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.     

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.     

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.     

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.     

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。     

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.     

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.     

Selective separation of virgin and post-consumer polymers (PET and PVC) by flotation method

More and more polymer wastes are generated by industry and householders today. Recycling is an important process to reduce the amount of waste resulting from human activities. Currently, recycling technologies use relatively homogeneous polymers because hand-sorting waste is costly. Many promising technologies are being investigated for separating mixed thermoplastics, but they are still uneconomical and unreliable. At present, most waste polymers cause serious environmental problems. Burning polymers for recycling is not practiced since poisonous gases are released during the burning process. Particularly, polyvinyl chloride (PVC) materials among waste polymers generate hazardous HCl gas, dioxins containing Cl, etc., which lead to air pollution and shorten the life of the incinerator. In addition, they make other polymers difficult to recycle.Both polyethylene terephthalate (PET) and PVC have densities of 1.30–1.35 g/cm³ and cannot be separated using conventional gravity separation techniques. For this reason, polymer recycling needs new techniques. Among these techniques, froth flotation, which is also used in mineral processing, can be useful because of its low cost and simplicity.The main objective of this research is to recycle PET and PVC selectively from post-consumer polymer wastes and virgin polymers by using froth flotation. According to the results, all PVC particles were floated with 98.8% efficiency in virgin polymer separation while PET particles were obtained with 99.7% purity and 57.0% efficiency in post-consumer polymer separation.     

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.     

Biopolymers in the Existing Postconsumer Plastics Recycling Stream

The existing plastic bottle reclaiming industry has working technology, satisfied customers, raw material, and investors. Adding new materials to the current mix requires satisfying all four needs for those materials. Rigid plastic container recycling focuses on high-density polyethylene (HDPE) and polyethylene terephthalate (PET) bottles, the overwhelming percentage of bottles sold in North America. Bottles of other resins, including polyvinyl chloride (PVC), polypropylene and biopolymers, lack critical mass necessary for independent reclamation. To be mechanically recycled, biopolymers must be either completely fungible with existing recycled resins or be available in sufficient quantity to achieve the needed critical mass. So far, biopolymer volume projections are not encouraging. Biopolymers, like all minor bottle resins, must pay their own way in sorting and processing without subsidy from PET and HDPE recycling. Based on limited data, some biopolymers may have little effect on recycled HDPE performance, but will represent a yields loss and added economic burden at some level of occurrence. Biopolymers have not been shown to be compatible with PET and likely will represent performance problems and economic burdens at even low levels of occurrence. Applications for biopolymers should be carefully selected so as to not interfere with currently recycled materials unless critical mass can be achieved quickly.

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.     

Effect of Recycling on Material Properties of Glass-filled Polyethylene Terephthalate

Recycled plastics are considered low performance materials because their properties are expected to decrease drastically with recycling. The objective of this study was to characterize a 15 wt.% glass filled polyethylene terephthalate (rPET-15GF) using six recycle generations and four recycle ratios. Mechanical properties such as tensile strength, elastic modulus, and percent elongation to failure of the PET composite were determined for various recycle generations and recycle ratios. Results show that the mechanical properties of rPET-15GF decrease slightly per recycle generation. In contrast, thermal properties of rPET-15GF were not at all affected by the recycling process. This data demonstrates that recycled glass filled PET can be used effectively to fabricate components without significantly affecting their mechanical performance.     

Methanolysis and Hydrolysis of Polycarbonate Under Moderate Conditions

Alkali-catalyzed methanolysis and hydrolysis of polycarbonate (PC) in a solvent in which PC can substantially dissolve such as N-methyl-2-pyrrolidone, 1,4-dioxane, tetrahydrofuran and so on were studied. Reaction conditions were optimized for the purpose of recycling PC in the form of bisphenol A and carbon carbonate. The results showed that both the methanolysis and hydrolysis of PC could take place under moderate conditions. Under the conditions of reaction temperature 40 °C, m(PC):m(MeOH) = 1:1, m(PC):m(NaOH) = 50:1, reaction time 35 min and using tetrahydrofuran as solvent, the methanolysis conversion of PC was almost 100% and the yield of bisphenol A was over 95%. Moreover, under the conditions of reaction temperature 100 °C, m(PC):m(H₂O) = 1:0.7, m(PC):m(NaOH) = 10:1, reaction time 8 h and using 1,4-dioxane as solvent, the hydrolysis conversion of PC was almost 100% and the yield of bisphenol A was over 94%.     

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.

     

Resource recovery from urban stock,the example of cadmium and tellurium from thin film module recycling

Raw material supply is essential for all industrial activities. The use of secondary raw material gains more importance since ore grade in primary production is decreasing. Meanwhile urban stock contains considerable amounts of various elements. Photovoltaic (PV) generating systems are part of the urban stock and recycling technologies for PV thin film modules with CdTe as semiconductor are needed because cadmium could cause hazardous environmental impact and tellurium is a scarce element where future supply might be constrained. The paper describes a sequence of mechanical processing techniques for end-of-life PV thin film modules consisting of sandblasting and flotation. Separation of the semiconductor material from the glass surface was possible, however, enrichment and yield of valuables in the flotation step were non-satisfying. Nevertheless, recovery of valuable metals from urban stock is a viable method for the extension of the availability of limited natural resources.     

Supercritical methanol for polyethylene terephthalate depolymerization: observation using simulator

To apply PET depolymerization in supercritical methanol to commercial recycling, the benefits of supercritical methanol usage in PET depolymerization was investigated from the viewpoint of the reaction rate and energy demands. PET was depolymerized in a batch reactor at 573 K in supercritical methanol under 14.7 MPa and in vapor methanol under 0.98 MPa in our previous work. The main products of both reactions were the PET monomers of dimethyl terephthalate (DMT) and ethylene glycol (EG). The rate of PET depolymerization in supercritical methanol was faster than that of PET depolymerization in vapor methanol. This indicates supercritical fluid is beneficial in reducing reaction time without the use of a catalyst. We depicted the simple process flow of PET depolymerization in supercritical methanol and in vapor methanol, and by simulation evaluated the total heat demand of each process. In this simulation, bis-hydroxyethyl terephthalate (BHET) was used as a model component of PET. The total heat demand of PET depolymerization in supercritical methanol was 2.35 x 10(6)kJ/kmol Produced-DMT. That of PET depolymerization in vapor methanol was 2.84 x 10(6)kJ/kmol Produced-DMT. The smaller total heat demand of PET depolymerization in supercritical methanol clearly reveals the advantage of using supercritical fluid in terms of energy savings.     

A Novel Biodegradable Fluorine-Containing Copolymer Surfactant

A novel fluorine-containing copolymer surfactant was synthesized via free radical copolymerization from maleic anhydride and rapeseed oil firstly, and then followed by an esterification reaction with dodecafluoro heptanol. The reaction progresses were monitored on-line by FTIR and the copolymerization was characterized by molecular weight (GPC) analysis. Simultaneously, the surface tension and critical micelle concentration (CMC) together with the biodegradability of the fluorine-containing copolymer surfactant were investigated in detail. The results indicate that this fluorine-containing surfactant with Mw of 66000 g/ mol and Mn of 38800 g/mol shows a strong surface tension lowering ability, the CMC is 0.1 g/L, the surface tension value at the CMC (γ_CMC) is 22.5 mN m⁻¹ and less than the corresponding copolymeric hydrocarbon surfactant; the evaluation of biodegradability indicates that the biological respiration curve of the fluorine-containing copolymer surfactant with concentration of 1000 mg/L is above the endogenous respiration curve; the BOD₅/COD value is higher than 0.45; the COD and TOC removal ratios after 5 days of biodegradation reach 91.0 and 89.4%, respectively, showing good biodegradability and environmental-friendly feature.     

Alternative polymer separation technology by centrifugal force in a melted state

In order to upgrade polymer waste during recycling, separation should take place at high purity. The present research was aimed to develop a novel, alternative separation opportunity, where the polymer fractions were separated by centrifugal force in melted state. The efficiency of the constructed separation equipment was verified by two immiscible plastics (polyethylene terephthalate, PET; low density polyethylene, LDPE), which have a high difference of density, and of which large quantities can also be found in the municipal solid waste. The results show that the developed equipment is suitable not only for separating dry blended mixtures of PET/LDPE into pure components again, but also for separating prefabricated polymer blends. By this process it becomes possible to recover pure polymer substances from multi-component products during the recycling process. The adequacy of results was verified by differential scanning calorimetry (DSC) measurement as well as optical microscopy and Raman spectroscopy.     

Crystallization and Mechanical Properties of Recycled Poly(ethylene terephthalate) Toughened by Styrene–Ethylene/Butylenes–Styrene Elastomer

Recycled poly(ethylene terephthalate) (R-PET) was blended with 15–30 wt% of styrene–ethylene/butylenes–styrene (SEBS) block copolymer and maleic anhydride grafted SEBS (SEBS-g-MA). Effects of nucleation and toughening of the elastomers were evaluated systematically by study of morphology, crystallization, thermal and mechanical properties of the blend. The addition of 30 wt% SEBS promoted the formation of co-continuous structure of the blend and caused the fracture mechanism to change from strain softening to strain hardening. Addition of SEBS-g-MA resulted in significant modification of phase morphology and obviously improved the impact strength. The compatibilization reaction of PET with SEBS-g-MA accelerated the crystallization of PET and increased the crystallinity. The shifts in glass transition temperature of PET towards that of SEBS-g-MA and the higher modulus for R-PET/SEBS-g-MA (70/30) blend found by DMA are also indications of better interactions under the conditions of compatibilization and interpenetrating structure.     

A New Unsaturated Poly(ester-urethane) Based on Terephthalic Acid Derived from Polyethylene Terephthalate (PET) of Waste Bottles

The new unsaturated poly(ester-urethane) was synthesized by the reaction of 4,4??-methylenediphenyldiisocyanate with 4,4??-di(2,3-butenhydroxyl) terephthalate in the ratio of 1:1. 4,4??-di(2,3-butenhydroxyl) terephthalate was first prepared by reacting 2?mol of cis-2-butene-1, 4-diol with 1?mol of terephthalic acid. The terephthalic acid used was derived from the recycling of PET bottles via subjection to saponification process. The synthesized compounds were characterized by CHN analysis, FT-IR, ¹H NMR and UV?CVis spectroscopy, with consistency of results showing the presence of the new unsaturated poly(ester-urethane) II. Thermal properties of the new polymer was verified by differential scanning calorimetry and thermogravimetric analysis, whereas the mechanical properties were characterized by tensile, elongation, hardness, adhesion and impact testing. The electrical conductivity and the electrical resistance of the compound were observed with increasing applied voltage.