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.     

Surface ozonation of polyvinyl chloride for its separation from waste plastic mixture by froth floatation

Selective surface modification of polyvinyl chloride (PVC) by ozonation was evaluated to facilitate the separation of PVC from other heavy plastics with almost the same density as PVC, especially polyethylene terephthalate (PET), by the froth flotation process. The optimum froth flotation conditions were investigated, and it was found that at 40°C, 90% of PVC and PET plastics floated. The bubble size became larger and the area covered with bubbles on the plastic surface was reduced with increasing temperature. Optimum PVC separation was achieved with the flotation solution at 40°C and mixing at 180–200 rpm, even for sheet samples 10 mm in size. Combined treatment by ozonation and froth flotation is a simple, effective, and inexpensive method for PVC separation from waste plastics.     

Application of dissolved air flotation on separation of waste plastics ABS and PS

The aim of this research was to separate waste plastics acrylonitrile butadiene styrene (ABS) and polystyrene (PS) by dissolved air flotation in a self-designed dissolved air flotation apparatus. The effects of wetting agents, frother, conditioning time and flotation time on flotation behavior of waste plastics ABS (w-ABS) and PS (w-PS) were investigated and the optimized separation conditions were obtained. The results showed that when using 25 mgL(-1) tannic acid, 5 mgL(-1) terpineol, 15 min conditioning time and 15 min flotation time, mixtures of w-ABS and w-PS were separated successfully by dissolved air flotation in two stages, the results revealed that the purity and recovery rate of w-PS in the floated products were 90.12% and 97.45%, respectively, and the purity and recovery rate of w-ABS in the depressed products were 97.24% and 89.38%, respectively. Based on the studies of wetting mechanism of plastic flotation, it is found that the electrostatic force and hydrophobic attraction cannot be the main factor of the interaction between wetting agent molecules and plastic particles, which can be completed through water molecules as a mesophase, and a hydrogen bonding adsorption model with hydration shell as a mesophase was proposed.     

Combination of three-stage sink-float method and selective flotation technique for separation of mixed post-consumer plastic waste

The aim of this research was to separate the different plastics of a mixed post-consumer plastic waste by the combination of a three-stage sink-float method and selective flotation. By using the three-stage sink-float method, six mixed-plastic wastes, belonging to the 0.3-0.5 cm size class and including high density polyethylene (HDPE), polypropylene (PP), polyvinylchloride (PVC), polystyrene (PS), polyethylene terephthalate (PET) and acrylonitrile-butadiene-styrene copolymers (ABS) were separated into two groups, i.e., a low density plastic group (HDPE and PP) and a high density plastic group (PET, PVC, PS and ABS) by tap water. Plastic whose density is less than that of the medium solution floats to the surface, while the one whose density is greater than that of the medium solution sinks to the bottom. The experimental results elucidated that complete separation of HDPE from PP was achieved by the three-stage sink-float method with 50% v/v ethyl alcohol. To succeed in the separation of a PS/ABS mixture from a PET/PVC mixture by the three-stage sink-float method, a 30% w/v calcium chloride solution was employed. To further separate post-consumer PET/PVC and PS/ABS based on plastic type, selective flotation was carried out. In order to succeed in selective flotation separation, it is necessary to render hydrophilic the surface of one or more species while the others are kept in a hydrophobic state. In flotation studies, the effects of wetting agent, frother, pH of solution and electrolyte on separation were determined. The selective flotation results showed that when using 500 mg l(-1) calcium lignosulfonate, 0.01 ppm MIBC, and 0.1 mg l(-1) CaCl2 at pH 11, PET could be separated from PVC. To separate ABS from PS, 200 mg l(-1) calcium lignosulfonate and 0.1 mg l(-1) CaCl2 at pH 7 were used as a flotation solution. Wettability of plastic increases when adding CaCl2 and corresponds to a decrease in its contact angles and to a reduction in the recovery of plastic in the floated product.     

Separation of packaging plastics by froth flotation in a continuous pilot plant

The objective of the research was to apply froth flotation to separate post-consumer PET (Polyethylene Terephthalate) from other packaging plastics with similar density, in a continuously operated pilot plant. A representative sample composed of 85% PET, 2.5% PVC (Polyvinyl Chloride) and 11.9% PS (Polystyrene) was subjected to a combination of alkaline treatment and surfactant adsorption followed by froth flotation. A mineral processing pilot plant, owned by a Portuguese mining company, was adapted for this purpose. The experimentation showed that it is possible to produce an almost pure concentrate of PET, containing 83% of the PET in feed, in a single bank of mechanical flotation cells. The concentrate grade attained was 97.2% PET, 1.1% PVC and 1.1% PS. By simulation it was shown that the Portuguese recycling industry specifications can be attained if one cleaning and one scavenger stages are added to the circuit.     

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.     

Processing plastics from ASR/ESR waste: separation of poly vinyl chloride (PVC) by froth flotation after microwave-assisted surface modification

The feasibility of the selective surface hydrophilization of poly vinyl chloride (PVC) using microwave treatment to facilitate the separation of PVC via froth flotation from automobile shredder residue (ASR) and electronic waste shredder residue (ESR) was evaluated. In the presence of powder-activated carbon (PAC), 60-s microwave treatment selectively enhanced the hydrophilicity of the PVC surface (i.e., the PVC contact angle decreased from 86.8° to 69.9°). The scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) results are consistent with increased hydrophilic functional groups (i.e., ether, hydroxyl, and carboxyl), amounting to significant changes in the morphology and roughness of the PVC surface after treatment. After only 60 s of microwave treatment, 20 % of the PVC was separated in virgin and ASR/ESR plastics with 33 and 29 % purity, respectively, as settled fractions by froth flotation at a 150 rpm mixing speed. The microwave treatment with the addition of PAC had a synergetic effect with the froth flotation, which brought about 100 and 90 % selective separation of PVC from the other virgin and ASR/ESR plastics, with 91 and 82 % purity. The use of the combined froth flotation and microwave treatments is an effective technology for separating PVC from hazardous waste plastics.     

Deplasticization and dechlorination of flexible polyvinyl chloride in NaOH solution by microwave heating

This study investigated the deplasticization and dechlorination of flexible polyvinyl chloride (PVC) containing 59.2% PVC, 29.7% dioctyl phthalate (DOP), and approximately 12% stabilizers. Flexible PVC was treated with NaOH solutions at concentrations in the range 2–16 mol/l and heated by microwaves to temperatures between 100° and 250°C for 0–120 min. DOP was extracted from flexible PVC into the NaOH solution as a phthalic acid salt; the remaining PVC was subsequently dechlorinated by increasing the temperature. On internal heating using microwaves, the plasticizer was 100% extracted during processing at 150°C for 30 min, whereas the chlorides were 100% removed during processing at 235°C for 30 min; the residue was converted into hydrocarbon compounds. The maximum weight loss ratio was 71% compared to the pretreatment state. It was also found that 100% deplasticization and dechlorination was possible using 8 mol/l NaOH solution, which is almost half the concentration employed when using conventional external heating systems.     

Factors affecting degradation of polyethylene terephthalate (PET) during pre-flotation conditioning

In general, plastics are exposed to different degrading agents in every procedure involved in their recovery from waste mixture and from subsequent recycling. In this study, two methods of pre-flotation conditioning were used to determine how these methods affect the general properties of the pre-conditioned PET particles to be recovered from the PET-PVC mixture. The first method comprised the conditioning of PET samples using an alkaline solution of nonionic surfactant (Triton X-100) based on the patent by the Goodyear Tire and Rubber Company. The second method, developed in this study, was a conditioning process which used an alkali-less solution of the same nonionic surfactant (Triton X-100) used in the first method. The following analytical methods were used to characterize properties of the pre-conditioned PET samples that were correlated to relative degradation of the samples: differential scanning calorimetry (DSC), for thermal behavior of the samples; FT-IR spectroscopy, for functional groups present in the samples; and, Pohl’s method, for carboxyl end-group concentration count. Results show that in addition to water the presence of NaOH in the conditioning solution contributes to the further degradation of the polymer.     

Environmentally Friendly Oil-Modified Polyesters as Polymeric Plasticizers for Poly(vinyl chloride)

Oil-modified polyesters were synthesized to serve as polymeric plasticizers for PVC. A total of four polymeric plasticizers with different average molecular weights were prepared. Characterizations were done using Fourier-transformed infrared spectroscopy, proton nuclear magnetic resonance spectroscopy, and gel permeation chromatography. Some of the tests conducted on PVC films include thermal stability test using thermogravimetric analyser, determination of glass transition temperature (T_g), plasticizer migration and leaching resistance test, morphology study of plasticized PVC films using field emission scanning microscope, toxicity test, and tensile test. Owing to the plasticizing effect of the palm oil-based compound, T_g of the plasticized PVC has decreased to an average of 65 °C at 20 wt% loading. The polymeric plasticizer is also able to contribute positively to the thermal stability and mechanical properties of the PVC films. Some of the advantages of incorporating polymeric plasticizer with high molecular weight includes lower rate of leaching from plastic, and improved tensile strength and elongation at break. Besides, thermal stability of the plastic studied using Kissinger’s and Flynn–Wall–Ozawa’s approaches shows that PVC blended with high molecular weight oil-modified polyester is more thermally stable, evidenced by the increase in the activation energy of decomposition, E_d. Toxicity test using brine shrimp egg shows encouraging results, where the oil-based plasticizer is considerably less toxic compared to some of the commercial plasticizers.     

Solubility parameters for determining optimal solvents for separating PVC from PVC-coated PET fibers

Poly(vinyl chloride) (PVC) in PVC-coated poly(ethylene terephthalate) (PET) fabrics can be separated through dissolution in a suitable solvent, leaving only the PET fibers. We investigated the solubility of PVC in 30 solvents using swelling tests. The results were compared with those obtained using the Hansen, Gutmann, Swain, E _T(30), and Kamlet–Taft parameters. For this purpose, Gaussian plots of the PVC swellability versus solubility parameter were used to decide the applicability of the solubility parameter system. Only Gutmann’s electron acceptor–donor parameter (AN + DN) and the Kamlet–Taft parameters β and π* could describe the PVC-solvent system satisfactorily. Tetrahydrofuran (THF), methyl ethyl ketone (MEK), N,N-dimethylformamide (DMF), cyclohexanone, and cyclopentanone were tested for separating PVC from PET at different temperatures. THF dissolved PVC at 20 °C, while cyclohexanone and cyclopentanone did so at 40 °C. Traces of PVC remained on the PET fibers when DMF was used. Complete dissolution of PVC was not achieved at any temperature with MEK. The present work shows that solubility parameters are a helpful tool for the search for suitable solvents. It shows also that solubility parameters have to be selected carefully, since their usefulness depends strongly on the polymer properties.     

Valorization of post-consumer waste plastic in cementitious concrete composites

The sheer amount of disposable bottles being produced nowadays makes it imperative to identify alternative procedures for recycling them since they are non-biodegradable. This paper describes an innovative use of consumed plastic bottle waste as sand-substitution aggregate within composite materials for building application. Particularly, bottles made of polyethylene terephthalate (PET) have been used as partial and complete substitutes for sand in concrete composites. Various volume fractions of sand varying from 2% to 100% were substituted by the same volume of granulated plastic, and various sizes of PET aggregates were used. The bulk density and mechanical characteristics of the composites produced were evaluated. To study the relationship between mechanical properties and composite microstructure, scanning electron microscopy technique was employed. The results presented show that substituting sand at a level below 50% by volume with granulated PET, whose upper granular limit equals 5mm, affects neither the compressive strength nor the flexural strength of composites. This study demonstrates that plastic bottles shredded into small PET particles may be used successfully as sand-substitution aggregates in cementitious concrete composites. These new composites would appear to offer an attractive low-cost material with consistent properties; moreover, they would help in resolving some of the solid waste problems created by plastics production and in saving energy.     

Floatability of polymer materials modulated by frothers

Flotation tests of 35 polymer materials were carried out to investigate their floatability modulated by frothers. Results of flotation tests demonstrated that polymer resins and soft PVC showed high floatability, floatability of hard PVC plastics was relatively low and was related to the frothers, and there exists significant difference in the floatability of different post-consumer plastics. Flotation rate of post-consumer plastics varies from 0% to 100%. Furthermore, three-category low-energy surface (LES) was defined based on the hydrophile index of the materials involved in this paper, and an adsorption model was proposed to explain the results of flotation and to discuss the floatability of polymer materials modulated by frothers. Frother molecules are prone to adsorb on the surface of bubble rather than LES at relatively low concentration, bubble adsorbed by frother molecules is prone to approach first-category LES rather than third-category LES, and the structure of liquid film is formed on the first-category LES at large concentration. Floatability of polymer materials modulated by frothers is further discussed: frothers increase the floatability of the first-category LES but decrease the floatability of the third-category LES, while the floatability of the second-category LES is related to the type of frothers.     

土壤残留塑料的热降解脱附研究

针对土壤的塑料污染问题,提出一种采用热脱附降解技术修复污染土壤的方法.选取4种土壤中常见的残留塑料(聚乙烯(PE)、聚氯乙烯(PVC)、聚对苯二甲酸乙二酯(PET)、聚丙烯(PP))为研究对象,通过控制热解温度和土壤含水率对各污染土壤的修复效果进行探究.实验结果表明:在500℃的最佳热解温度下处理60 min,PE、P...     

Boiling treatment of ABS and PS plastics for flotation separation

A new physical method, namely boiling treatment, was developed to aid flotation separation of acrylonitrile–butadiene–styrene (ABS) and polystyrene (PS) plastics. Boiling treatment was shown to be effective in producing a hydrophilic surface on ABS plastic. Fourier Transform Infrared analysis was conducted to investigate the mechanism of boiling treatment of ABS. Surface rearrangement of polymer may be responsible for surface change of boiling treated ABS, and the selective influence of boiling treatment on the floatability of boiling treated plastics may be attributed to the difference in the molecular mobility of polymer chains. The effects of flotation time, frother concentration and particle size on flotation behavior of simple plastic were investigated. Based on flotation behavior of simple plastic, flotation separation of boiling treatment ABS and PS with different particle sizes was achieved efficiently. The purity of ABS and PS was up to 99.78% and 95.80%, respectively; the recovery of ABS and PS was up to 95.81% and 99.82%, respectively. Boiling treatment promotes the industrial application of plastics flotation and facilitates plastic recycling.     

Recovery of benzene-rich oil from the degradation of metal- and metal oxide-containing poly(ethylene terephthalate) composites

Pure poly(ethylene terephthalate) (PET) resin and metal-/metal oxide-containing PET composites were thermally decomposed in the presence of Ca(OH)₂ using a tube reactor. The effects of batch and continuous processing, the presence of Ca(OH)₂, and PET size on benzene production were investigated. A maximum benzene yield and purity of 82.9 % and 78.8 wt%, respectively, were obtained at 700 °C in the presence of Ca(OH)₂ when using small PET particles; further, a continuous feed reactor was favored over a batch reactor. Effective contact between PET and Ca(OH)₂ was important in the PET degradation, which promoted hydrolysis of PET and decarboxylation of terephthalic acid, whereas pyrolysis was suppressed. Furthermore, the results of thermal decomposition of PET-based waste—PET-based X-ray films, magnetic tape, and prepaid cards—indicated that the metal and metal oxides contained in the waste had no significant catalytic effect on PET degradation or on the recovery of benzene-rich oil in the presence of Ca(OH)₂.     

Electrostatic separators of particles: Application to plastic/metal, metal/metal and plastic/plastic mixtures

Electrostatic separation is a generic term given to a significant class of technologies of industrial waste processing, widely used for the sorting of granular mixtures due to electric forces acting on particles whose average size is approximately 5mm. The focus of this paper is on three electrostatic processes of separation used for processing of different types of mixtures: (i) role-type electrostatic separator, used to sort mixtures containing metal/plastic particles (copper/PVC for example); (ii) plate-type electrostatic separator, used to sort mixtures containing metal/metal particles (copper/lead for example) and (iii) free-fall electrostatic separator, used to sort mixtures of plastic/plastic particles (PVC/PE for example). Experiments carried out on industrial samples using laboratory electrostatic separators confirm the efficiency of these processes and show that the processes can improve the recovery and purity of products resulting from industrial wastes.     

钙法提钒尾渣的浮选脱硫试验

根据钙法提钒尾渣的矿物特性,采用浮选法分离其中的石膏以实现脱硫,分别考察了矿浆pH、矿浆液固比、捕收剂添加量及浮选中水循环次数等因素对浮选指标的影响,并进行了理论分析,确定了钙法提钒尾渣浮选脱硫的优选工艺参数.试验结果表明,在矿浆pH为7、矿浆液固比为5:1、捕收剂添加量为0.6～0.8 kg/t的条件下,可获得w(S...     

Separation of polycarbonate and acrylonitrile–butadiene–styrene waste plastics by froth flotation combined with ammonia pretreatment

The objective of this research is flotation separation of polycarbonate (PC) and acrylonitrile–butadiene–styrene (ABS) waste plastics combined with ammonia pretreatment. The PC and ABS plastics show similar hydrophobicity, and ammonia treatment changes selectively floatability of PC plastic while ABS is insensitive to ammonia treatment. The contact angle measurement indicates the dropping of flotation recovery of PC is ascribed to a decline of contact angle. X-ray photoelectron spectroscopy demonstrates reactions occur on PC surface, which makes PC surface more hydrophilic. Separation of PC and ABS waste plastics was conducted based on the flotation behavior of single plastic. At different temperatures, PC and ABS mixtures were separated efficiently through froth flotation with ammonia pretreatment for different time (13 min at 23 °C, 18 min at 18 °C and 30 min at 23 °C). For both PC and ABS, the purity and recovery is more than 95.31% and 95.35%, respectively; the purity of PC and ABS is up to 99.72% and 99.23%, respectively. PC and ABS mixtures with different particle sizes were separated effectively, implying that ammonia treatment possesses superior applicability.     

Removal of carbon constituents from hospital solid waste incinerator fly ash by column flotation

Hospital solid waste incinerator (HSWI) fly ash contains a large number of carbon constituents including powder activated carbon and unburned carbon, which are the major source of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in fly ash. Therefore, the removal of carbon constituents could reduce PCDD/Fs in fly ash greatly. In this study, the effects of the main flotation parameters on the removal of carbon constituents were investigated, and the characteristics of the final product were evaluated. The results showed that loss on ignition (LOI) of fly ash increased from 11.1% to 31.6% during conditioning process. By optimizing the flotation parameters at slurry concentration 0.05 kg/l, kerosene dosage 12 kg/t, frother dosage 3 kg/t and air flow rate 0.06 m³/h, 92.7% of the carbon constituents were removed from the raw fly ash. Under these conditions, the froth product has LOI of 56.35% and calorific values of 12.5 MJ/kg, LOI in the tailings was below 5%, and the total toxic equivalent (TEQ) of PCDD/Fs decreased from 5.61 ng-TEQ/g in the raw fly ash to 1.47 ng-TEQ/g in the tailings. The results show that column flotation is a potential technology for simultaneous separation of carbon constituents and PCDD/Fs from HSWI fly ash.