to studies done by Martinez-Sanchez et al. (1989a, 1989b) and
Martin-Martinez et al. (1989), carbonization step of activated carbon production was carried
out at low temperatures and the chars were demineralized by acid treatment before activation
step in this study.

O. Ylmaz et al. / Resources, Conservation and Recycling 49 (2007) 436448

443

Table 5
Some properties of washed and unwashed chars with acid
Pyrolyis temperature
450 C
Before washing
Ash content (wt.%)
Char from CT
Char from VT
Char from BD

19.5
8.0
14.0

Calorific value (kcal kg1 )


Char from CT

Char from VT

Char from BD

600 C
After washing
8.5
2.3
4.7
4578
5919
4338

Before washing
22.6
9.7
15.5

After washing
16.2
4.2
13.5
4314
6009
4884

By demineralization, the ash content of chars obtained by pyrolysis at 450 C was considerably decreased, however acid washing had no considerable effect on demineralization
of chars obtained at 600 C, especially obtained from CT and BD. This shows that inorganic materials in leather wastes were converted to acid-insoluble form at high pyrolysis
temperature.
As expected, the maximum decrease in ash content by acid washing was obtained in
chars derived from VT (Table 5); the ash content of chars obtained at 450 and 600 C was
decreased at the ratio of 71.2% and 56.7%, respectively.
To obtain the activated carbon, acid washed and non-washed chars were activated
with CO2 . Fig. 1 shows the influence of activation time on the degree of burn-off in
CO2 achieved for both washed and non-washed chars. The type of char used in each run
is seen in Table 6. The chars from pyrolysis at 450 C of buffing dust, chromium- and
vegetable-tanned shaving were denoted as CBD-450, CCT-450 and CVT-450, respectively,
in Table 6. The carbon burn-off exhibited an increase with increasing activation time for

Fig. 1. Carbon burn-off in CO2 for chars obtained from pyrolysis of leather wastes.

444

O. Ylmaz et al. / Resources, Conservation and Recycling 49 (2007) 436448

Table 6
Surface areas of activated chars
Char type

Activation time (h)

BET surface area (m2 g1 )

C-1, CBD-450 (washed with acid)


C-1 (CBD-450, washed with acid)
C-2 (CCT-450, washed with acid)
C-3 (CCT-450, unwashed with acid)
C-4 (CCT-600, unwashed with acid)
C-5 (CVT-600, unwashed with acid)

10
8
10
6
6
8

617.2
551.6
799.5
82.9
61.8
295.0

both demineralized and non-demineralized of chars. As can be seen from Fig. 1, in the
case of demineralized CCT-450, a burn-off value of 70% was obtained for the activation
time of 10 h. However, an activation time of 6 h was enough to reach the similar burn-off
value in the case of non-demineralized char (C-1 and C-2). It is clear that acid treatment
decreased the reactivity of char, since char reactivity is related to the ash content of the
carbonaceaus materials (Ucar et al., 2005). Several researchers have also mentioned that
some inorganic compounds showed catalytic effect on gasification (Cazorla-Amoros et al.,
1996; Cunliffe and Williams, 1999; Samaras et al., 1996).
A key property of activated carbon is their surface area. Commercial activated carbons
typically have a surface area in the range from 400 to 1500 m2 g1 . The BET surface areas
of activated carbons derived from leather wastes are presented in Table 6.
The ash content, most of which were chromium compounds, and activation temperature were main parameters for the enhancement of activated carbons. There is extreme
difference between BET surface areas of activated carbons obtained from mineralized and
non-demineralized chars. The surface area of activated carbon from C-2 is approximately
10 times higher that that of activated carbon from C-3. This different behavior is not surprising considering the large ash content of the carbons, especially for high CO2 burn-off.
In previous report (Martin-Martinez et al., 1989), it was concluded that the Cr2 O3 particles
are partially blocking micropores in carbons from chromium-tanned leather; if a portion of
these particles is eliminated by previous extraction of the leather, the adsorption capacity
is considerably increased. It should be noted that the surface area of activated carbon from
C-1 (10 h) was lower than that of activated carbon from C-2, although former activated
carbon has lower ash content than later activated carbon. The reason may be due to the char
sample. It may be suggested that the inorganics up to limited amounts improve the surface
area. It has been reported that although Cr2 O3 is blocking the micropores is also acting as
a frame for the structure of the activated carbon (Martinez-Sanchez et al., 1989c).
Activation time had also an effect on the surface area. In activation of demineralized
CBD-450, the increase of activation time from 8 to 10 h, the BET surface area increased at
the ratio of approximately 10%.
As conclusion, to obtain the activated carbon, leather wastes should be pyrolyzed at
450 C and then demineralized with HCl before activation at 900 C. The activated carbon
having highest surface area was obtained from chromium-tanned shavings.
The EDS results (Table 7) are based on elemental analysis of selected particles on the
activated carbon surface. It merits mentioning that there was a noticeable scattering of
inorganics particles, mainly chromium compounds, present on activated carbons.

O. Ylmaz et al. / Resources, Conservation and Recycling 49 (2007) 436448

445

Table 7
Summary of EDS analysis of activated carbons
Activated carbon

A-BD
A-CTS

Element (wt.%)
C

Mg

Cl

Cr

Fe

Cu

Zn

59.08
34.98

2.47
1.88

2.08
2.16

3.58

27.46
42.16

2.39
16.97

1.63
0.71

1.30
1.14

3.5. Aqueous adsorption characteristics


Aqueous adsorption tests were conducted on selected activated carbons with the aim of
assessing potential applications in the water treatment industry. Two adsorbate compounds
were used in this study cover a range of molecular sizes, which makes them useful for
the investigation of adsorption in pores of different dimensions. Phenol is preferentially
adsorbed in small and medium sized micropores while methylene blue is mainly adsorbed
in medium and large micropores (Miguel et al., 2003).
In order to optimize the design of an adsorption system to remove dye or phenol from
effluents, it is important to find the best isotherm equations. The isothermal equilibrium
data were processed employing Langmuir and Freundlich isotherm equations.
The Freundlich model is considered to be suitable for highly heterogeneous surfaces and
indicates that significant adsorption takes place at low concentrations, but the increase in the
amount adsorbed with concentration becomes less significant at higher concentration (Teng
and Hsieh, 1998). On the other hand, Langmuir model is used for homogenous surfaces and
demonstrate monolayer coverage of the adsorbate at the outer surface of the adsorbent.
Table 8 shows the Langmuir (Ce /Qe = 1/KL SM + Ce /SM , where SM is the saturated adsorp1/n
tion and KL is the constant related to the adsorption energy) and Freundlich (Qe = KF Ce ,
where Qe is the amount adsorbate, Ce the equilibrium concentration of the adsorbate, KF
and n are the constants) parameters obtained by fitting the MB and phenol adsorptions
on activated carbons. In the case of MB, Langmuir model was found to fit the data well
(R2 > 0.95). The Langmuir capacity (SM ) of A-BD was more than that of A-CTS. For phenol
adsorption, both equations were found to fit the data well (R2 > 0.95).
Results in Table 8 shows that activated carbon obtained from BD have higher adsorption
capacity for phenol and methylene blue than activated carbon from CTS. Tseng et al.
Table 8
Parameters of the Langmuir and Freundlich adsorption models of MB and phenol
Activated carbon

Langmuir model
SM

Methylene blue
A-BD
A-CTS
Phenol
A-BD
A-CTS

(mg g1 )

200
166.7
84.745
56.179

Freundlich model
KL

(l mg1 )

7.14
30.00
0.0282
0.04052

R2

1/n

KF

R2

0.99
0.99

0.1913
0.1715

116.98
88.94

0.55
0.59

0.99
0.97

0.4783
0.4369

7.0048
6.014

0.98
0.96

446

O. Ylmaz et al. / Resources, Conservation and Recycling 49 (2007) 436448

(2003) obtained SM values of 556 and 240.6 mg g1 for the adsorption of MB and phenol,
respectively, on the activated carbon prepared from pinewood. A SM value of 46.95 mg g1
for adsorption of phenol onto activated carbon from sewage sludge (Chen et al., 2002) and
a SM value of 225.64 mg g1 for adsorption of MB onto activated carbon from jute fiber
(Senthilkumaar et al., 2005).
As conclusion, owing to their poorly developed micropore structure, activated carbons
obtained from leather wastes showed low adsorption capacity for phenol. In contrast, activated carbons possessed relatively higher adsorption capacity for methylene blue due to
their highly developed mesopore structure. It can be concluded that one important aspect of
activated carbons prepared from chromium-tanned leather is the high volume of macropores,
which is important for the adsorption from solutes, such as dyes, in aqueous solution.
4. Conclusion
In this study, three types of leather wastes were pyrolyzed at the temperatures of 450 and
600 C under nitrogen atmosphere. Pyrolysis of leather wastes yielded the charred residue
and ammonium carbonate besides gas and oil products. Pyrolysis yields varied with the type
of leather waste. Pyrolysis temperature significantly affected the acid solubility of inorganic
constituents in chars.
The char from vegetable-tanned leather wastes was suitable to use a solid fuel because
of its high calorific value and low ash content. On the other hand, the activated carbons
having the high volume of macropores were produced from the chars obtained at 450 C
char by physical activation. The experiments related to aqueous adsorption characteristics of
activated carbons showed that the prepared activated carbons could be used as an adsorbent
for the effective removal of dyes from aqueous solutions.
Consequently, the results of this work showed that waste leather is a useful recycling
resource and the conversion of wastes into activated carbon and fuels may be recognized as
an attractive approach. This work can be considered complimentary to other studies which
have concentrated on protein isolation and chromium recovery. However, in our case, as in
the case of other works further works are necessary before large-scale application of these
studies is realisable.
Acknowledgement
We would like to thank to Ege University for financial support under the contract 04CSUM-001.

References
Caballero JA, Font R, Esperanza MM. Kinetics of the thermal decomposition of tannery waste. J Anal Appl
Pyrolysis 1998;47:16581.
Caballero JA, Font R, Marcilla A, Conesa JA. Characterization of sewage sludges by primary and secondary
pyrolysis. J Anal Appl Pyrolysis 1997;40/41:43350.

O. Ylmaz et al. / Resources, Conservation and Recycling 49 (2007) 436448

447

Cabeza LF, Taylor MM, Brown EM, Marmer WN. Isolation of protein products from chrome-containing leather
waste using two consecutive enzymes and purification of final chromium product: pilot plant studies. J Soc
Leather Technol Chem 1996;83(1):149.
Cabeza LF, Taylor MM, Brown EM, Marmer WN. Influence of pepsin and trypsin on chemical and
physical properties of isolated gelatin from chrome shavings. J Am Leather Chem Assoc 1997;92(8):
2007.
Cabeza LF, Taylor MM, Brown EM, Marmer WN. Chemical and physical properties of protein products isolated from chromium-containing leather waste using two consecutive enzymes. J Soc Leather Technol Chem
1998;82(5):1739.
Cassano A, Drioli E, Molinari R, Bertolutti C. Quality improvement of recycled chromium in the tanning operation
by membrane processes. Desalination 1997;108(13):193203.
Cazorla-Amoros D, Ribes-Perez D, Roman-Martinez MC, Linares-Solano A. Selective porosity development by
calcium-catalyzed carbon gasification. Carbon 1996;34:86978.
Chen X, Jeyaseelan S, Graham N. Physical and chemical properties study of the activated carbon made from
sewage sludge. Waste Manage 2002;22:75360.
Cunliffe AM, Williams PT. Influence of process conditions on the rate of activation of chars derived from pyrolysis
of used tires. Energy Fuels 1999;13:16675.
Font R, Caballero JA, Esperanza MM, Fullana A. Pyrolytic products from tannery wastes. J Anal Appl Pyrolysis
1999;49:24356.
Girgis BS, Ishak MF. Activated carbon from cotton stalks by impregnation with phosphoric acid. Mater Lett
1999;39:10714.
Gonzalez MT, Rodriguez-Reinoso F, Garcia AN, Marcilla A. CO2 activation of oilive stones carbonized under
different experimental conditions. Carbon 1997;35(1):15965.
Imai T, Okamura H. Studies on incineration of chrome leather waste. J Am Leather Chem Assoc
1991;86(8):28194.
Inguanzo MA, Dominguez JA, Menendeo CG, Blanco JJ. On the pyrolysis of sewage sludge: the influence of
pyrolysis conditions on solid, liquid and gas fractions. J Anal Appl Pyrolysis 2002;63:20922.
Jagtoyen M, Derbyshire F. Activated carbons from yellow poplar and white oak by H3 PO4 activation. Carbon
1998;36(7/8):108597.
Lua AC, Yang T, Gua J. Effects of pyrolysis conditions on the properties of activated carbons prepared from
pistachio-nut shells. J Anal Appl Pyrolysis 2002;72:27987.
Martin-Martinez JM, Rodriquez Reinso F, Martinez-Sanchez MA, Orgiles-Barcelo C. Role of chromium oxide in
the texture of carbons from leather. In: Ferrero GL, Maniatis K, Buekens A, Bridgwater AV, editors. Pyrolysis
and gasification. Elsevier Science Publishers; 1989. p. 4526.
Martinez-Sanchez MA, Orgiles-Barcelo C, Martin-Martinez JM, Rodriquez Reinso F. The role of chromium
oxide in the adsorptive behaviour of activated carbons from leather waste. In: Proceedings of the 19th biennial
conference on carbon; 1989a.
Martinez-Sanchez MA, Orgiles-Barcelo C, Martin-Martinez JM, Rodriquez Reinso F. Activated carbons from
chromium-tanned leather waste. In: Ferrero GL, Maniatis K, Buekens A, Bridgwater AV, editors. Pyrolysis
and gasification. Elsevier Science Publishers; 1989b. p. 43943.
Miguel GS, Fowler GD, Sollars CJ. A study of the characteristics of activated carbons produced by steam and
carbon dioxide activation of waste tire rubber. Carbon 2003;41:100916.
Mu C, Lin W, Zhang M, Zhu Q. Towards zero discharge of chromium-containing leather waste through improved
alkali hydrolysis. Waste Manage 2003;23:83543.
Namasivayan C, Kadirvelu K. Activated carbons prepared from coir pith by physical and chemical activation
methods. Bioresour Technol 1997;62:1237.
Petruzelli D, Passino R, Tiravanti G. Ion exchange process for chromium removal and recovery from tannery
wastes. Ind Eng Chem 1995;34:26127.
Philip CA, Girgis BS. Adsorption characteristics of microporous carbons from apricot stones activated by phosphoric acid. J Chem Technol Biotechnol 1996;67:24854.
Samaras P, Diamadopoulos E, Sakellaropoulos GP. The effect of mineral matter and pyrolysis conditions on the
gasification of Greek lignite by carbon dioxide. Fuel 1996;75:110814.
Senthilkumaar S, Varadarajan PR, Porkodi K, Subbhuraam CV. Adsorption of methylene blue onto jute fiber
carbon: kinetics and equilibrium studies. J Colloid Interface Sci 2005;284(1):7882.

448

O. Ylmaz et al. / Resources, Conservation and Recycling 49 (2007) 436448

Sivaparvathi M, Suseela K, Nanda SC. Hydrolytic action of Pseudomonas Aeruginosa on chrome shavings. Leather
Sci 1986a;33(1):811.
Sivaparvathi M, Suseela K, Nanda SC. Purification and properties of Pseudomonas Aeruginosa protease causing
hydrolysis of chrome shavings. Leather Sci 1986b;33(11):3037.
Teng H, Hsieh CT. Influence of surface characteristics on liquid-phase adsorption of phenol by activated carbon
prepared from bituminous coal. Ind Eng Chem Res 1998;37(8):361824.
Tseng RL, Wu FC, Juang RS. Liquid-phase adsorption of dyes and phenols using pinewood-based activated
carbons. Carbon 2003;41:48795.
Ucar S, Karagoz S, Ozkan AR, Yanik J. Evaluation of two different scrap tires as hydrocarbon source by pyrolysis.
Fuel 2005;84:188492.
Yanik J, Yuksel M, Saglam M, Olukcu N, Bartle K, Frere B. Characterization of the oil fractions of shale oil
obtained by pyrolysis and supercritical water extraction. Fuel 1995;74(1):4650.

You might also like