This article was downloaded by: [Universite Laval]

On: 08 October 2014, At: 22:23

Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered office:
Mortimer House, 37-41 Mortimer Street, London W1T 3JH, UK

Journal of Macromolecular Science, Part A:

Pure and Applied Chemistry
Publication details, including instructions for authors and subscription
information:
http://www.tandfonline.com/loi/lmsa20

Alkaline Hydrolysis of Waste Poly(Ethylene

Terephthalate): A Modified Shrinking Core
Model
a a
Santosh Kumar & Chandan Guria
a
Department of Polymer Engineering , Birla Institute of Technology ,
Ranchi, India
Published online: 07 Feb 2007.

To cite this article: Santosh Kumar & Chandan Guria (2005) Alkaline Hydrolysis of Waste Poly(Ethylene
Terephthalate): A Modified Shrinking Core Model, Journal of Macromolecular Science, Part A: Pure and
Applied Chemistry, 42:3, 237-251, DOI: 10.1081/MA-200050346

To link to this article: http://dx.doi.org/10.1081/MA-200050346

PLEASE SCROLL DOWN FOR ARTICLE

Taylor & Francis makes every effort to ensure the accuracy of all the information (the “Content”)
contained in the publications on our platform. However, Taylor & Francis, our agents, and our
licensors make no representations or warranties whatsoever as to the accuracy, completeness, or
suitability for any purpose of the Content. Any opinions and views expressed in this publication
are the opinions and views of the authors, and are not the views of or endorsed by Taylor &
Francis. The accuracy of the Content should not be relied upon and should be independently
verified with primary sources of information. Taylor and Francis shall not be liable for any
losses, actions, claims, proceedings, demands, costs, expenses, damages, and other liabilities
whatsoever or howsoever caused arising directly or indirectly in connection with, in relation to or
arising out of the use of the Content.

This article may be used for research, teaching, and private study purposes. Any substantial
or systematic reproduction, redistribution, reselling, loan, sub-licensing, systematic supply, or
distribution in any form to anyone is expressly forbidden. Terms & Conditions of access and use
can be found at http://www.tandfonline.com/page/terms-and-conditions
 Journal of Macromolecular Sciencew, Part A: Pure and Applied Chemistry, 42:237–251, 2005
Copyright # Taylor & Francis, Inc.
ISSN 1060-1325 print/1520-5738 online
DOI: 10.1081/MA-200050346

Alkaline Hydrolysis of Waste Poly(Ethylene

Terephthalate): A Modified Shrinking Core Model

SANTOSH KUMAR AND CHANDAN GURIA

Department of Polymer Engineering, Birla Institute of Technology, Ranchi, India

Hydrolytic decomposition of waste poly(ethylene terephthalate) (PET) is studied in the

presence of an aqueous potassium hydroxide solution. A modified shrinking core model
Downloaded by [Universite Laval] at 22:23 08 October 2014

with a depleting product layer of waste PET is developed under finite solution volume
conditions. An analytical solution is obtained for the model based on average molar
distribution coefficient of aqueous potassium hydroxide solution. This model assumes
the first order depolymerization kinetics with respect to the concentration of
potassium hydroxide solution. The convrsion of the waste PET is determined after
filtration of the unreacted PET left after depolymerization. The conversion of PET is
also compared with the amount of terephthalic acid obtained after acidification of
the filtrate. Infra red (IR) spectroscopy studies of unreacted PET samples at different
hydrolysis time intervals are carried out. It is observed that the transmittance at
1700 cm21 decreases gradually with reaction time, which confirms the increased
concentration of carbonyl group generated from aryl carboxylic acid group and the
major reaction is occurring on the polymer chain end on the solid PET surface.
Average molar distribution coefficient of aqueous potassium hydroxide solution,
intrinsic PET depolymerization rate constant, frequency factor and activation energy
of PET depolymerization are estimated based on the modified shrinking core model.

Keywords waste PET, recycle, depolymerization, hydrolysis, shrinking core

model

Introduction
Poly(ethylene terephthalate) (PET) is a thermoplastic saturated polyester and is largely
consumed in textile industries for fabrics, electronic industries for audio-video tapes,
and the packaging industry for soft drink bottles. Wide applications of PET in the
packaging industries is mainly due to its high strength, low weight, low permeability to
gases (mainly CO2), good light transmittance, smooth surface and no side effects on
human bodies. To prevent ecological imbalance, the main interest in PET recycling is con-
tinuously increasing due to its substantial production in waste stream and its high resist-
ance to the atmospheric and biological agents. Considering the economic aspects,
chemical recycling of waste PET, a post consumer condensation polymer, has been
gaining growing attention in recent years (1). The common methods of chemical
recycling or depolymerization of waste PET is reviewed by Paszun and Spychaj (2) and

Received and accepted June 2004

Address correspondence to Chandan Guria, Department of Polymer Engineering, Birla Institute
of Technology, Mesra-835215, Ranchi, India. Fax: þ91-0651-2275401. E-mail: [email protected]

237
 238 S. Kumar and C. Guria

these methods are methanolysis, glycolysis, and hydrolysis of which hydrolysis of PET
to terephthalic acid (TA) and mono ethylene glycol (MEG) is the prime importance. In
hydrolytic decomposition, TA and MEG are recovered and can be used directly for the
synthesis of virgin bottle grade PET (3 –5). Industrial hydrolytic decomposition of PET
is carried out at a high temperature, which is usually above the melting point of the
resin using zinc acetate as a catalyst (6–8). Hydrolysis of PET is usually carried out in
the presence of strong acids (e.g. sulphuric acid (9–13), nitric acid (14) and hydrochloric
acid (15, 16)) and strong bases (e.g. sodium hydroxide (17, 18) and potassium hydroxide.
(18–20)) Neutral hydrolysis (21–23) is also reported in the presence of water and/or
steam. Hydrolytic decompositions of waste PET with strong acid is usually carried out at
a high temperature for a prolonged period to get reasonable conversion of PET (12–16).
Decompositions of waste PET particles with a strong base is usually carried out at a high
temperature under autogeneous pressure (17, 18). Alkaline hydrolysis of PET in the
presence of an organic solvent is also reported in the literature (24–27). However, very
few have studied the reaction kinetics of alkaline hydrolysis (18) of PET. Zeronian et al.
Downloaded by [Universite Laval] at 22:23 08 October 2014

(28, 29) have studied PET depolymerization kinetics at ambient temperature with sodium
hydroxide and fails to predict the high conversion of PET depolymerization. Wan
et al. (17) have studied the solid-state hydrolysis by NaOH and KOH and concluded that
hydrolysis by KOH is superior over NaOH due to improved conversion. They have also
reported the kinetic parameters for the PET depolymerization at elevated pressure in
aqueous KOH solution (18). The existence of a moving boundary during hydrolytic
decomposition of PET particles in acid and alkaline medium is reported by Yoshioka
(13, 14) and Wan et al. (18), respectively. A kinetic model based on alkaline hydrolysis
is developed by Wan et al. (18) and assumes a negligible change in the surface area of
the reacting PET particles during hydrolysis, which is not true during hydrolysis of PET
particles. Moreover, this model does not hold well at complete conversion of the PET
particles. The proposed model of Wan et al. (18) gives the contradicting relationship
between conversion and size of the PET particles, which is not in accord with solid-
liquid non catalytic reactions (30, 31). This model also assumes the identical KOH concen-
tration at the bulk and surface of PET particles. It is not applicable at low bulk concentration
of the aqueous KOH solution, as well as at higher PET conversion. Therefore, the present
work involves the development of a moving boundary transport model for hydrolytic depo-
lymerization of waste PET particles considering the shrinking core behavior of reacting PET
particles with a continuous depleting product layer (i.e., formation of MEG and salt of TA)
accounting for the effect of surface concentration (molar distribution coefficient) of aqueous
KOH solution under finite solution volume conditions. The effects of particle size, molar
ratio between PET repeating units to potassium hydroxide, and the reaction temperature
on PET depolymerization are also studied. Depolymerization parameters like intrinsic
reaction rate constant, frequency factor and activation energy for PET decomposition are
estimated through the proposed modified shrinking core model. This model also predicts
the average molar distribution coefficient of aqueous KOH solution during PET
depolymerization.

Experimental

Model Development
The possibility of the moving boundary process in hydrolytic decomposition of waste
PET arises when conversion of PET to potassium salt of TA and MEG involves
 Alkaline Hydrolysis of Waste Poly(Ethylene Terephthalate) 239

the consumption of alkaline hydroxide. In this moving boundary problem under finite
solution volume conditions, depolymerization products are completely soluble in an
aqueous alkali solution and shrinking behavior arises due to the gradual depletion of
solid PET materials from the surface. Depolymerization of PET in the presence of
aqueous potassium hydroxide solution occurs via random scission of ester linkage on
the solid PET surface and requires two moles of potassium hydroxide for disappearance
of each mole of PET repeating unit. However, the decomposition reaction of PET
repeating units proceeds according to Eqs. (1) and (2) (18):
Downloaded by [Universite Laval] at 22:23 08 October 2014

Here, the first reaction indicates the formation of potassium salt at the polymer chain
end, whereas the second reaction shows the complete dissociation of one PET repeating
unit giving MEG and potassium salt of TA. Assuming Eq. (1) is the rate-determining
step (18), depolymerization of PET follows first order kinetics with respect to the
potassium hydroxide concentration. The overall hydrolytic decomposition of PET can
be written in the following simplified form:

A (solid) þ 2B (liquid)
! C (liquid) þ D (liquid) ð3Þ

where, A, B, C, and D are the PET repeating unit, KOH, MEG and potassium salt of
TA, respectively. In order to describe the moving boundary process of PET depoly-
merization kinetics with a depleting soluble product layer under finite solution
volume conditions, the following assumptions and simplifications are made in the
present work:
The depolymerization of PET is a slow process and overall hydrolysis is kinetically
controlled.
Reaction takes place at the boundary of the liquid and solid.
 240 S. Kumar and C. Guria

Reversible reaction of PET decomposition is neglected due to the formation of soluble

salt of TA and MEG.
The PET particles consist of isotropic spherical particles of equal constant diameter.
The PET particles are considered as quasi-homogeneous phase for mathematical
treatment.
Molar distribution coefficient of aqueous KOH solution remains constant during a
given set of depolymerization experiment.
The PET particles undergo negligible swelling during depolymerization.
Net reaction volume is constant throughout the depolymerization process.
According to assumptions 1– 8, the rate of depolymerization reaction (13, 14, 18)
(2rA) of waste PET through alkaline hydrolysis (or the rate of formation of MEG or
the salt of TA) can be written in the following form (30, 31):
1 dNA b dNB

¼
¼ bk C B ð4Þ
4pr 2 dt 4pr 2 dt
Downloaded by [Universite Laval] at 22:23 08 October 2014

Where, NA is the number of moles of PET repeating units present in the polymer chain, NB
is the number of moles of KOH, r is the radius of the PET particles (moving reaction
front), C̄B is the molar concentration of aqueous KOH solution at the surface of the
PET particles, k is the intrinsic depolymerization rate constant, t is the depolymerization
time and b is a constant, which is related to the stoichiometric coefficient in the PET
depolymerization reaction in Eq. (3) Writing Eq. (4) in terms of the shrinking core
radius (r) gives:
dr

rA ¼ bk C B ð5Þ
dt
where, rA is the molar density of PET particles.
KOH concentration at the PET surface can be correlated with the bulk concentration
of KOH using following equilibrium relation:

C B ¼ lCB ð6Þ

where, l is the molar distribution coefficient of aqueous KOH solution. Here it is assumed
that instantaneous equilibrium is established at the PET interface during a slow depoly-
merization reaction.
Substituting CB ¼ [NA0(M 2 2XA)]/V0 and r ¼ r0(1 2 XA)1/3, one can obtain the
following expression for the conversion of PET particles (XA) using Eqs. (5) and (6):
dXA 2
¼ K ðM
2XA Þð1
XA Þ3 ð7Þ
dt
where, K is a modified first order depolymerization rate constant and is given by:
3blkNA0
K¼ ð8Þ
rA r 0 V 0
Here, V0 is the total volume of the reaction mixture at the start of the batch, NA0 is the
initial number of moles of PET repeating units, r0 is the initial size of PET particles M
is the initial molar ratio of potassium hydroxide to PET repeating units, respectively.
Assuming the molar distribution coefficient is independent of the change in the concen-
tration of KOH during the hydrolytic decomposition of PET for a given set of experiments,
 Alkaline Hydrolysis of Waste Poly(Ethylene Terephthalate) 241

Eq. (7) can be integrated for M . 2 and/or M , 2 with the appropriate initial conditions
(i.e., at t ¼ 0 and XA ¼ 0) to yield:

 pffiffiffi  
1 ðc + zÞ3 3 2z + c
ln + arctan p ffiffiffi
4c2 c3 + z3 2c2 c 3

3
pffiffiffi  
1 ð c + 1Þ 3 2+c
¼
Kt þ 2 ln 3 + 2 arctan pffiffiffi ð9Þ
4c c +1 2c c 3
where,
 
 ð M
2Þ 
3 
c ¼  ð10Þ
2 
1
z ¼ ð1
XA Þ3 ð11Þ
Downloaded by [Universite Laval] at 22:23 08 October 2014

Here, the upper sign is applicable to M . 2 and the lower one for M , 2. If M ¼ 2,
Eq. (9) can be integrated to yield:
1 4
2=3
¼ Kt þ 1 ð12Þ
ð 1
XA Þ 3
Equations (9) and (12) represent the conversion of PET particles as a function of time
at any given value of the molar ratio. The left hand side of Eqs. (9) and (12) can be plotted
against t, and K can be evaluated from the slope of the linear plot. Hence, the values of lk
for different molar ratio of KOH to PET repeating units can be evaluated for values b, NA0,
rA, r0 and V0.
Commercially available mineral water, beverage and soft drink bottles, which consti-
tuted the bulk of waste PET, were used to carry out the depolymerization experiments.
These waste PET bottles were cut into small pieces by kneaders. To determine the depoly-
merization rate, PET particles were sieved to obtain four fractions (I-IV) with average
particle diameters (r0) 0.00168, 0.0012, 0.0010, and 0.00070 m. Size fraction III consti-
tuted the bulk of the waste PET particles and the density of these particles was found to
be 1385.40 kg m23. Intrinsic viscosity, [h] of waste PET particles was measured in a
6 : 4 (w/w) phenol/1,1,2,2 tetrachloroethane solution at 308C using Ubbelohde visco-
meter and was estimated as 0.8085 dL g21 (Fig. 1). The average molecular weight
(MW) of the waste PET particles is determined from the Mark-Houwink equation (18)
Eq. (13) and was found to be 26.468 kg mol21.

MW ¼ 3:61  104 ½h1:46 ð13Þ

PET depolymerization was carried out in a standard glass lined micro-autoclave. The
micro-autoclave was dipped in a silicon oil bath equipped with an agitator and automatic
temperature controller to maintain a constant temperature for depolymerization. The waste
PET particles with the desired particle size and aqueous KOH solution with fixed molar
ratio (PET repeating units to KOH) were charged together into the autoclave and
placed into the thermostatic bath at the desired temperature. For molar ratio of 1 : 4,
1.0 gm of PET particles (r0 ¼ 0.001 m) and 1.1667 gm dry KOH were added in 10 mL
of double distilled water to the autoclave. At regular time intervals, the depolymerization
mixture was taken out and quickly quenched to room temperature by spraying cold water.
The cooled reaction mixture was filtered to complete the removal of the potassium salt of
TA and MEG by washing with double distilled water. Unreacted PET was dried under
 242 S. Kumar and C. Guria
Downloaded by [Universite Laval] at 22:23 08 October 2014

Figure 1. Intrinsic viscosity of waste PET particles.

vacuum at 808C for 24 h and weighed. The filtrate was acidified with dilute acetic acid
to get the precipitate of TA, which was then dried under vacuum at 808C for 24 h.
Conversion of the waste PET was calculated from the decrease in the weight of PET
particles and was confirmed with the amount of terephthalic acid produced after
precipitation. Unreacted PET samples (r0 ¼ 0.001 m and molar ratio ¼ 1 : 4) at different
time intervals (at 0, 4 and 8 h, respectively) were also analyzed by a Perkin-Elmer 1430
infra red (IR) spectrometer (see Fig. 2). The IR film was made by dissolution of
unreacted PET with phenol and 1,1,2,2 tetrachloroethane. It was observed that all
transmittance peaks were identical except the peak at 1700 cm21 and the trans-
mittance at this position decreased with the depolymerization time (20). The decreased
transmittance at 1700 cm21 was due to the increasing surface concentration of the
.C55O group, which is generated from a substituted aryl carboxylic acid group
( –COOH). This proves that the major hydrolytic decomposition reaction occurs at the
polymer chain end section of the PET surface and increases the concentration of aryl
carboxylic acid.
To find the effect of particle size, the depolymerization rates were measured for each
particle size fraction (I-IV) and the conversion of PET particles vs. the decomposition time
were plotted in Fig. 3. Here, the molar ratio of PET repeating units to KOH was taken as
1 : 4 for all size fractions. In each experiment, 1.1667 gm of dried KOH was taken per gm
of waste PET particles. 10 mL of twice distilled water was taken for each experiment and
temperature was kept at 403 K. A logarithmic plot of quarter time (t1/4) for PET depoly-
merization vs. initial radius (r0) of PET particles is shown in Fig. 4 at 403 K. It was found
that the rate of depolymerization was inversely proportional to the initial size of the PET
particles. An inverse relationship proves that depolymerization kinetics was controlled by
chemical reaction alone (30, 31), whereas the model developed by Wan et al. (18) gives an
inverse relationship between the square of the radius and the depolymerization time, which
is not consistent with the present test results.
 Alkaline Hydrolysis of Waste Poly(Ethylene Terephthalate) 243
Downloaded by [Universite Laval] at 22:23 08 October 2014

Figure 2. IR analysis of unreacted waste PET particles (M ¼ 1 : 4, r0 ¼ 0.001 m, t ¼ 0.0 h, 4.0 h and
8.0 h, T ¼ 403 K).
 244 S. Kumar and C. Guria
Downloaded by [Universite Laval] at 22:23 08 October 2014

Figure 3. Effects of PET particle size on depolymerization (M ¼ 1 : 4; T ¼ 403 K).

Figure 4. Plot of ln(r0) vs. ln(t1/4).

 Alkaline Hydrolysis of Waste Poly(Ethylene Terephthalate) 245

The effect of the molar concentration of KOH on the depolymerization kinetics was
measured with PET particles having size fraction III (r0 ¼ 0.001 m) at 403 K. Here, molar
ratios of PET repeating units to KOH were taken to be 1 : 6, 1 : 4, 1 : 2, and 1 : 1. The results
were shown in Fig. 5 and showed that bulk concentration has a marked effect on depoly-
merization kinetics, which is in accord with the kinetically controlled model.
The effect of temperature on depolymerization kinetics was studied at four different
temperatures (383 K, 393 K, 403 K, and 408 K) for size fraction III (r0 ¼ 0.001 m) and 1 : 4
molar ratio of PET repeating units to KOH. The conversion of PET to reaction time is
shown in Fig. 6 and the rate of depolymerization increases with an increase in reaction
temperature.

Results and Discussion

The shrinking core model with depletion of a soluble product developed above was tested.
Downloaded by [Universite Laval] at 22:23 08 October 2014

Bear in mind that in developing the mathematical model for hydrolytic decomposition of
PET, the constancy of molar distribution coefficient l was assumed in order to facilitate
the analytical integrations for a given initial bulk concentration of KOH. As l is more
sensitive to dilute solution (i.e., l increases with an increase in the dilution), this assump-
tion is true only at higher molar concentrations of KOH where the change of l is negli-
gible, and at lower conversions of PET particles. Therefore, it is assumed that an
average molar distribution coefficient (l̄) exists during any given set of depolymerization
experiment.

Figure 5. Effects of bulk concentration of KOH solution on PET depolymerization (r0 ¼ 0.001 m;
T ¼ 403 K).
 246 S. Kumar and C. Guria
Downloaded by [Universite Laval] at 22:23 08 October 2014

Figure 6. Effects of temperature on PET depolymerization.

To test the modified shrinking model with a depleting product layer (consisting of
potassium salt of TA and MEG), the left hand sides of Eqs. (9) and (12), which are
functions of the PET conversion, were evaluated and plotted against the depolymerization
time (t) based on Fig. 3 for four different particle sizes at 403 K and 1 : 4 molar ratio of
PET repeating units and KOH (Fig. 7). The slope of the linear plot (Fig. 7) will give
the different values of K. Substituting appropriate values r0, V0, b, NA0 and rA
(V0 ¼ 1025 m3, b ¼ 0.5, NA0 ¼ 5.2085  1023 mol and rA ¼ 52.3426 mol m23) in Eq.
(8), individual values of l̄k for four different particle sizes are calculated and almost
identical values of l̄k (average value 1.68  1026 m h21) is obtained (Fig. 8). This
indicates that at a given bulk concentration of aqueous KOH and reaction temperature,
l̄ is constant for the given value of k. Similarly, using Eq. (9) (M = 2) and Eq. (12)
(M ¼ 2), K values are obtained from the slope of the linear plot (Fig. 9) based on the
data of Fig. 5 at different molar ratios of PET repeating unit to KOH under isothermal
condition (r0 ¼ 0.001 m and T ¼ 403 K). The corresponding values of different l̄k are
obtained at four different values of molar bulk concentration of aqueous KOH solution.
The plot of l̄k vs. CB0 (Fig. 10), gives an idea to estimate the value of the intrinsic
reaction rate constant (k) and hence, the average molar distribution coefficient (l̄). It is
observed that in Fig. 10 as CB0 increases, l̄k decreases and reaches a constant value
asymptotically, which indicates that the value of l̄ approaches unity at higher bulk
molar KOH concentrations, and is independent of the bulk concentration of aqueous
KOH solution. Therefore, at the limiting value of CB0, the value of l̄k will be equal to
k, which helps calculate the intrinsic depolymerization rate constant at the given tempera-
ture. The intrinsic depolymerization rate constant (k) at the limiting CB0 is
1.30  1026 m h21 at 403 K and limiting CB0 is found to be 4000 mol m23. Thus, l̄
 Alkaline Hydrolysis of Waste Poly(Ethylene Terephthalate) 247
Downloaded by [Universite Laval] at 22:23 08 October 2014

Figure 7. Test of Eqs. (9) and (12) for different particle size of PET on depolymerization (M ¼ 1 : 4;
T ¼ 403 K).

Figure 8. Variation of l̄k with particle size of PET particles (M ¼ 1 : 4, T ¼ 403 K).
 248 S. Kumar and C. Guria
Downloaded by [Universite Laval] at 22:23 08 October 2014

Figure 9. Test of Eqs. (9) and (12) for different initial bulk concentration of KOH solution
(r0 ¼ 0.001 m; T ¼ 403 K).

Figure 10. Variation of l̄k with initial bulk concentration of KOH solution (r0 ¼ 0.001 m;
T ¼ 403 K).
 Alkaline Hydrolysis of Waste Poly(Ethylene Terephthalate) 249

corresponding to each experiment (for different CB0) was evaluated by knowing the values
of k. The values of l̄ for molar ratio 1 : 6, 1 : 4, 1 : 2, and 1 : 1 calculated as 1.005, 1.288,
2.798, and 4.690, respectively. The effect of temperature on the intrinsic PET depolymeri-
zation rate constant (k) can be evaluated by knowing l̄ (independent of temperature) at
given CB0 (molar ratio of PET repeating units to KOH ¼ 1 : 4). For given l̄ (1.288), k
values at different temperatures (i.e., 408 K, 403 K, 393 K, and 383 K) were evaluated,
the slope of Eqs. (9) and (11) (Fig. 11) for the data based on Fig. 6 and the corresponding
values of the intrinsic reaction rate constant (k) are determined as: 1.66  1026,
1.30  1026, 1.12  1026, 9.10  1027 m h21, respectively. Arrhenius plot (Fig. 12)
was made to evaluate the frequency factor (k0) and DE/R, where DE is the activation
energy and R is the universal gas constant (kJ mol21 K21). The value of k0 and DE/R
are evaluated as 0.009178 m h21 and 3537.7 K, respectively.
Downloaded by [Universite Laval] at 22:23 08 October 2014

Conclusions
The hydrolytic depolymerization of waste PET, with an aqueous potassium hydroxide
solution, was investigated. An IR spectroscopy study of unreacted PET samples shows
that the major decomposition reaction occurring on the polymer chain end section on
the solid PET surface. An improved moving boundary transport model (modified
shrinking core model) for kinetically controlled depolymerization of PET particles was
developed to account the continuous depletion of the product layer by incorporating the
molar distribution coefficient. Kinetic parameters, i.e., the intrinsic rate constant (k),

Figure 11. Test of Eqs. (9) and (12) at different PET depolymerization temperatures (r0 ¼ 0.001 m;
M ¼ 1 : 4).
 250 S. Kumar and C. Guria
Downloaded by [Universite Laval] at 22:23 08 October 2014

Figure 12. Arrhenius plot for PET depolymerization (r0 ¼ 0.001 m; M ¼ 1 : 4).

frequency factor (k0), activation energy of depolymerization (DE ) and the average molar
distribution coefficient of aqueous KOH solution (l̄) were evaluated based on the above
model.

References
1. Nir, M.M., Miltz, J., and Ram, A. (1993) Update on plastics and the environment: progress and
trends. Plast. Eng., 49 (3): 75 – 93.
2. Paszun, D. and Spychaj, T. (1997) Chemical recycling of poly(ethylene terephthalate). Ind. Eng.
Chem. Res., 36 (4): 1373– 1383.
3. Cudmore, W.J.G. (1986) Poly(ethylene terephthalate) Saponification. U.S. Patent 4 578 502.
4. Doerr, M.L. (1986) Process for minimizing formation of low molecular weight oligomers during
hydrolytic depolymerization of condensation polymers. U.S. Patent 4 578 510.
5. Rosen, B.J. (1991) Preparation of purified terephthalic acid from waste PET. U.S. Patent 5 095
145, CA 123: 257937.
6. Campanelli, J.R., Kamal, M.R., and Copper, D.G. (1993) A kinetic study of hydrolytic degra-
dation of poly(ethylene terephthalate) at high temperatures. J. Appl. Polym. Sci., 48 (3):
443– 451.
7. Campanelli, J.R., Copper, D.G., and Kamal, M.R. (1994) Catalyzed hydrolysis of poly(ethylene
terephthalate) melts. J. Appl. Polym. Sci., 53 (8): 985– 991.
8. Kao, C., Wan, B., and Cheng, W. (1998) Kinetics of hydrolytic depolymerization of melt poly
(ethylene terephthalate). Ind. Eng. Chem. Res., 37 (4): 1228– 1234.
9. Brown, G.E., Jr.; O’Brien, R.C. (1976) Method of recovering terephthalic acid and ethylene
glycol from polyester materials. U.S. Patent 3 952 053.
 Alkaline Hydrolysis of Waste Poly(Ethylene Terephthalate) 251

10. Pusztaszeri, S.F. (1982) Method for recovery of terephthalic acid from polyester scrap. U.S.
Patent 4 355 175.
11. Sharma, N.D.; Vaidya, A.A.; Sharma, P. (1985) Recovery of pure terephthalic acid from
polyester materials. Ind. Patent 163 385, CA 112: 76613d.
12. Yoshioka, T., Sato, T., and Okuwaki, A.J. (1994) Hydrolysis of waste PET by sulphuric acid at
1508C for Chemical recyclying. J. Appl. Polym. Sci., 52 (9): 1353– 1355.
13. Yoshioka, T., Motoki, T., and Okuwaki, A.J. (2001) Kinetics of hydrolysis of poly(ethylene
terephthalate) powder in sulfuric acid by a modified shrinking-core model. Ind. Eng. Chem.
Res., 40 (1): 75 – 79.
14. Yoshioka, T., Okayama, N., and Okuwaki, A. (1998) Kinetics of hydrolysis of PET powder in
nitric acid by a modified shrinking-core model. Ind. Eng. Chem. Res., 37 (2): 336– 340.
15. Ravens, D.A.S. (1960) The chemical reactivity of poly(ethylene terephthalate): heterogeneous
hydrolysis by hydrochloric acid. Polymer, 1: 375– 383.
16. Davies, T., Goldsmith, P.L., Ravens, D.A.S., and Ward, M.I. (1962) The Kinetics of the
hydrolysis of poly(ethylene terephthalate) film. J. Phys. Chem., 66 (1): 175–176.
17. Kao, C., Cheng, W., and Wan, B. (1998) Investigation of alkaline hydrolysis of poly(ethylene
Downloaded by [Universite Laval] at 22:23 08 October 2014

terephthalate) by differential scanning calorimetric and thermo- gravimetric analysis. J. Appl.

Polym. Sci., 70 (10): 1939– 1945.
18. Wan, B., Kao, C., and Cheng, W. (2001) Kinetics of depolymerization of poly(ethylene tereph-
thalate) in a potassium hydroxide solution. Ind. Eng. Chem. Res., 40 (2): 509– 514.
19. Mandoki, J.W.. Depolymerization of condensation polymers. U.S. Patent 4 605 762, 1986.
20. Guclu, G., Yalcinyuva, T., Ozgumus, S., and Orbay, M. (2003) Hydrolysis of waste poly(ethy-
lene terephthalate) and characterization of products by differential scanning calorimetry. Ther-
mochimia Acta, 404 (1– 2): 193– 205.
21. Sammon, C., Yarwood, J., and Evarall, N. (2000) An FT-IR study of the effect of hydrolytic
degradation of on the structure of thin PET films. Polym. Degrad. Stab., 67 (1): 149– 158.
22. Launay, A., Thominette, F., and Verdu, J. (1994) Hydrolysis of poly(ethylene terephthalate):
a kinetic study. Polym. Degrad. Stab., 46 (3): 319– 324.
23. Kao, C., Wan, B., and Cheng, W. (1998) Kinetics of hydrolytic decomposition of melt
poly(ethylene terephthalate). Ind. Eng. Chem. Res., 37 (4): 1228–1234.
24. Kirby, J.R., Baldwin, A.J., and Heigner, R.H. (1965) Experimental reactor thermal-neutron acti-
vation analysis sensitivities. Anal. Chem., 37 (1): 129– 132.
25. Namboori, C.G.G. and Haith, M.S. (1968) Steric effects in the base hydrolysis of poly(ethylene
terephthalate). J. Appl. Polym. Sci., 12 (9): 1999– 2005.
26. Tindall, G.W.; Perry, R.L. (1991) Ester hydrolysis and depolymerization of polyester and poly-
carbonate polymers. U.S. Patent 5 045 122.
27. Tindall, G.W.; Perry, R.L.; Spaugh, A.T. (1994) Depolymerization of substantially amorphous
polyester. U.S. Patent 5 328 982.
28. Collins, M.J. and Zeronian, S.H.J. (1992) The molecular weight distribution and oligomers of
sodium hydroxide hydrolyzed poly(ethylene terephthalate). J. Appl. Polym. Sci., 45 (5):
797– 804.
29. Holmes, S.A. and Zeronian, S.H.J. (1995) Surface area of aqueous sodium hydroxide hydro-
lyzed high-speed spun poly(ethylene terephthalate) fibers. J. Appl. Polym. Sci., 55 (11):
1573– 1581.
30. Carberry, J.J. (1976) Chemical and Catalytic Engineering; McGraw-Hill: New York.
31. Levenspiel, O. (1999) Chemical Reaction Engineering; Wiley: New York.