Mechanism of Depolymerization Reaction of Polyethylene Terephthalate: Experimental and Theoretical Studies

The depolymerization reaction of polyethylene terephthalate (PET) was analyzed on the basis of both experimental data and numerical data obtained from quantum chemistry calculations. Various alcohols were used as solvents in the search for the reaction mechanism. The activation energy obtained from the optimized structures of the ground state and the transitional state was compared with our experimental data. Based on these comparisons, it was found that the formation of rings from alkoxyl groups and carbonyl carbon atoms at the transitional state is highly important when the ester bonds of PET are broken. Moreover, the most appropriate alcohol was suggested for the depolymerization reaction.     

聚对苯二甲酸乙二醇酯废料的回收方法

介绍了聚对苯二甲酸乙二醇酯传统的化学回收方法：甲醇醇解法、水解法和醣酵解法;简述了聚酯新的回收工艺：伊斯曼乙二醇水解工艺、超临界水水解工艺和Reco-PET工艺,及有关国家聚酯回收的工业化实践,并对聚酯回收的前景及影响聚酯回收的因素进行了分析。     

Depolymerization of Waste PET with Phosphoric Acid–Modified Silica Gel Under Microwave Irradiation

Chemical recycling of waste poly(ethylene terephthalate) (PET) using phosphoric acid–modified silica gel as a solid catalyst is reported. Advantageously, microwave irradiation was used to progress the depolymerization of PET. In this study, depolymerization of PET with a small amount of water is suggested as a suitable method. The depolymerized product, terephthalic acid was obtained and assigned by ¹H NMR and FT-IR spectroscopy. Finally, over 90 % conversion to terephthalic acid was achieved when waste plastic bottles were treated with the method. This results confirm the importance of the microwave power technique as a promising recycling method for plastic bottles made from PET, resulting in monomer recovery in addition to substantial energy saving.     

Investigation of conventional analytical methods for determining conversion of polyethylene terephthalate waste degradation via aminolysis process

Journal of Material Cycles and Waste Management - There is a growing interest in the depolymerization of polyethylene terephthalate (PET) waste for both environmental and economic reasons by...     

Supercritical water oxidation of landfill leachate

In this paper, ammonia as an important ingredient in landfill leachate was mainly studied. Based on Peng-Robinson formulations and Gibbs free energy minimization method, the estimation of equilibrium composition and thermodynamic analysis for supercritical water oxidation of ammonia (SCWO) was made. As equilibrium is reached, ammonia could be totally oxidized in SCW. N(2) is the main product, and the formation of NO(2) and NO could be neglected. The investigation on SCWO of landfill leachate was conducted in a batch reactor at temperature of 380-500 °C, reaction time of 50-300s and pressure of 25 MPa. The effect of reaction parameters such as oxidant equivalent ratio, reaction time and temperature were investigated. The results showed that COD and NH(3) conversion improved as temperature, reaction time and oxygen excess increased. Compared to organics, NH(3) is a refractory compound in supercritical water. The conversion of COD and NH(3) were higher in the presence of MnO(2) than that without catalyst. The interaction between reaction temperature and time was analyzed by using response surface method (RSM) and the results showed that its influence on the NH(3) conversion was relatively insignificant in the case without catalyst. A global power-law rate expression was regressed from experimental data to estimate the reaction rate of NH(3). The activation energy with and without catalyst for NH(3) oxidation were 107.07 ± 8.57 kJ/mol and 83.22 ± 15.62 kJ/mol, respectively.     

Recycling of waste PET into useful textile auxiliaries

Polyethylene terephthalate (PET) waste fibers were initially depolymerized using a glycolysis route in the presence of sodium sulfate as a catalyst, which is a commonly used chemical and ecofriendly as compared to heavy metal catalysts. Good yield of the pure monomer bis(2-hydroxyethylene terephthalate) (BHET) was obtained. Further, to attempt its reuse, the purified BHET was converted to different fatty amide derivatives to obtain quaternary ammonium compounds that have a potential for use as softener in the textile finishing process. The products were characterized by infrared spectroscopy. Application of these synthesized compounds was carried out on cotton fabric; they were evaluated for performance and were found to give good results. The chemicals used during depolymerization and reuse of PET are inexpensive and comparatively less harmful to the environment, and thus offer advantages in the chemical recycling of polyester waste fibers.     

Evaluation of Poly(ethylene-terephthalate) Products of Chemical Recycling by Differential Scanning Calorimetry

Poly (ethylene-terephthalate), (PET) bottles waste was chemically recycled by glycolysis and hydrolysis. The depolymerization processes were carried out in different time intervals from 5 to 360 min, in two different molar ratios of PET/EG, 1:5 and 1:18 and at different temperatures. The PET glycolysis leads to formation of bis(2-hydroxy-ethyl)terephthalate (BHET) monomer and PET oligomers with hydroxyl and carboxyl end groups while PET hydrolysis is followed by formation of monomers terephthalic acid (TPA) and ethylene glycol (EG). Fractions of monomers and oligomers were further characterized by FTIR spectroscopy and by differential scanning calorimetry (DSC). The results show that DSC is successful method to describe the different structures of oligomers formed during chemical recycling of PET.     

Catalytic hydrothermal depolymerization of nylon 6

Depolymerization of nylon 6 to produce ε-caprolactam using an environmentally friendly heteropoly acid catalyst was studied at temperatures between 553 and 603 K in water. The products of depolymerization were analyzed qualitatively and quantitatively by means of mass spectrometry and high-performance liquid chromatography. The results showed that the depolymerized product was mainly ε-caprolactam with a little 6-aminocaproic acid and oligomers. The phosphotungstic heteropoly acid used as a catalyst can improve the hydrolysis rate and yield of ε-caprolactam. The optimum hydrolysis conditions for ε-caprolactam yield were as follows: phosphotungstic heteropoly acid content, 3%; reaction temperature, 573 K; and reaction time, 85 min. Under these conditions, the yield of ε-caprolactam was 77.96%. In the temperature range 553–603 K, the activation energy of 3% phosphotungstic heteropoly acid-catalyzed depolymerization was evaluated as 77.38 kJ/mol, which is lower than the 86.64 kJ/mol value for no catalyst.     

One-Pot Reaction of Waste PET to Flame Retardant Polyurethane Foam,via Deep Eutectic Solvents-Based Conversion Technology

Depolymerization of polyethylene terephthalate (PET) is a promising technology for producing recycled monomers. Using a deep eutectic solvent (DES)-based catalyst, the PET glycolysis process produces bis-(2-hydroxyethylene terephthalate) (BHET). This recycled monomer reacts with isocyanate and forms polyurethane foam (PUF). The DES-based one-pot reaction is advantageous because it is a low-energy process that requires relatively lower temperatures and reduced reaction times. In this study, choline chloride/urea, zinc chloride/urea, and zinc acetate/urea based DESs were adopted as DES catalysts for glycolysis. Subsequently, the conversion of PET, BHET yield, and OH values were evaluated. Both filtered and unfiltered reaction mixtures were used as polyols for PUF polymerization after characterization of the acid and hydroxyl values of the polyols, as well as the NCO (–N=C=O) value of isocyanate. In the case of unfiltered reaction mixtures, PUF was obtained via a one-pot reaction, which exhibited higher thermal stability than PUF made from the filtered polyols. This outcome indicated that oligomeric BHET containing many aromatic moieties in unfiltered polyols contributes to the thermal stability of PUF. This environmentally friendly and relatively simple process is an economical approach for upcycling waste PET.

     

Synthesis of copolyesters containing poly(ethylene terephthalate) and poly(ε-caprolactone) units and their susceptibility toPseudomonas sp. lipase

Copolyesters containing poly(ethylene terephthalate) (PET) and poly(-caprolactone) (PCL) were synthesized from PET and PCL homopolymers by transesterification reaction at 270°C in the presence of catalyst. The copolyesters were characterized by¹³C-NMR and differential scanning calorimetry (DSC). The degradation behavior of PCL byPseudomonas sp. lipase in buffer solution (pH 7) and tetrahydrofuran (THF) was investigated by gel permeation chromatography (GPC) and¹H-NMR. From these experiments, it was found thatPseudomonas sp. lipase acted endoenzymatically on PCL. Using this lipase, degradation tests for PET/PCL copolyesters whose PCL content was below 50% by weight were also performed in buffer solution (pH 7). However, evenPseudomonas sp. lipase with high degradation activity on PCL did not easily degrade the PCL unit in PET/PCL copolyesters.     

Modification of Thermo-Mechanical Properties of Recycled PET by Vinyl Acetate (VAc) Monomer Grafting Using Gamma Irradiation

Vinyl acetate (VAc) monomer of different percentage was grafted onto the recycled polyethylene terephthalate (r-PET) films using gamma irradiation. The properties of these modified films were characterized by Fourier transform infrared spectroscopy (FTIR), mechanical properties testing (Tensile strength, Elongation at break), dynamic mechanical analysis (DMA) and thermo-gravimetric analysis (TGA). The Tensile Strength (TS) of the modified PET film increased by 132.25?% to the highest value of 50.12 MPa at 15% VAc monomer concentration at 3 kGy gamma dose, while the elongation at break (EB) decreased by 31.83?%. FTIR was used to investigate the molecular interaction of the modified films. TGA revealed that curve of the modified PET film shifted toward higher temperature region by 95?°C, which is very close to that of PET film made from virgin flakes. The results indicate that modified PET films of better mechanical and thermal properties were successfully prepared using VAc monomer grafting by gamma irradiation technique.     

Synthesis of unsaturated polyester resin from glycolysed postconsumer PET wastes

The purpose of this study was to explore ways to extend the chemical recycling of poly(ethylene terephthalate) (PET) as a valuable feedstock for chemical processes. First, PET wastes were depolymerised using a glycolysis method in the presence of sodium carbonate, which is considered to be a less environmentally damaging option for a catalyst. Good yields of the monomer bis(2-hydroxyethyl) terephthalate (BHET) were obtained (80 %). Second, to develop an economically viable recycling programme for the reclaimed BHET, the conversion of purified BHET into unsaturated polyester resins (UPR) was studied. The recovered monomer was thus polyesterified with maleic anhydride and subsequently mixed with styrene monomer to prepare UPRs. The resins were casted by a crosslinking reaction using methyl ethyl ketone peroxide and cobalt 2-ethylhexanoate as the initiator and catalyst, respectively. The polyesterification reaction was followed by gel permeation chromatography. The curing process was studied by differential scanning calorimetry and infrared spectroscopy. The cured resin was subjected to various characterisation methods in order to determine its chemical, physical and mechanical properties. Resins with suitable properties for commercial application were obtained.     

Thermogravimetric analysis of biowastes during combustion

The combustion of sewage sludge (SS), animal manure (AM) and the organic fraction of municipal solid waste (OFMSW) was assessed and compared with that of a semianthracite coal (SC) and of a PET waste by thermogravimetric (TG) analysis. Differences were found in the TG curves obtained for the combustion of these materials accordingly to their respective proximate analysis. Non-isothermal thermogravimetric data were used to assess the kinetics of the combustion of these biowastes. The present paper reports on the application of the Vyazovkin model-free isoconversional method for the evaluation of the activation energy necessary for the combustion of these biowastes. The activation energy related to SS combustion (129.1 kJ/mol) was similar to that corresponding to AM (132.5 kJ/mol) while the OFMSW showed a higher value (159.3 kJ/mol). These values are quite higher than the one determined in the same way for the combustion of SC (49.2 kJ/mol) but lower than that for the combustion of a PET waste (165.6 kJ/mol).     

Chemical depolymerisation of PET complex waste: hydrolysis vs. glycolysis

The huge increase in the generation of post-consumer plastic waste has produced a growing interest in eco-efficient strategies and technologies for their appropriate management and recycling. In response to this, PROQUIPOL Project is focused on developing, optimizing and adapting feedstock recycling technologies as an alternative for management for the treatment of complex plastic waste. Among the different plastic wastes studied, PROQUIPOL Project is working on providing a suitable treatment to the highly colored and complex multilayered post-consumer waste fractions of polyethylene terephthalate (PET) by chemical depolymerisation methods. Glycolysis and alkali hydrolysis processes have been studied with the aim of promoting the transformation of PET into the bis(2-hydroxyethyl) terephthalate monomer and terephthalic acid, respectively. In both cases operational conditions such as temperature, reaction time, catalyst to PET rate and solvent to PET rate have been considered to optimize product yield, achieving values near to 90 % and monomer purities over 95 % in both processes. This paper presents results obtained for each treatment as well as a simplified comparison of technical, economic and environmental issues.     

The consumption and recycling collection system of PET bottles: A case study of Beijing,China

After studying the recycling collection system of polyethylene terephthalate (PET) bottles worldwide, the authors conducted an intercept survey in Beijing. Two separate questionnaires were issued, one questionnaire to PET bottle consumers and one to PET bottle recyclers. In this study, consumers are defined as people that consume PET-bottled beverages in their daily life. Recyclers were defined as those involved in the collection and recycling of PET bottles. These include scavengers, itinerant waste buyers, small community waste-buying depots, medium/large redemption depots, and recycling companies. In total, 580 surveys were completed, including 461 by consumers and 119 by recyclers. The authors found that consumption of PET bottles in Beijing was nearly 100,000 tonnes in 2012. Age, occupation, gender, and education were identified as significant factors linked to PET-bottled beverage consumption, while income was not a significant factor. 90% Of post-consumed PET bottles were collected by informal collectors (i.e., scavengers and itinerant waste buyers). The survey also found that nearly all PET bottles were reprocessed by small factories that were not designed with pollution control equipment, which allows them to offer higher prices for waste recyclable bottles. As Beijing is trying to build a formal recycling collection system for recyclables, subsidies should be given to the formal recycling sector rather than being charged land use fees, and attention should also be given to informal recyclers that make their living from the collection of recyclables. Informal and formal sectors may work together by employing the scavengers and itinerant waste buyers for the formal sectors. In addition to the recycling of PET bottles, concern should also be allocated to reduce consumption, especially among young people, as they, compared to other groups, have a stronger demand for PET-bottled beverages and will be the main body of society.     

镁铝水滑石制备复合金属氧化物及其催化处理废弃聚酯材料

采用共沉淀法合成了镁铝水滑石并将其在不同温度下煅烧得到复合金属氧化物。将两者作为催化剂用于醇解聚对苯二甲酸乙二醇酯(PET)反应中。实验结果表明:复合金属氧化物的催化活性明显高于其前体,最佳煅烧温度为500℃;在催化剂与PET质量比为1.0%、醇解反应时间为50 min时,产物对苯二甲酸乙二醇酯(BHET)的产率可达到81%。镁铝水滑石煅烧后得到的复合金属氧化物是一种高效、环境友好型醇解PET催化剂,可以替代目前常用的均相催化剂。     

Kinetics and Thermodynamics of Hydrolytic Depolymerization of Polyamide Waste at Various Temperature and Autogenious Pressure by High-Pressure Autoclave

Hydrolytic depolymerization of polyamide waste in water was studied using 0.5 L high pressure autoclave at temperatures of 235, 240, 245, 250 °C and at autogenious pressure 480, 500, 520, and 600 psi (pound per square inch).The reaction rate constant, energy of activation, enthalpy of activation, entropy of activation and equilibrium constant were calculated from the experimental data obtained. The maximum depolymerization (59.2%) of polyamide waste into monomer caprolactum was obtained at 250 °C and 600 psi pressure. The reaction rate constant was obtained on basis of measurement of amine value and residual weight. The depolymerization reaction was found to be pseudo first order with reaction rate constant of the order of 10⁻³ min⁻¹. The enthalpy, entropy and free energy of activation were recorded as 85.75, −0.1354 and 156.59 kJ mol⁻¹ respectively at the experimental conditions for maximum depolymerization of polyamide waste. The thermodynamic equilibrium constant for this hydrolysis reaction was found to be 2.3 × 10⁻¹⁶.     

Aminolytic Depolymerization of Polyethylene Terephthalate Wastes Using Sn-Doped ZnO Nanoparticles

Journal of Polymers and the Environment - Poly(ethylene terephthalate) (PET) is one of the most consumed polymers because of its excellent thermal and mechanical properties. By increasing in PET...     

Chemical Recycling of PET Waste with Multifunctional Pentaerythrytol in the Melt State

Chemical recycling of poly(ethylene terephthalate) PET waste in the melt state through alcoholysis with multifunctional alcohol—pentaerythrytol (PENTE)—was performed in a internal mixer Haake Rheomix 600, at 250 °C, 60 rpm, for 10 min, in presence of zinc acetate. The following PET:PENTE molar ratios 1:0; 1:0.16; 1:0.48 and 1:3.4 were studied. The chemical structure of the end-products was characterized by FT-IR. Thermal properties and X-ray diffractograms were also assessed. The esterification and alcoholysis reactions took place and were dependent on the molar ratio. The first one is dominant in compositions rich in PET leading to the formation of star-branching copolymer. The second one brings about the PET oligomerization and an oligoester named herein bis(tri-hydroxylneopentyl) terephthalate (BTHNPT) was obtained. The end-products have potential application as asphalt additive or adhesive.     

The Chemical Recycling of PET in the Framework of Sustainable Development

In this investigation, all the techniques used in the chemical recycling of polyethylene terephthalate (PET) are critically reviewed according to the overall benefits together with the environmental surcharge that they cause. Those, which are consistent with the principles of sustainable development, are indicated. Experimental data are presented for the acid hydrolysis of PET and compared with previous results on the alkaline hydrolysis of PET with, or without, the use of a phase transfer catalyst. Overall material balances are carried out for the hydrolysis of PET. Finally, it can be postulated that recycling according to the scheme: is the only one within the framework of sustainable development. 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.