International Journal of Engineering Sciences, 2(9) September 2013, Pages: 435-441

TI Journals
ISSN
2306-6474

International Journal of Engineering Sciences

www.tijournals.com

Pyrolysis of Some Polymeric Waste Materials and

the Adsorptivity of the Pyrolytic Chars
Khaled M. Elsousys *
(Assoc. professor/chemistry department)
Alaqsa University/ Gaza/ Gaza Strip/ Palestinian Territories.
AR TIC LE INF O

AB S TR AC T

Keywords:

Pyrolysis of four waste polymeric materials under the same conditions were conducted (polyvinyl
chloride PVC, poly urethane PU, moderate density fabric MDF, and tire derived rubber particles
(TDRP). Concerning aqueous adsorptivity, chars of the polymeric materials were compared with
commercial activated carbon. TDRP was chosen to have more detailed study; it was pyrolyzed at various
temperatures, heating rates, heating times under water vapor atmosphere. The resulting chars were tested
for their aqueous adsorption characteristics. Methylene blue value MBV and iodine number IN tests
were conducted to compare the adsorptivity of each product char. Kinetics of the adsorption process for
methylene blue in aqueous media was studied. The results show that pyrolysis of TDRP was optimum at
700 C and gave a char yield of approximately 43%. Methylene blue number and iodine value were
affected by pyrolysis temperature, pyrolysis time. Pyrolysis of TDRP at 700C and 60 min residence
time is the optimum conditioned process. Adsorption saturation isotherms were developed for the
produced chars. Linearized Langmuir models were applied and the related constants were obtained.
Kinetics of adsorption of methylene blue was first order kinetics in each of char dose and MB. The
adsorption rate constants were obtained. Adsorption thermodynamics were tested. Influence of
adsorption temperature on the equilibrium adsorption constant keq was studied, adsorption
thermodynamic parameters were obtained.

Reuse tier rubber

Pyrolysis
Adsorption
Thermodynamics
kinetics

2013 Int. j. eng. sci. All rights reserved for TI Journals.

1.

Introduction

The composition of some scrap polymeric materials hinders their recycling. Pyrolysis of these materials to produce usable chars is thought
to be in some cases the proper way of reuse. The last argument is true mainly for cross-linked and/or networked polymers. Car tire mostly
is manufactured from diverse kinds of natural and synthetic rubber, including styrene-butadiene co-polymers. [1, 2, 3] As many other
polymeric wastes, scrap car tires are discarded mainly in landfills, city lots, rivers and lakes all over the word.
Pyrolysis of hardly recycled polymeric hydrocarbons produces liquid hydrocarbons, gaseous components and a solid residue (char)
composed mostly of carbon.[4, 5, 6] Previous investigations have demonstrated that the produced oil can be used directly as a fuel oil and
as a raw material in petrochemical processes. [7] The gas can be used as fuel gas, while the char can be employed a raw material for the
production of activated carbon. [8, 9, 10] Some recent investigations have focused on producing activated carbon from scrap tires, some
other studies were concerning to characterize the produced chars. [11,12] Generally the quality of active carbons is evaluated in terms of
their adsorptive characteristics and superficial area, using different analytical methods for liquid and gas phase adsorption. Used
automotive tires contain polymeric aromatic structures which are similar to those of coal in some respects in addition to some metallic and
nonmetallic additives (Zn, S etc.). Therefore, pyrolysis of waste tires to produce valuable products is currently receiving some attention.
Pyrolysis may be carried out in mildly oxidizing atmospheres, such as steam and carbon dioxide, to improve the quality of pyrolytic
products. [12, 13, 14] Specifically tire pyrolysis performed in an inert environment produced 33-38 wt % of carbon residue. It has been
reported that the char yield increases with decreasing pyrolysis temperature and decreasing heating rate [9]. The surface area of tire char
also depends on pyrolysis temperature and heating rate. The surface area of a tire char produced by pyrolysis in an inert gas usually ranges
from 30 to 90 m2/g. [15, 10, and 11] Activation of tire chars performed in high pressure CO, at 900C environment gave higher surface
areas. Similar behavior was also reported for tire char activation in steam. [l2]
The total surface area in units of (m2 /g) is actually a measure of activation or efficiency for producing activated carbon. Pyrolysis of
granulated and non-granulated tires has shown recoveries of gases, liquid oils and solid char. The product yields vary with the variation of
pyrolysis condition and pretreatment. The sulfur within tire rubber was found advantageous for char product after pyrolysis. It was reported
that the surface areas of tire chars are comparable with those of carbon blacks in rubber products, but too low if compared with that of
commercial activated carbon. Therefore, an activation process is thought to be required for producing activated carbon from tire chars.
* Corresponding author.
Email address: khasousi@yahoo.com

Khaled M. Elsousys

436

Int ernational Journal of Engi neering Sciences, 2( 9) Sept e mber 2013

According to USA standard test method (ASTM D4607-94, 2006) for determination of iodine number of activated carbon; iodine number
IN is a relative indicator of porosity in an activated carbon, although it may not necessarily provide a measure of the carbon`s ability to
absorb other species. However iodine number may be used as an approximation of surface area and micro-porosity of active carbons with
good precision. [13, 14. 15]
Methylene blue Value MBV as a rough estimation of large molecule adsorption capacity was used to evaluate miso-porosity of char
surface. [12, 13. 14] The standard method (ASTM D3860-98, 2003) was used to obtain MBV. [12]
The objective of this investigation was to pyrolyze some polymeric waste materials in identical way as tire derived rubber particles TDRP.
The pyrolyzed products were compared with respect to aqueous adsorptivity. Influences of the pyrolysis parameters (pyrolysis temperature,
heating rate and residence time) were evaluated in the case of TDRP. The porous texture of the prepared active carbons was investigated
with IN and MBV. Adsorption equilibrium isotherms were developed for the char using MB and I2 as the adsorbent. Linearized Langmuir
model was applied and the related constants were obtained. Kinetics of adsorption of MB on the produced char was studied. Influence of
adsorption temperature and thermodynamics of aqueous adsorption was studied; the thermodynamic parameters were calculated. Influence
of each of Ionic strength and pH were also tested.

2.

Experimental

2.1 Materials
Polyvinyl chloride PVC, poly urethane foam powder PU, moderate density fabric saw dust MDF, were collected locally as waste polymeric
materials. The collected samples were cleaned using distilled water, and used with no further treatment. TDRP was Envio-ESI/ Type A/
made in china was taken as the main raw material for pyrolysis, table 1 show the results of analysis for some chemical additives of the used
TDRP, the experiments were performed by the department of Activated carbon/ Nuchar Pelletized/West vacco/ Covington/VA/USA.
Methylene blue (C16 H18N 3SCl); 319.85 g/mole), Commercial activated carbon BDH/ England product was heated at 300oC for 24 hours
before used. I2 ,KI, H2SO4 ,NaOH, and other used materials were analytical grade, purchased from Akross/ Italy.
Table 1. Concentrations of metal additives in the material of (TDRP).
Zn
15690
2078

Ag
0
-

Pb
7.6
1.3

Fe
1183
465

Co
7.2
0.24

Mg
462
28

Ca
2398
585

Metal
mg/ kg
S.D

2.2 Instruments
Atomic absorption spectrophotometer, GBC932 plus was used to analyze the concentrations of metals in TDRP, Thermo controlled,
BIFATHERM, model RA electric furnace was used for pyrolysis. Visible spectrophotometer, SC, labomed, Inc. USA was used for
spectrometric measurements. Particle size distribution of the powdered char was determined using Image tool, scope image with the aid of
(400:1) computerized microscope.
2.3 Methodology
Pyrolysis was carried out in a muffle furnace. Each sample (10g of polymer with 20 ml of distilled water) was placed in a covered ceramic
crucible and placed in the furnace. Samples were heated to various pyrolysis temperatures (500-1000C). Various heating periods
(residence time) were tested with the desired heating rate (2-10C/min).
The solid pyrolysis residues were cooled in the oven down to 100C then out of the oven to room temperature, powdered by ceramic mortar
(7-25 micron average radius) and transferred to undergo washing. Samples were washed sequentially, several times with hot de-ionized
water and finally with cold de-ionized water until the solutions were neutral to litmus paper. The washed samples were dried at 120C to be
used as experimental adsorbent with no any further activation process.
The end product was characterized concerning to yield %, iodine number ID and methylene blue value MBV. The yield is defined as the
ratio of the mass of activated carbon obtained to the initial mass of the polymer powder, both based on dry weight method. [12]. Iodine
number was obtained according to the USA standard test method (ASTM D4607-94, 2006) for IN determination. [12] The amount of iodine
adsorbed (mg/g carbon) at a residual iodine concentration of 0.02 N was reported as the iodine number. The standard method (ASTM
D3860-98, 2003) was used to obtain MBN in (mg/g char). [13] The amount of MB adsorbed (mg/g) at a residual MB concentration 100
mg/ l was reported as MBV.
The equilibrium adsorption behavior was studied using batch technique. Removal efficiency of methylene blue (mg/g) for various initial
concentrations of adsorbent was evaluated. Aqueous solutions of methylene blue were placed in 250 ml flasks and shaken at 25 C for
24 hours with a 0.1 g samples including commercial char. The relation was plot between the adsorption capacity and equilibrium
concentration.

Pyrolysis of Some Polymeric Waste Materials and the Adsorptivity of the Pyrolytic Chars

437

Internat ional Jour nal of Engineeri ng Science s, 2(9) Septe mber 2013

The concentrations used were in the range of 30 to 300 ppm MB and 100 to 1000 ppm I 2/I- solutions. All experiments were carried out in
triplicates with respect to each condition and mean values were used for calculations. Identical blanks were used in every condition. That
was because of the expected loss of water by evaporation, or any other unconsidered factors. The final concentration of the blank was taken
as C0 and not the preparation concentration. The maximum deviation in each procedure was in the range 2 %.
Effect of changing pH on the adsorption capacity was studied with pH (3 to 12) using standard solutions of NaOH and H2SO4 . Activated
carbon (0.1g) was mixed with 10mg/100ml of methylene blue solution for each pH sample. Influence of ionic strength on the adsorption
capacity was studied. Solutions from 0.001 to 0.1M of Na 2SO4 were used. 0.1g of activated carbon was mixed with 10.0mg/100ml
solutions of methylene blue for each sample.
The adsorption kinetic study was performed in batch method; using 100 ml aqueous MB solutions of identical concentrations (30 ppm) in
250 ml Erlenmeyer flasks and varying amounts of char (0.1 -0.4g) were added to each flask. The systems were maintained at constant
temperature under constant shaking rate of 150 rpm. The uptake was calculated from the initial and moment concentrations. Pseudo first
order kinetic model was applied and the specific rate constant k was calculated in s-1g-1.

3.

Results and discussion

3.1 Pyrolysis of different starting polymer powders

It follows from table 1 that differences are present in the product % yield, iodine number IN and methylene blue value MBV. Differences in
% yield are thought to be according to the original heavy elements percentage and the bonding strength generally. IN was varying
according to the total surface areas; MBV is a measure of the mesopores intensity at the surface of the char cool particles.
Table 2. Characteristics of the pyrolysis products of polymeric particles, pyrolysis temperature 500o C, 10.0 g starting mass,
20g H2 O, residence time 1.0 hr., heating rate 10 oC/min.
Comm.
-149
360

TDRP
48
296
571

MDF
6
291
505

PU
18
230
626

PVC
42
294
1305

Char
Yield %
MBV
IN

3.2 Influence of temperature on pyrolysis of TDRP

Choosing TDRP for further study, keeping all other parameters fixed, the products of different temperatures pyrolysis were characterized as
shown in table 2.
Table 3. Characteristics of TDRP pyrolysis Chars of different pyrolysis temperatures 10.0 g starting TDRP mass,
20g H2O, residence time 1.0 hr., heating rate 10 oC/min.
1000
23
213
603

900
35
347
614

800
39
344
606

700
43
337
607

600
45
325
607

500
48
296
571

Temp., oC
Yield %
MBV
IN

It is obvious that the optimum pyrolysis temperature is 700oC, Concerning the yield, Iodine number and methylene blue value.
3.3 Influence of residence time on the pyrolysis of TDRP
Pyrolysis residence time influence is depicted in table 4. It can be observed that under the present experimental conditions 60 minutes of
residence time is optimum to reach the highest adsorption capacity comparable with the loss % of the starting polymer mass.
Table 4. Characteristics of TDRP chars of different pyrolysis residence times, 10.0 g starting TDRP mass,
20g H2O, pyrolysis temperature 500oC, heating rate 10 o C/min.
180
34
320
606

150
37
317
614

120
40
305
606

90
43
301
607

60
48
296
607

30
58
189
571

Time, min.
Yield %
MBV
IN

3.4 Influence of pyrolysis heating rate on pyrolyzed chars

Pyrolysis heating rate gave no significant influence under the present pyrolysis conditions using the present procedure. Other recent studies
proved that increasing the heating rate had more positive influence on the produced char surface area. [15]

Khaled M. Elsousys

438

Int ernational Journal of Engi neering Sciences, 2( 9) Sept e mber 2013

3.5 Adsorption isotherms

It follows from figure 1 that the adsorption isotherm of I2/ TDRP char is starting to level on around 2500 mg/l equilibrium concentration
while the adsorptivity around this point is 650 mg/g char. The adsorption capacity is comparable with other commercial chars without any
more activation.

Figure 1. Adsorption isotherm for I2/ TDRP char, 700oC, 0.1g char, T=25oC, pH 7, 100 ml (I2/I-).

It follows also from figure 2 that the maximum adsorptivity of MB by TDRP char is around 280 mg/g at 100 mg/l which is also
comparable with commercial chars again without further activation.
Equilibrium for I2 and MB adsorption on TDRP char were modeled with the Langmuir. According to equation 1:

Ce/qe = Ce/qm + 1/ (Ka . qm) (1)

Where qm mg/g and Ka (l/mg) are Langmuir constants related to adsorption capacity and energy of adsorption, respectively. The constants
qm and Ka can be calculated from the plot between Ce /qe and Ce (Eq. 1). Ce mg/l and qe mg/g are the equilibrium concentration and the
amount of dye adsorbed at equilibrium, respectively.

Figure 2. Adsorption isotherm for MB/ TDRP char, 700oC, 0.1 g char, T=25oC, pH 7, 100 ml solution volume.

Linear plot of specific adsorption (Ce/qe ) against the equilibrium concentration Ce was obtained. It follows from Figure. 3 and 4 for I2 and
MB respectively that the adsorption obeys strongly the Langmuir model.

Pyrolysis of Some Polymeric Waste Materials and the Adsorptivity of the Pyrolytic Chars

439

Internat ional Jour nal of Engineeri ng Science s, 2(9) Septe mber 2013

Figure 3. Linearized Langmuir isotherm for I2/ TDRP char 700o C, 0.1 g char, T=25oC, pH 7, 100 ml solution volume.

Figure 4. Linearized Langmuir isotherm for MB/ TDRP char 700o C, 0.1 g char, T=25oC, pH 7, 100 ml solution volume.

The Langmuir constants qm and Ka were determined from the slopes and intercepts of the two plots for each I2 and MB adsorption. The
resultant values are presented in Table 5.
Table 5. Data from Langmuir linearized plot of the adsorption of I2 and MB on TDRP char.

Co, mg/l
100
1000

RL
0.49
7.2x10-4

R2
0.9988
0.9468

Ka
0.0101
1.3929

qm
0.0038
0.9762

Adsorbate
MB
I2

The value of the correlation coefficient for MB and I2 adsorption (0.9468 and 0.9988) obtained from Langmuir expression indicates
that Langmuir expression provided a good linearity.
Characteristics of the Langmuir isotherm can be expressed in terms of a dimensionless constant separation factor R L that is given by the
following equation [14]:

RL = 1/ (1+ Ka. Co) (2)

Where C0 mg/l is the initial concentration of adsorbate and Ka l/mg is Langmuir constant. The value of RL indicates the shape of the
isotherm which is unfavorable (RL>1), linear (RL=1), favorable (0 < R L < 1), or irreversible (RL= 0). The RL values for the adsorption of
I2 and MB are observed to be in the range 01, indicating that the adsorption was a favorable process. After this point; MB
adsorption on Char of (700oC, 60.0 minutes residence time and 10oC/minuets heating rate) was selected for further study under the
mentioned experimental conditions.

Khaled M. Elsousys

440

Int ernational Journal of Engi neering Sciences, 2( 9) Sept e mber 2013

3.6 Influence pH and ionic strength

From the experimental tests; it was found that neither pH change (controlled by H 2SO4 and NaOH) nor ionic strength of different
concentration of K2 SO 4 (0.01 - 0.1 M) has any significant effect on the adsorption equilibrium of MB by TDRP char 700 oC under the
mentioned experimental conditions. The absence of any effect supports thinking that adsorption process does not include any ions or ionic
reactions [16].
3.7 Adsorption kinetics
The elimination percentage of methylene blue by adsorption on TDRP char with respect to contact time was followed. Char of (700oC, 60.0
minutes residence time and 10oC/minuets heating rate) was used under the mentioned experimental conditions. As shown in Fig. 5 the
adsorption follows pseudo-first order kinetics for MB. The natural logarithm of (Co/C) has a straight line relation with time. Dose of char
influenced the adsorption rate. The slopes in Fig. 1 shows that the rate increases directly with the increase of the amount of char used up to
0.4g/100ml. The average specific rate constant and t1/2 (half-life) of adsorption were calculated to be (k= 0.13 s-1 g-1 and t1/2 = ~ 4 s g-1). The
relation is pseudo first order in the studied range. It can be estimated also that a 24 hours period is more than adequate time to achieve
practical equilibrium.

Figure 5. The relation between ln (C o /C) vs. time to verify pseudo first order kinetics of MB
adsorption on 0.1, 0.2 g, 0.3, 0.4 char 700oC, T=25oC, pH 7, 100 ml solution volume.

3.8 Adsorption thermodynamics

Rising adsorption temperature was enhancing the adsorption capacity, where the adsorption equilibrium constant Keq was increasing by
temperature rise. From fig 6 which represents Vant Hoff plot; it can be observed that the adsorption is endothermic process.
Thermodynamic parameters for adsorption of MB on the char surface were calculated from the slope and intercept.

Figure 6. Vant Hof plot of ln K eq vs. 1/ T for MB/ TDRP char 700o C, 0.1 g char, T=25oC, pH 7, 100 ml solution volume.

Pyrolysis of Some Polymeric Waste Materials and the Adsorptivity of the Pyrolytic Chars

441

Internat ional Jour nal of Engineeri ng Science s, 2(9) Septe mber 2013

Change in free energy G (kJ/ mol), enthalpy H (kJ/ mol) and entropy S (J/K. mole) were determined using the following equations:

Keq = Csolid / Cliquid (3)

G = -RT lnKeq (4)
InKeq = (S/ R) (H/RT) (5)
Where Keq is the standard equilibrium constant, Csolid is the solid phase concentration at equilibrium (mg/l), Cliquid is the liquid phase
concentration at equilibrium (mg/l), T is the temperature in Kelvin and R is the gas constant in (J/K.mole). According to the results it could
be thought that physisorption is much more favorable for the adsorption of MB by TDRP char. The value of H(-4.824 kJ/ mole )shows the
low endothermic nature of adsorption which governs the possibility of physical adsorption. It also shows that the adsorption is favorable
and spontaneous.
The negative value of G ( -30.0 kJ/ mole ) shows that the adsorption is favorable and spontaneous. The positive value of S (117 J
K-1.mole-1) shows the increased disorder at the solid solution interface components. The enhancement of adsorption capacity of the TDRP
char at higher temperatures was attributed to the enlargement of pore size and/ or activation of the adsorbent surface.

References
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
[10]
[11]
[12]
[13]
[14]

Dez, C., Snchez M. E., Haxaire, P., Martnez, O., Morn, A. : Journal of Analytical and Applied Pyrolysis (2005) 74(1-2):254-258.
Cunliffe, A. M. and Williams, P. T.: Journal of Analytical and Applied Pyrolysis (1998) 44(2):131-152.
Zabaniotou, A. A. and Stavropoulos, G.: Journal of Analytical and Applied Pyrolysis (2003) 70(2):711-722.
Dez, C., Martinez, O., Calvi, L. F., Cara, J. and Morn, A.: Waste Management (2004) 24(5):463-469.
Mui, E., Ko D. and McKay G.: a review. Carbon (2004) 42(14):2789-2805.
Itodo, A. U., Abdulrahman, F. W.,Hassan, L. G. and Maigandi, S. A.: Int. J Chem.Sci. (2008) 1(2):214-220.
Rodriguez, I. M., Laresgoiti, M. F., Cabrero, M. A., Torres, A., Chomn, M. J., Caballero, B.: Fuel Processing Technology (2001) 72:9-22.
Laresgoiti MF, Caballero BM, Marco I, Torres A, Cabrero MA, Chomn M. J. :Journal of Analytical and Applied Pyrolysis (2001) 71(2):917-934.
Miguel, GS, Fowler, GD, Sollars, C. J.: Carbon (2003) 41(5):1009-10016.
Cui, H., Yang, J. and Liu, Z.: Termochimica Acta (1999) 333(2):173-175.
Roy, C., Chaala, A. and Darmstadt, H.: Journal of Analytical and Applied Pyrolysis (1999) 51(1-2):201-221.
Roy, C., Darmstadt, H., Benallal, B. and Amen-Chen, C.: Fuel processing Technology (1997) 50(1):87-103.
Dubinin, M. M.: In Chemistry and Physics of Carbon/A Series of Advances. Marcel Dekker Inc.; (1965) 51-120.
D. H. Everett,: Manual of Symbols and Terminology for Physicochemical Quantities and Units, Appendix II: Definitions, Terminology and Symbols in
Colloid and Surface Chemistry. Pure and Applied Chemistry (1972); 31(4):577-638.
[15] Teng, H., Serio, M.A., Wojtowicz, M.A., Bassilakis, R., Solomon, P. R.: J. Ind. Eng. Chem. Res., (1995) 34: 3102-3111.
[16] K. J., Laidler and J. H., Meiser,: Physical Chemistry, 4th ed. Addison (2003) 392.