CHEMICAL RECYCLING OF PET Hydrolytic depolymerization under microwave irradiation

D.S. Achilias, D.N. Bikiaris, K.A.G. Katsogiannis and G.P. Karayannidis

Laboratory of Organic Chemical Technology, Department of Chemistry Aristotle University of Thessaloniki, 541 24 Thessaloniki GREECE E-mail: axilias@chem.auth.gr

ABSTRACT Recycling of poly(ethylene terephthalate) (PET) taken from common soft-drink bottles is examined using hydrolytic depolymerization in an alkaline solution, under microwave irradiation. The main objective is to test if depolymerization using microwave energy could be carried out in milder experimental conditions and/or shorter reaction times. The reaction was carried out in a sealed microwave reactor in which the pressure and temperature were controlled. The main products were the monomers terephthalic acid (TPA) (obtained in pure form) and ethylene glycol, which were analyzed and identified. The effect of reaction temperature, time and alkaline concentration on the degree of PET depolymerization and TPA recovery was investigated. Microwave irradiation was found to shorten very much the time needed to achieve a specific degradation of PET as well as a TPA yield. Also, using a phase transfer catalyst (TOMAB) was found to result in the same unreacted PET amount but at significantly lower depolymerization temperatures.

1. INTRODUCTION During last decades, the great population increase worldwide together with the need of people to adopt improved conditions of living led to a dramatical increase of the consumption of polymers (mainly plastics). Materials that appears interwoven with the consuming society where we live. Current statistics for Western Europe estimate the annual total consumption of plastic products at 48.8 million tons for 2003 corresponding to 98 kg per capita. The same quantity a decade before, i.e. in 1993 was approximately 64 kg/capita [1]. Among other polymers, poly(ethylene terephthalate) (PET) represents a great percentage of this total. The overall world consumption of PET amounts to about 26 million tons a year compared to about 13 million tons, reported in 1997 [1]. PET is one of the versatile engineering plastics showing excellent thermal and mechanical properties. Although its main application was by far the textile industry, tremendous quantities of this material are consumed in the manufacture of video and audio tapes, X-ray films, food packaging and especially of soft-drink bottles. In Greece, a great part of olive and other seed-oils, as well as of mineral water, is offered in PET bottles. Since the duration of life of PET wastes (mainly from mineral-water and soft-drink bottles) is very small, there is a vast waste stream that reaches each year to the final recipients creating a serious environmental problem. Disposing of the waste to landfill is becoming undesirable due to legislation pressures (waste to landfill must be reduced by 35% over the period from 1995 to 2020), rising costs and the poor biodegradability of commonly used polymers. Therefore other ways of polymer wastes treatment, like recycling, should be adopted. PET recycling represents one of the most successful and widespread examples of polymer recycling. PET bottle collection in Europe is growing steadily. By 2006, Petcore announced that European post-consumer PET collection rates reached 796,000 tons, a 15% increase over the previous year [2]. The main driving force responsible for this extremely increased recycling of postconsumer PET is its widespread use, particularly in the beverage industry, since it does not have any side effects on the human organism. Therefore, the recycling of PET does not only serve as a partial solution to the solid waste problem but also contributes to the conservation of raw petrochemical products and energy. The recycling of waste polymers including PET can be carried out in many ways. Four main approaches have been proposed [3-6]: 1. Primary recycling refers to the in-plant recycling of the scrap material of controlled history. This process remains the most popular as it ensures simplicity and low cost, dealing however only with the recycling of clean uncontaminated single-type waste. 2. Mechanical Recycling. In this approach, the polymer is separated from its associated contaminants and it can be readily reprocessed into granules by conventional melt extrusion. Mechanical recycling includes the sorting and separation of the wastes, size reduction and melt filtration. The main disadvantage of this type of recycling is the deterioration of product properties in every cycle. This occurs since the molecular weight of the recycled resin is reduced due to chain scission reactions caused by the presence of water and trace acidic impurities. Strategies for maintaining the polymer average molecular weight during reprocessing include intensive drying, reprocessing with degassing vacuum, the use of chain extender compounds, etc. 3. Chemical recycling has been defined as the process leading in total depolymerization of PET to the monomers, or partial depolymerization to oligomers and other chemical substances. Chemical

recycling processes for PET are divided as follows: (i) Glycolysis, (ii) Methanolysis, (iii) Hydrolysis and (iv) other processes. Glycolysis involves the insertion of ethylene glycol (or diethylene glycol and propylene glycol) in PET chains to give bis (hydroxyethyl) terephthalate (BHET) which is a substrate for PET synthesis and other oligomers. The production of secondary useful products, such as alkyd resins, obtained from the glycolysis of PET has also been proposed [5]. The main advantage of this method is that it can be easily integrated into a conventional PET production plant and the recovered BHET can be blended in with fresh BHET. However, there is always the risk of contaminants. On the other hand, the main disadvantage is that the reaction products are not discrete chemicals but BHET along with higher oligomers, which are difficult to purify with conventional techniques. Methanolysis actually is the degradation of PET by methanol at high temperatures and high pressures with main products: dimethyl terephthalate (DMT) and ethylene glycol (EG). The main advantage of this method is that an installation of methanolysis can be located in the polymer production line, since the DMT produced has a product quality identical to virgin DMT. Disadvantages of the method include the high cost associated with the separation and refine of the mixture of the reaction products (glycols, alcohols and phthalate derivatives) if water does perturb the process it poisons the catalyst and forms various azeotropes. Hydrolysis of PET can be carried out in an acid, alkaline or neutral environment to produce the monomers TPA and EG. The growing interest in this method is connected with the development of new factories for PET synthesis directly from TPA and EG. Acid hydrolysis is performed most frequently using concentrated sulfuric, nitric or phosphoric acid. Alkaline Hydrolysis of PET is usually carried out with the use of an aqueous alkaline solution of NaOH, or KOH of a concentration of 420 wt-% [3]. The reaction products are EG and the disodium terephthalate salt TPA-Na2. Pure TPA can be obtained by neutralization of the reaction mixture with a strong mineral acid (e.g. H2SO4). The main advantage of this method is that it can tolerate highly contaminated post-consumer PET such as magnetic recording tape, metallized PET film, or photographic (X-ray) film. The process is relatively simple and less costly. Neutral Hydrolysis is carried out with the use of hot water or steam. The process usually runs in high-pressure autoclaves at temperatures 200-300oC and pressure 1-4 MPa and with excess water [3]. The products are high purity TPA and EG. Neutral hydrolysis has the main advantage in comparison to acid and alkaline hydrolysis that formation of substantial amounts of inorganic salts, which is difficult to dispose of, is avoided. Its main drawback is that all mechanical impurities present in PET are left in the TPA, thus the product can be considered of worse purity than the product of acid or alkaline hydrolysis. 4. Energy recovery refers to the recovery of plastics energy content. Incineration aiming at the recovery of energy is currently the most effective way to reduce the volume of organic materials. Although polymers are actually high-yielding energy sources, this method has been widely accused as ecologically unacceptable owing to the health risk from air born toxic substances e.g. dioxins (in the case of chlorine containing polymers). Among the recycling techniques, incineration meets with strong societal opposition and mechanical recycling can be carried out only on single-polymer waste streams. Thus, from the aforementioned approaches we focused our attention on a specific method which should conform to the sustainable development principles and the new trends in the industrial production of PET. In other words: chemical recycling by hydrolysis leading to the monomers TPA and EG. During last years hydrolysis of waste PET was investigated in our laboratory as potential method for the chemical recycling of soft drink bottles [4-5]. As a step further, in this paper, PET hydrolysis is examined under microwave irradiation. The main advantages of using microwave energy include depolymerization in milder experimental conditions and/or shorter reaction times [7-8]. Therefore,

in this study, depolymerization of PET, taken from common soft drink bottles, was subjected to alkaline hydrolysis in a lab-scale microwave reactor in order to study the effect of microwave irradiation on the reaction kinetics. The reaction was carried out in a sealed microwave reactor in which pressure and temperature were controlled. The main products were the monomers terephthalic acid (obtained in pure form) and ethylene glycol which were analyzed and identified. The effect of several process parameters on the degree of PET depolymerization and TPA recovery was investigated. 2. MATERIALS AND METHODS 2.1 Materials PET flakes were prepared from used clear PET bottles, from which the labels and glue had been removed. The bottles were cut and fed to a rotary cutter producing flakes with a maximum size of 6 mm. The chemicals used were reagent grade. The phase transfer catalysts, TriOctylMethyl Ammonium Bromide (TOMAB) and HexadecylTriMethylAmmonium Bromide (HTMAB) were obtained from Aldrich. 2.2 Hydrolytic depolymerization The PET decomposition reaction was conducted in a microwave reactor (CEM corporation) equipped with a digital temperature control system and pressure sensors inserted directly into the 10 mL PTFE reaction tube. Pellets of sodium hydroxide (5 g) were dissolved in 100 mL of distilled water and the resultant NaOH solution (1.25 M, 5%w/v) was used for the experiments. PET flakes (0.5 g) together with 5 mL of NaOH solution were added into the reactor, sealed and the heat-up period to the desired set-point started. In some experiments 0.012 g of TOMAB (0.01 mol/mol of PET) were also fed into the reactor. When the set temperature was reached the reaction time begun and PET decomposition was followed for a specified time period. After that time period the reaction vessels were automatically cooled and the reaction mixture was filtered to remove the unreacted PET solids. The TPA in the mixture was precipitated by acidification with H2SO4 to a pH of 2.5. Finally, the mixture was filtered and washed with absolute ethanol. The solid TPA produced was dried in a vacuum oven at 40oC and weighed. The final unreacted PET was also measured upon filtration of the final mixture through a G3 glass filter, washing with water, drying in a vacuum oven at 40oC and weighing. 2.3 Analysis of the Results The % yield in TPA was calculated using the formula:
TPA Yield (%) = NTPA 100 NTPA,0

(1)

where, NTPA and NTPA,0 refer to the number of moles weighted and the theoretical number of TPA moles that will be produced upon complete decomposition of PET, respectively. The percent degradation of PET was calculated using the following equation:

PET Degradation (%) =

WPET ,0 WPET , f WPET ,0

100

(2)

where, WPET,0 and WPET,f refer to the initial and final weight of PET, respectively.

2.4 Characterization The determination of purity of terephthalic acid was performed by titration with KOH solution N/2. About 1 g of TPA is weighed to the nearest miligram into a 250 mL conical flask. To dissolve the sample 25 mL of analytical grade pyridine is added by pipette and the suspension is heated with a reflux condenser until a clear solution is obtained. The condenser is then washed out by the addition of about 5 mL of pure pyridine through the top and the content of the flask is titrated with approximately 0.5 N standard potassium hydroxide solution to a phenolphthalein endpoint.

The TPA separated, was dissolved in deuterated dimethyl sulfoxide and its purity was also examined by 1H NMR analysis.
3. RESULTS AND DISCUSSION 3.1 Depolymerization reaction Waste PET flakes were first hydrolyzed in sodium (or potassium) hydroxide to yield the disodium (or dipotassium) salt and ethylene glycol, according to the following chemical reaction:
O H O CH2CH2 O C O C n OH

2n NaOH

O n NaO C

O C ONa + n HOCH2CH2OH + H2O

The TPA-Na2 salt was continuous acidified with sulfuric acid to yield the TPA.
O NaO C O C ONa + H2SO4 HO O C O C OH + Na2SO4

3.2 PET alkaline hydrolysis under microwave irradiation The effect of depolymerization temperature on the alkaline hydrolysis of PET at different depolymerization time periods is shown in Figure 1. As expected, an increase in the reaction temperature leads to increased decomposition of PET. In the same Figure results are included on the TPA yield with and without the use of microwave irradiation. On comparing the corresponding values obtained, it can be postulated that at all temperatures investigated, the time required for the degradation of PET at a certain level has much been shortened when using microwave irradiation. Specifically, the time required to achieve 98 wt-% TPA yield at 180oC has been shortened from 1 h to 0.5 h. Correspondingly at 150oC, the time required to achieve 76 wt-% TPA yield has been shortened from 5 h to 1h and at 120oC the time required for 33 % TPA yield from 7 h to 1.5 h. Therefore, it seems that the effect of microwave irradiation on PET hydrolytic degradation is very important. Shortening of the required depolymerization time results in minimization of the labor costs and consequently to a more profitable process.

100

80

TPA Yield (%)

60

40

120 C o 150 C o 180 C

20

0 0 1 2 3 4 5 6 7

Reaction time (hr)

Figure 1. Effect of temperature on the TPA yield versus depolymerization time, during alkaline hydrolysis with NaOH concentration: 5 wt.-%. Filled and open symbols represent experiments without and with the use of microwave irradiation Results on the amount of unreacted PET measured at different temperatures with the use of microwave irradiation are presented in Table 1. Again PET degradation is favored by increased temperature and reaction time. At 180oC and after only 30 min PET has depolymerized almost completely, while at 120oC even after 2 h of reaction almost half of the PET remains unchanged. TABLE 1. Unreacted PET (wt.-%) remained after alkaline hydrolysis of PET flakes under microwave irradiation at different temperatures and times Addition of phase Depolymerization transfer catalyst Time (min)
180 Temperature (oC) 150 120

10 20 30 60 120

8.6 4.1 1.0 -

41.3 36.6 32.0 22.6 18.7

92.6 88.3 86.8 78.3 54.9

Furthermore, the effect of using a phase transfer catalyst on the TPA yield during alkaline hydrolysis of PET under microwave irradiation is presented in Figure 2. It is obvious that the results obtained with trioctyl methyl ammonium bromide (TOMAB) are superior than the other catalyst hexadecyl trimethyl ammonium bromide (HTMAB) and much higher compared to no-added catalyst experiments. Therefore, some extra experiments were carried out using always TOMAB. The effect of the amount of catalyst was investigated in Figure 3. From the results it was concluded that it does not influence much the PET degradation and monomer yield.

80 70 60

80

no added catalyst TOMAB HDTMAB

70 60

TPA yield (wt.-%)

50 40 30 20 10 0 0.0

TPA yield (wt-%)

50 40 30 20 10 mol of catalyst/ g PET

0.005 0.01 0.02 0.03

0.5 1.0 1.5 2.0

0.5

1.0

1.5

2.0

0 0.0

Reaction time (h)

Reaction time (h)

Figure 2. Effect of phase transfer catalyst type on the TPA yield versus depolymerization time, during alkaline hydrolysis of PET with NaOH, 5 wt.-% and under microwave irradiation

Figure 3. Effect of the amount of phase transfer catalyst on the TPA yield versus time, during alkaline hydrolysis of PET with NaOH conc. 5 wt.-% and under microwave irradiation

Using the phase transfer catalyst, TOMAB some extra experiments were carried out at depolymerization temperatures less than 100oC. The effect of temperature and alkaline concentration on the amount of unreacted PET and the TPA yield are included in Table 2. It is seen that the amount of unreacted PET is larger at these experiments compared to those in Table 1, which is attributed to the lower temperatures used. A very important observation was that when using the TOMAB, phase transfer catalyst, the results obtained at 70oC are similar to those at 120oC without its use. Therefore, it seems that this catalyst plays an important role on the reaction kinetics. Finally, it seems that increased alkaline concentration leads also to a larger amount of monomer yield. However, using concentrated alkaline solutions one has to balance between the extra cost and the larger amount of Na2SO4 produced with that of larger monomer recovery.
4. CONCLUSIONS

Hydrolytic depolymerization of PET in alkaline solution was investigated as an effective technique for the chemical recycling of PET and recovery of its monomers TPA and EG. Microwave irradiation was found to shorten very much the time needed to achieve a specific degradation of PET as well as a TPA yield. Also, use of a phase transfer catalyst (TOMAB) was found to result in the same unreacted PET amount but at significantly lower depolymerization temperatures. PET depolymerization is favored by increasing temperature, time and alkaline solution concentration, while it is not influenced much by the amount of catalyst used.
REFERENCES

[1] [2] [3] [4]

www.plasticseurope.org www.petcore.org (Petcore report 2007) Scheirs J. (1998) Polymer Recycling, J. Wiley & Sons, W. Sussex. Achilias D.S. and G.P. Karayannidis (2004) Chemical recycling of PET as an indicator of sustainable development Water, Air & Soil Pollution: Focus, 4, 385. [5] Karayannidis G.P. and D.S. Achilias (2007) Chemical recycling of poly(ethylene terephthalate) Macromolecular Materials & Engineering, 292, 128-146.

[6] Papaspyrides C. and J. Poulakis J. (1996), in J.C. Salamone (ed.), Encyclopedia of Polymeric Materials, CRC Press, Boca Raton, FL, USA, pp 7403-7418. [7] Liu L., D. Zhang, L. An, H. Zhang and Y. Tian (2004) Hydrolytic depolymerization of PET under microwave irradiation J. Applied Polymer Science, 95, 719-723. [8] Nikje M.M.A. and F. Nazari (2007) Microwave-assisted depolymerization of PET at atmospheric pressure Advances in Polymer Technology, 25, 242-246.

TABLE 2. Amount of terephthalic acid (TPA) produced and unreacted PET (wt.-%) remained, after alkaline hydrolysis of PET flakes under microwave irradiation at different temperatures and times (catalyst used TOMAB at concentration 0.01 mol/g of PET). T (oC) 70 Time (min) 10 30 60 120 80 10 30 60 120 90 10 30 60 120 90 10 30 60 120 90 10 30 60 120 90 10 30 60 120 NaOH (%w/v) 5 5 5 5 5 5 5 5 5 5 5 5 10 10 10 10 7.5 7.5 7.5 7.5 2.5 2.5 2.5 2.5 Unreacted PET (%) 95.0 85.6 80.0 68.0 88.7 78.5 66.9 57.3 68.6 63.6 49.6 42.6 61.1 49.5 40.1 15.2 65.0 54.8 43.9 29.1 73.3 67.4 60.9 54.4 TPA (%) 0.7 12.2 19.2 31.7 12.1 21.2 30.8 39.5 29.4 35.8 42.8 61.4 37.7 47.5 54.2 81.8 32.7 44.7 50.1 66.9 23.3 31.3 36.9 42.8