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R EACTOR E NGINEERING
Volume 8 2010 Article A150
∗
Iran University of Science and Technology, mr moghbeli@iust.ac.ir
†
Iran University of Science and Technology, namayandehsahar@yahoo.com
‡
Iran University of Science and Technology, hashemabadi@iust.ac.ir
ISSN 1542-6580
Copyright
2010
c The Berkeley Electronic Press. All rights reserved.
Wet Hydrolysis of Waste Polyethylene Terephthalate
Thermoplastic Resin with Sulfuric Acid and CFD
Simulation for High Viscous Liquid Mixing
Mohammad Reza Moghbeli, Sahar Namayandeh, and Seyed Hassan
Hashemabadi
Abstract
In this research, wet hydrolysis of polyethylene terephthalate (PET), as used
in beverage bottles, has been carried out using sulfuric acid. The hydrolysis reac-
tion has been investigated in a laboratory glass reactor, provided with an anchor
mixer and a digital torque meter. The hydrodynamics of viscous liquid in stirred
reactor has also been studied by computational fluid dynamics simulation. The
results of simulations give the operational conditions for optimum mixing into
the designed agitated reactor. In the stirred reactor, the used chopped PET pieces
were degraded into its constituent monomers, terephthalate acid (TPA) and ethy-
lene glycol, in an acidic medium. The hydrolysis of product was characterized
by (FT-IR) spectroscopy, while the efficiency of TPA production was measured
by (UV-Vis) spectrophotometer. The effects of different parameters such as tem-
perature, acid concentration and reaction time on PET degradation have been in-
vestigated. The experimental results show that the optimum reaction condition
occurred while the sulfuric acid to used PET ratio is 4:1 at a reaction temperature
of 90◦ C and reaction time of five hours.
The original citation for this article published on November 9, 2010 was as follows:
Namyandeh, S.; Hashemabadi, Seyed Hassan; and Moghbeli, M.R. (2010) “Wet Hydrolysis of
Waste Polyethylene Terephthalate Thermoplastic Resin with Sulfuric Acid and CFD Simulation
for High Viscous Liquid Mixing,” International Journal of Chemical Reactor Engineering: Vol.
8: A150.
Available at: http://www.bepress.com/ijcre/vol8/A150
Moghbeli, Mohammad Reza; Namayandeh, Sahar; and Hashemabadi, Seyed Hassan (2010) ”Wet
Hydrolysis of Waste Polyethylene Terephthalate Thermoplastic Resin with Sulfuric Acid and CFD
Simulation for High Viscous Liquid Mixing,” International Journal of Chemical Reactor Engi-
neering: Vol. 8: A150.
Available at: http://www.bepress.com/ijcre/vol8/A150
Moghbeli et al.: Wet Hydrolysis of Waste PET Resin with Sulfuric Acid 1
Introduction
PET is a thermoplastic resin of industrial importance (Kaplan, 2000). PET is
semi-crystalline polyester with high strength, transparency and safety. Large
quantities of PET are consumed in the manufacturing of beverage bottles, food
packaging, video and audio tapes. Recycling of these used PET products is an
important issue because of environmental concern (Ertas and Guclu, 2005, Cheng
et al. 2010).
The recycling of waste PET can be carried out in many ways. Three main
approaches for recycling PET are mechanical, chemical, and auto-clave recycling
(Scheirs, 1999; Paszun and Spychaj, 1997; Shukla and Harad, 2005; Zope et al.,
2003). One of the methods for PET chemical recycling is hydrolysis where
crashed PET reacts with aqueous acid, aqueous alkaline and/or neutral
environment. This results in terephthalic acid (TPA) and ethylene glycol (EG),
which can be used as raw material in many industrial processes (Brandrup et al.,
1996, Yoshioka et al. 2001). Alkaline hydrolysis of PET is usually carried out
with the use of alkaline solution of NaOH or KOH (Karayannidis et al., 2002).
Acidic hydrolysis is one of the traditional methods for de-polymerization of
polyesters. In acidic hydrolysis, nitric acid or sulfuric acid was used; however, the
use of sulfuric acid (98%) for hydrolysis was more common (De Carvalho et al.,
2006). The only disadvantage of this method is the corrosion caused by acidic
solution. The main advantage of this method is the fact that the process can take
place at ambient pressure, thereby giving favorable capital and operating costs.
In this paper, acidic hydrolysis of PET beverage bottles was carried out in
a stirred reactor, and the influence of different parameters such as temperature,
acid concentration and reaction time on PET hydrolysis has been investigated.
Experimental Works
Materials
Post-consume PET from soft drink bottles were crashed in the form of 8×8 mm2
small film pieces. Commercial sulfuric acid (98% purity), potassium hydroxide
(KOH), and distilled water were used in this experimental work.
Hydrolysis Process
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Moghbeli et al.: Wet Hydrolysis of Waste PET Resin with Sulfuric Acid 3
acidity of the filtrate was increased by adding 18 ml of sulfuric acid. TPA was
precipitated from new acidic solution and subsequently filtered. The white
precipitated TPA on filter media was dried at 105 oC in a vacuum oven.
Characterization
Where Y and X are the absorbance value with arbitrary unit and TPA
concentration respectively.
CFD Simulation
The main issue when simulating stirred vessels is that the problem geometry
varies with time due to the relative motion between the impeller and the baffles.
Several methods have been used in the literature to treat that kind of problems,
namely the IBC, the MRF and the SG methods (Gentric et al. 2005). For the
relative velocity formulation of MRF formulation, the governing equations of
fluid flow for a steadily rotating frame can be written as follows (Ranade, 2005):
Conservation of mass:
∂ρ
+ ∇ ⋅ ( ρu ) = 0 (2)
∂t
Conservation of momentum:
∂
( ρ ur ) + ∇ ⋅ ( ρ ur ur ) + ρ ( 2ω × ur + ω × ω × r ) = −∇p + ∇τ r + F (3)
∂t
The momentum equation contains two additional acceleration terms: the Coriolis
acceleration, and the centripetal acceleration.
Depending on the type of flow conditions (i.e. laminar/turbulent, steady
state/transient) then appropriate boundary conditions can be defined and
implemented. For example, in the case of steady state, the time dependency of
variables such as velocity is set to zero. As for the boundary condition, the
imaginary cylindrical wall which is assumed around the impeller is considered to
be moving with the impeller being stationary (named Multi Reference Frames,
MRF method). The reactor walls are subjected to no slip condition and constant
temperature. The flow regime in this simulation is laminar because of high
viscosity of mixing fluid. The viscosity of fluid during the reaction has been
assumed constant. Three-dimensional laminar flow and mixing predictions have
been carried out using MRF method. A tetrahedral mesh is used for the geometry
and unstructured (or irregular) grid size has been employed, with cell sizes
comparable to those of the reactor, giving a total cell number of 358,800. The
governing equations for continuity and momentum, Eqs. 2 and 3, have been
solved by finite volume technique (Patankar 1980, Versteeg and Malasekera
1995). The steady state simulation was carried out by using in house CFD code.
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Moghbeli et al.: Wet Hydrolysis of Waste PET Resin with Sulfuric Acid 5
(A)
(B)
(A)
(B)
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Moghbeli et al.: Wet Hydrolysis of Waste PET Resin with Sulfuric Acid 7
Inspection of the results reveals that near the wall flow goes down (negative
velocity) and in the central core the flow direction is opposite. Increasing of
rotational speed enhances the axial and tangential velocities in all regions. In
order to investigate the optimum impeller velocity, a mixing index was defined.
This index is the value of volume average velocity over the tank. The volume
average velocity is calculated by dividing the summation of the product of the
velocity and cell volume by the total volume of the cells. As this value is closer to
maximum velocity, it will show that a better mixing is occurred. Maximum
velocity is simply worked out from speed of the agitator but the volume average
velocity is computed from the averaging of the simulated whole flow field. In the
opinion of the authors the criteria employed here, i.e. the difference of the two
velocities, is the best way of identifying the mixing with more hydrodynamic
homogeneity. Also the energy consumption through the fluid mixing is important.
As it is known, the fluid kinetic energy is proportional to consumed mixing
power. Table 1 shows the results of a comparison between the average and
maximum velocities as well as the produced kinetic energy. From the results, it
can be concluded that the impeller velocity of 100 rpm has the minimum
difference (i.e. 71.30%) between the maximum and average velocities, with more
favorable power as typified by the extent of the prevailing kinetic energy, as
compared to rotational impeller speed of 120 rpm. The optimum rotational speed
creates a more homogeneous flow regime inside the tank and thereby providing a
better mixing within the system.
*
Round per minute
Experimental Results
Figure 4 shows the FT-IR (Fourier Transform Infrared Spectroscopy) spectra of
waste PET before the acidic hydrolysis reaction. As it is shown, the chemical
structure of PET in the wavelength between 3300 and 3700 cm-1, appearing the
OH group, is clear. The wavelength between 3000 and 3100 cm-1 shows an
aromatic compounds CH stretch (Donald et al. 2008). The wavelength between
2800 and 3000 cm-1 indicates the presence of hydrocarbon (hydrogen and carbon).
In the wavelength range between 1600 and 1700 cm-1 the carbonyl group was
demonstrated. In the wavelength between 600 and 800 cm-1 the aromatic ring was
shown. Figures 5A and 5B show the FT-IR spectra of the white produced powder
and pure TPA, respectively. The powder has been created using 45 ml of sulfuric
acid at reaction temperature of 90 oC and reaction time of 5 hours. The spectra for
produced powder and neat TPA show good similarity. From the spectra of
produced powder, the wave length between 1600 and 1700 cm-1 shows the
presence of carbonyl group and the wave length between 1000 and 1600 cm-1
shows the presence of aromatic ring, all of which confirming the presence of TPA
in the final precipitated powder.
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Moghbeli et al.: Wet Hydrolysis of Waste PET Resin with Sulfuric Acid 9
(A)
(B)
Figure 5: A) Typical FT-IR spectra of produced sediment powder from waste PET
hydrolysis, B) FT-IR spectra of neat TPA prepared from Merck Co.
1 3 5 10 15
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Moghbeli et al.: Wet Hydrolysis of Waste PET Resin with Sulfuric Acid 11
The effect of temperature on the yield of TPA is shown in Figure 6. Five different
reaction temperatures were examined in the range of 40 - 90 °C. A significant
increase in PET degradation with increasing reaction temperature was observed.
The experimental results show that at a constant reaction time, while the amount
of sulfuric acid increases the effect of temperature on TPA yield is pronounced.
The results depict that at a constant amount of sulfuric acid increasing the reaction
time caused the effect of temperature on the yield to increase. Furthermore, the
reaction time of 15 h resulted in the maximum yield but by increasing the reaction
time from 5 to 15 hours, the efficiency of TPA production is not considerable.
The effect of reaction time on the yield of TPA production is shown in Figure 7.
Five different reaction times were examined (in the range of 1-15 hours). The
results demonstrate that by increasing reaction time from 1 hour to 5 hours, the
efficiency of TPA product will increase but by promoting the reaction time from 5
to 15 hours, the TPA production efficiency growth is not considerable.
Figure 7: The effect of reaction time on TPA yield using 45 ml sulfuric acid
The results also demonstrate that for a given temperature increasing the amount of
sulfuric acid and reaction time enhances the yield of the TPA. Moreover, the
reaction temperature of 90 °C had the maximum yield when compared to other
reaction temperatures.
Conclusion
Acidic hydrolysis of PET beverage bottles has been studied in a stirred reactor
enabling the influence of different parameters such as temperature, acid
concentration and reaction time on PET hydrolysis to be investigated. The
experimental results highlighted that the optimum reaction condition can occur
when the acid to PET ratio is 4:1 at a reaction temperature of 90 oC and reaction
time of 5 hours. It has been established that the influence of temperature on the
acidic hydrolysis of waste PET is more significant than other degradation process
parameters. The results revealed that by increasing the reaction time from 1 hour
to 5 hours, the efficiency of TPA product increases proportionally but by
increasing the reaction time from 5 to 15 hours, the TPA production efficiency
growth is not considerable.
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Moghbeli et al.: Wet Hydrolysis of Waste PET Resin with Sulfuric Acid 13
Notation
F External Force in Eq. (3)
N Round per minute (rpm)
r r-coordinate
p Pressure
t Time
T Temperature
u Velocity
X TPA concentration
Y Absorbance value
z Height of Reactor
Greeks
ρ Density
τ Stress
ω Angular Velocity
Subscripts
ave Average
max Maximum
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Moghbeli et al.: Wet Hydrolysis of Waste PET Resin with Sulfuric Acid 15
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