Waste incineration,PVC, and dioxins

Waste incineration is becoming increasingly necessary to tackle the rapidly rising amounts of municipal solid waste (MSW); in China many large cities are already surrounded by a girdle of landfills. Still, the not-in-my-backyard (nimby) syndrome holds strong. This attitude stems from fear of dioxins. These have been associated with incineration (‘dioxin factories’) and at times also with polyvinylchloride. In this paper this issue is analysed. China should build additional trust in MSW incineration, following promulgation of stricter emission standards, enforced by stringent controls.     

TG/FTIR analysis on co-pyrolysis behavior of PE,PVC and PS

The pyrolysis and co-pyrolysis behaviors of polyethylene (PE), polystyrene (PS) and polyvinyl chloride (PVC) under N₂ atmosphere were analyzed by Thermal gravimetric/Fourier transform infrared (TG/FTIR). The volatile products were analyzed to investigate the interaction of the plastic blends during the thermal decomposition process. The TGA results showed that the thermal stability increased followed by PVC, PS and PE. The pyrolysis process of PE was enhanced when mixed with PS. However, PS was postponed when mixed with PVC. As for PE and PVC, mutual block was happened when mixed together. The FTIR results showed that the free radical of the decomposition could combine into a stable compound. When PE mixed with PVC or PS, large amount of unsaturated hydrocarbon groups existed in products while the content of alkynes was decreased. The methyl (CH₃) and methylene (CH₂) bonds were disappeared while PVC mixed with PE.     

Properties of lightweight aggregate concrete prepared with PVC granules derived from scraped PVC pipes

This paper aims to investigate the fresh and hardened properties of lightweight aggregate concretes that are prepared with the use of recycled plastic waste sourced from scraped PVC pipes to replace river sand as fine aggregates. A number of laboratory prepared concrete mixes were tested, in which river sand was partially replaced by PVC plastic waste granules in percentages of 0%, 5%, 15%, 30% and 45% by volume. Two major findings are identified. The positive side shows that the concrete prepared with a partial replacement by PVC was lighter (lower density), was more ductile (greater Poisson's ratios and reduced modulus of elasticity), and had lower drying shrinkage and higher resistance to chloride ion penetration. The negative side reveals that the workability, compressive strength and tensile splitting strength of the concretes were reduced. The results gathered would form a part of useful information for recycling PVC plastic waste in lightweight concrete mixes.     

Pyrolysis kinetics of waste PVC pipe.

The pyrolysis kinetics of waste PVC pipe was investigated with a thermal gravimetric analysis system at heating rates of 5, 10, and 30 degrees C/min in a nitrogen atmosphere. Freeman-Carroll method was employed to evaluate kinetic parameters. Two dominant peaks were observed on derivative gravimetric curves, hypothetically suggesting a two-stage apparent reaction model. The first-stage reaction was likely to be represented by stoichiometric reaction to yield volatiles (mainly HCl) and intermediates. The second-stage reaction might be described by thermal degradation of intermediates competitively into gas, liquid, and solid by-products. Quasi-isothermal operations were introduced to verify the reaction types of the first and second reaction. The generation reaction of intermediates achieved at lower temperatures was carried out independently with their decomposition reaction at higher temperatures. The effects of additives on the pyrolysis kinetics of waste PVC pipe seem to be significant, especially on the first-stage reaction. The first-stage reaction was retarded. A merged peak at low temperatures was observed on the derivative thermogravimetry (DTG) curve instead of two peaks usually observed for that of pure PVC resin. The first peak on the DTG curve of pure PVC resin may shift more, resulting in the complete overlap of two peaks. The quantity of evolved HCl was likely to decrease because of interaction of metal components of stabilizers with either HCl or active chlorine atom or both. The final residual fraction increased as a result of pyrolysis of organic forms of additives to yield extra char. On the other hand, the second-stage reaction kinetics demonstrates a similar pattern to that of pure PVC resin, implying that the effects of additives may be less significant in comparison with that at the first-stage reaction.     

VinylPlus, the new European PVC industry’s voluntary programme toward sustainability

Over the past 10?years, the Vinyl 2010 programme has been highly effective in assisting the European PVC industry tackling various stakeholder concerns related to PVC sustainability. The Vinyl 2010 partners decided in 2009 to launch a follow-up programme, VinylPlus. Vinyl 2010’s success was to a large extent due to the close cooperation of the entire PVC value chain, and to clear targets and deadlines allowing transparent progress monitoring. These key features have been retained. Climate change and availability of non-renewable resources are now widely recognised as major challenges. Health and safety concerns about chemical substances are increasingly prevalent. In this context, a fundamental assessment of the sustainability features of PVC as material and as industry was carried out. An in-depth reflection involving scores of business managers and industry experts, stakeholders and NGOs took place. It produced collective insights and a credible pathway for progress over the next 10?years. Both the reflection process and its results are described, with particular emphasis on recycling. The issue of “legacy additives”, a potential major hurdle of recycling, is given particular attention.     

Preparation and Characterization of PVC Matrix Composites with Biochemical Sludge

Biochemical sludge (BS), generated in the waste water treatment of paper mills, was pretreated by enzyme hydrolysis. The effect and action mechanism of the enzymatic treatment on the properties of polyvinyl chloride (PVC) matrix composites with BS were discussed. Results showed that when the filler content was 30 wt%, the tensile strength of the PVC composites filled with BS and its modified products which were pretreated by laccase, cellulase and hemicellulase can be increased by 38.64, 67.4, 63.5 and 66.3% than the PVC composite filled with calcium carbonate. When the dosage of filler was 40 wt%, the elastic modulus of PVC composites filled with BS and its above three modified products decreased by 53.3, 52.3, 50.0 and 46.3%, respectively. Meanwhile, the thermal stability of PVC composites can also be improved at the temperature of over 340 °C. It can be concluded that the enzyme pretreatment can improve the application performance of BS usage in PVC matrix composites.     

Simultaneous treatment of PVC and oyster-shell wastes by mechanochemical means

This work presents a new process for dechlorinating poly-vinyl chloride (PVC) by the use of oyster-shell waste. The process consists of milling of PVC waste with oyster-shell waste, followed by washing the milled sample with water. The milling of PVC and oyster-shell mixture results in size reduction and rupture in bonds, leading to mechanically induced reactions between the two to form CaCl2 and hydrocarbon with C=C bonds. Washing the milled mixtures with water at room temperature allows complete removal of chlorine from the milled sample. More than 95% of chlorine in PVC was removed when 2h grinding is conducted for the mixture. The present process could offer a potential route to the handling and disposal of oyster-shell and PVC wastes.     

Flame treatment for the selective wetting and separation of PVC and PET

Flame treatment has been used for many years to modify the surface of plastics to allow coatings to be added. The effect of the treatment is to produce hydrophilic species on the surface of the plastic making it water-wettable. The production of hydrophilic plastic surfaces is also required in the selective separation of plastics by froth flotation. For the process to be selective one plastic must be rendered hydrophilic while another remains hydrophobic. In this study the potential for separation of PVC and PET has been investigated. Flame treatment was shown to be very effective in producing a hydrophilic surface on both plastics, although the process was not selective under the conditions investigated. Raising the temperature of the plastics above their softening point produced a hydrophobic recovery. As the softening point of PVC was significantly lower than for PET it was possible to produce a significant difference in hydrophobicity, as judged using contact angle measurement. When immersed in water the contact angle of the PVC was found to be strongly dependent on the pH. Good separation efficiency of the two plastics was achieved by froth flotation from pH 4 to 9. One particular advantage of the technique is that no chemical reagents may be required in the flotation stage. The practicalities of designing a flake treatment system however have to be addressed before considering it to be a viable industrial process.     

Characteristics of PVC pyrolysis products under electric field

Journal of Material Cycles and Waste Management - This paper studied the effect of dielectric barrier discharge (DBD) on pyrolysis product characteristics of polyvinyl chloride (PVC) through...     

Kinetics of thermal de-chlorination of PVC under pyrolytic conditions

Although PVC-containing wastes are an important potential source of energy they are frequently disposed in landfill. In thermal treatment processes such as pyrolysis and gasification, the presence of poly(vinyl chloride) (PVC), a compound with 56.7% of chlorine, may cause problems concerned with environmental protection, as consequence of the formation of hydrochloric acid, chlorine gas and dioxins, as well as corrosion phenomena of the reactor/equipment materials. Thus, a possible solution may involve a previous removal of the chlorine from PVC containing waste through a pyrolysis process at low temperatures before the material being submitted to a subsequent thermal treatment, for energetic valorization. In this work, a kinetic model for the thermal decomposition of PVC has been developed, in view of its de-chlorination. DTA/TGA testing at different temperatures indicated a first order reaction and an activation energy of 133,800J/mol. An almost completed de-chlorination reaction was obtained at 340°C under an inert atmosphere. The resulted material is a C(n)H(n) type polymer with potential to be used in an energy recovery process. Validation test performed at laboratory scale indicate that the temperature of 340°C enables the removal of ～99.9% of the chlorine present in PVC. The chloride can be fixed in the form of an aqueous solution of HCl or calcium chloride, driving to an alternative full process with environmental benefits and reduction of the costs associated to the PCV - containing materials/wastes management.     

PVC生产行业含汞废物特性分析与处置对策

本文对我国PVC生产行业含汞废物的特性和处理处置技术进行了系统的梳理,明确了现有各类技术的原理、优缺点及适用性,找出了该行业含汞废物处理技术的关键通用性规律。在以上研究基础上,结合含汞废物特性,提出了有针对性的含汞废物综合治理技术。     

Effect of additives on dechlorination of PVC by mechanochemical treatment

Polyvinyl chloride (–CH₂–CHCl–) _n (PVC) was ground with a powdered inorganic material (CaO, CaCO₃, SiO₂, Al₂O₃, or slag) in a planetary ball mill under atmospheric conditions to investigate the effect of additions on its dechlorination. The grinding causes a dehydrochlorinating reaction, forming a mixture of partially dechlorinated PVC and inorganic chloride, depending on the grinding time. The dechlorination increases as the grinding progresses, and is improved with increasing amounts of additives. The most effective additive is a mixture of CaO, SiO₂, and Al₂O₃, which has the same constituent components as blast furnace slag. CaO, a mixture of CaO, SiO₂, and blast furnace slag, are also effective, but CaCO₃ is the least effective additive tired. Received: August 3, 2000 / Accepted: September 21, 2000     

Alkaline hydrolysis of PVC-coated PET fibers for simultaneous recycling of PET and PVC

Journal of Material Cycles and Waste Management - Polyvinyl chloride (PVC)-coated poly(ethylene terephthalate) (PET) woven fibers are one of the hardest-to-recycle polymeric materials. Herein we...     

Effect of Metal Compounds and Experimental Conditions on Distribution of Products from PVC Pyrolysis

Effects of heating rate, gas flow rate, and type of metal compounds on the amount of hydrogen chloride, liquid, gas, and solid pyrolyzate obtained from the pyrolysis of poly(vinyl chloride) (PVC) were investigated. The pyrolysis experiments were carried out in both a thermogravimetric analysis (TGA) instrument and a fixed-bed reactor. Products from the fixed-bed reactor were collected and analyzed by using Fourier transform infrared spectroscopy (FTIR), gas chromatography-mass spectroscopy (GC-MS), titration technique, and gravimetry. It was found that heating rate in the TGA experiments did not affect the amount of released hydrogen chloride. However, the TGA profiles significantly changed with the rate. The onset of dehydrochlorination increased with the rate. In addition, as the heating rate was increased from 10 to 20°C/min, there was no solid residue left. The amount of liquid pyrolyzate obtained from the fixed-bed reactor can be either increased or decreased with the heating rate, depending on the gas flow rate and the actual residence time in the reactor. FTIR and GC-MS analysis indicated that the liquid pyrolyzates were mainly benzene, toluene, and styrene. By comparing the efficiency of various metal compounds in trapping the HCl, it was found that Ca(OH)₂ was more efficient than Mg(OH)₂, and that CaO was more efficient than MgO. These results are discussed in light of the reaction mechanism between HCl and the metal compounds.     

Physical Morphology and Quantitative Characterization of Chemical Changes of Weathered PVC/Pine Composites

This study investigated weathering effects on polyvinyl chloride (PVC) based wood plastic composites (WPC), with a focus on the color and structure that is attributed to the material composition. It is directed towards quantifying the main chemical modifications, such as carbonyl and vinyl groups which are formed during weathering. These composites were subjected to three weathering regimes: exterior, accelerated xenon-arc, and accelerated UVA. The change in color was monitored using colorimetry. Fourier transform infrared spectroscopy was used to identify and quantify the chemical modifications (carbonyl formation and vinyl propagation) due to weathering. Additionally, scanning electron microscopy was employed to observe the physical morphological changes that occurred. The results showed that exterior and accelerated xenon-arc and UVA weathering regimes increased the degree of lightness, total color change, carbonyl concentration, and wood loss on the surfaces of the weathered composites. The increased carbonyl concentration during weathering implied that degradation had occurred by oxidation process. Also, oxidation and lignin (from the wood) degradation influenced the color (lightness) of PVC based WPC upon weathering.     

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.     

聚氯乙烯生产中的废水综台利用

介绍了新疆天业化工园区聚氯乙烯生产中废水的处理技术和综合利用情况,包括乙炔上清液的回收、含汞废液处理及聚合母液水的处理回收利用。利用节水技术,每年可回用水近580万t,氯化氢气体5万t,产生经济效益5380万元。     

The influence of additives on the steam gasification of PVC waste

This study is concerned with the influence of additives on the steam gasification of polyvinyl chloride (PVC) waste. Three types of PVC waste, namely pipe waste, cable waste, and flooring, were tested. The presence of additives proved to have a profound effect on the carbon-to-gas conversion. Plasticizers and other organic additives caused an increase in carbon-to-gas conversion. Inorganic additives, especially calcium, caused a decrease in carbon-to-gas conversion, resulting in an overall decrease in the yield of syngas for all three types of waste. This decrease is probably caused by the deposition of Ca on the surface of the alumina bed material. In addition, calcium reacts with the HCl formed to give CaCl₂. This results in a decrease in the recovery of hydrochloric acid. Received: July 19, 2000 / Accepted: October 9, 2000     

Degradation of PVC Containing Mixtures in the Presence of HCl Fixators

Degradation of a model polymer mixture (PVC/PS/PE) and a waste polymer mixture in the presence of HCl fixators (Red Mud, precipitated CaCO₃ and dolamite) was studied using thermal gravimetric analysis (TGA) and a cycled-spheres-reactor. The experiments in cycled-spheres reactor model were performed by stepwise pyrolysis. Liquid products and HCl from each step were collected separately. For the model polymer mixture, the precipitated CaCO₃ showed the best effect on the fixation of evolved HCl and the reduction of chlorine content in the liquid products whereas RM yielded the best result for the waste polymer mixture. In addition, using HCl fixator also affected the degradation of both types of polymer mixture, leading to the formation of more gaseous and less residue.     

喷淋工艺处理PVC塑料生产废气

采用喷淋工艺处理PVC塑料生产废气,将专利的吸收液与改型的喷淋塔相结合,在中试成功的基础上进行了实际工业化应用。应用结果表明:采用该工艺处理某PVC塑料生产企业的生产废气,吸收液在喷淋塔循环液中所占体积分数为15%时,废气中各污染物指标的去除率达85%以上,对于难处理的苯系物也能较好地去除;处理后废气中各污染物指标的含量满足GB 14554—1993《恶臭污染物排放标准》和DB 44/27—2001《大气污染物排放限值》的要求;该工艺装置运行费用较低,仅为电费和少量药剂费用,吸收液可循环使用,设备保养及维护简单,可满足市场需求。