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.     

Characterization of char derived from various types of solid wastes from the standpoint of fuel recovery and pretreatment before landfilling

Carbonization is a kind of pyrolysis process to produce char from organic materials under an inert atmosphere. In this work, chars derived from various solid wastes were characterized from the standpoint of fuel recovery and pretreatment of waste before landfilling. Sixteen kinds of municipal and industrial solid wastes such as residential combustible wastes, non-combustible wastes, bulky wastes, construction and demolition wastes, auto shredder residue, and sludges were carbonized at 500 degrees C for 1h under nitrogen atmosphere. In order to evaluate the quality of char as fuel, proximate analysis and heating value were examined. The composition of raw waste had a significant influence on the quality of produced char. The higher the ratio of woody biomass in waste, the higher heating value of char produced. Moreover, an equation to estimate heating value of char was developed by using the weight fraction of fixed carbon and volatile matter in char. De-ashing and chlorine removal were performed to improve the quality of char. The pulverization and sieving method seems to be effective for separation of incombustibles such as metal rather than ash. Most char met a 0.5 wt% chlorine criterion for utilization as fuel in a shaft blast furnace after it was subjected to repeated water-washing. Carbonization could remove a considerable amount of organic matter from raw waste. In addition, the leaching of heavy metals such as chrome, cadmium, and lead appears to be significantly suppressed by carbonization regardless of the type of raw waste. From these results, carbonization could be considered as a pretreatment method for waste before landfilling, as well as for fuel recovery.     

Diopside-based glass-ceramics from MSW fly ash and bottom ash

By utilising MSW fly ash from the Shanghai Yuqiao municipal solid waste (MSW) incineration plant as the main raw material, diopside-based glass-ceramics were successfully synthesized in the laboratory by combining SiO(2), MgO and Al(2)O(3) or bottom ash as conditioner of the chemical compositions and TiO(2) as the nucleation agent. The optimum procedure for the glass-ceramics is as follows: melting at 1500 degrees C for 30 min, nucleating at 730 degrees C for 90 min, and crystallization at 880 degrees C for 10h. It has been shown that the diopside-based glass-ceramics made from MSW fly ash have a strong fixing capacity for heavy metals such as lead (Pb), chromium (Cr), cadmium (Cd) etc.     

Recovery of solid fuel from municipal solid waste by hydrothermal treatment using subcritical water

Hydrothermal treatments using subcritical water (HTSW) such as that at 234 °C and 3 MPa (LT condition) and 295 °C and 8 MPa (HT condition) were investigated to recover solid fuel from municipal solid waste (MSW). Printing paper, dog food (DF), wooden chopsticks, and mixed plastic film and sheets of polyethylene, polypropylene, and polystyrene were prepared as model MSW components, in which polyvinylchloride (PVC) powder and sodium chloride were used to simulate Cl sources.While more than 75% of carbon in paper, DF, and wood was recovered as char under both LT and HT conditions, plastics did not degrade under either LT or HT conditions. The heating value (HV) of obtained char was 13,886-27,544 kJ/kg and was comparable to that of brown coal and lignite. Higher formation of fixed carbon and greater oxygen dissociation during HTSW were thought to improve the HV of char.Cl atoms added as PVC powder and sodium chloride to raw material remained in char after HTSW. However, most Cl originating from PVC was found to converse into soluble Cl compounds during HTSW under the HT condition and could be removed by washing.From these results, the merit of HTSW as a method of recovering solid fuel from MSW is considered to produce char with minimal carbon loss without a drying process prior to HTSW. In addition, Cl originating from PVC decomposes into soluble Cl compound under the HT condition. The combination of HTSW under the HT condition and char washing might improve the quality of char as alternative fuel.     

Experimental and kinetic modeling of oxygen-enriched air combustion of municipal solid waste

The characteristics of oxygen-enriched air combustion of raw municipal solid waste (MSW) were studied by thermogravimetric analysis. Experiments on oxidative pyrolysis of MSW were carried out under different atmospheres (N(2), N(2):O(2)=7:3, N(2):O(2)=5:5, N(2):O(2)=4:6, and N(2):O(2)=2:8) at 30 degrees C/min. Two distinct peaks of weight loss were obtained according to the derivative thermogravimetric curves; one of them is centered on 305 degrees C with about 40% weight loss, and the second is centered on 420 degrees C with about 20% weight loss. Effects of oxygen concentration on the decomposition process and char combustion were analyzed, and then the process of oxygen-enriched air combustion of MSW was divided into four steps. Kinetic parameters were observed by direct non-linear regressions. According to the obtained data, the apparent activation energy and reaction order decreases along with the combustion process, while that of char combustion increases as oxygen concentration increases.     

Effects of the type of sintering atmosphere on the chromium leachability of thermal-treated municipal solid waste incinerator fly ash

The sintering process offers an opportunity to combine detoxification and resource recovery for the treatment of municipal solid waste (MSW) incinerator fly ash. However, the chromium (Cr) in the sintered fly ash becomes more readily leachable with increasing sintering time and temperature, thus posing severe threats to the environment and human health when the sintered ash is recycled or reused. This study investigated the enhanced leachability of fly ash containing Cr, by heating the chromium (III) oxide (Cr2O3)-spiked fly ash to 800 degrees C in atmospheres containing air, nitrogen gas (N2), and 5% H2 + 95% N2, respectively. The results indicated that trivalent chromium was converted to its soluble hexavalent form during sintering in the air atmosphere; whereas sintering in a nitrogen atmosphere significantly reduced the leachability of Cr due to lack of oxygen (O2) to oxidize. The effects of the sintering temperature on the total chromium content and the leaching concentration in the toxicity characteristic leaching procedure (TCLP) extract are also discussed.     

Auto shredder residue recycling: Mechanical separation and pyrolysis

Directive 2000/53/EC sets a goal of 85% material recycling from end-of-life vehicles (ELVs) by the end of 2015. The current ELV recycling rate is around 80%, while the remaining waste is called automotive shredder residue (ASR), or car fluff. In Europe, this is mainly landfilled because it is extremely heterogeneous and often polluted with car fluids. Despite technical difficulties, in the coming years it will be necessary to recover materials from car fluff in order to meet the ELV Directive requirement. This study deals with ASR pretreatment and pyrolysis, and aims to determine whether the ELV material recycling target may be achieved by car fluff mechanical separation followed by pyrolysis with a bench scale reactor. Results show that flotation followed by pyrolysis of the light, organic fraction may be a suitable ASR recycling technique if the oil can be further refined and used as a chemical. Moreover, metals are liberated during thermal cracking and can be easily separated from the pyrolysis char, amounting to roughly 5% in mass. Lastly, pyrolysis can be a good starting point from a "waste-to-chemicals" perspective, but further research should be done with a focus on oil and gas refining, in order both to make products suitable for the chemical industry and to render the whole recycling process economically feasible.     

Analyses of incinerated ash of paper sludge: comparison with incinerated ash of municipal solid waste

Fourteen paper sludge samples were collected at seven representative pulp and paper mills in Japan, and were analyzed to obtain fundamental data on the reuse of paper sludge-incinerated ash as papermaking material. For comparison, incinerated ashes of municipal solid waste (MSW) were collected at MSW incineration plants in Tokyo, and analyzed by similar methods. Elementary and X-ray diffraction analyses revealed that the predominant elements in paper sludge samples are calcium, silicon, aluminum, and magnesium, which are derived from paper fillers, coating pigments, and coagulants used in papermaking and process effluent treatments. Similar results were also obtained for the MSW-incinerated ashes, indicating that major components in the collected MSW are paper-related materials. Incineration of paper sludge around 800°C is recommended in terms of high brightness of the incinerated ash, which has about 60% brightness. Calcium, silicon, and aluminum components in the paper sludge are fused or sintered by heating. Although paper-sludge-incinerated ashes have irregular shape and large particle size distributions, they may be used as papermaking materials after pulverization using a ball mill. The MSW-incinerated ashes have 5%–30% water-soluble fractions and low brightness, and thus incineration conditions must be changed to reuse the MSW-incinerated ash as a papermaking material.Part of this paper was presented at the 68th Research Conference of Japan Tappi, Tokyo, 2001     

Prediction of syngas quality for two-stage gasification of selected waste feedstocks

This paper compares the syngas produced from methane with the syngas obtained from the gasification, in a two-stage reactor, of various waste feedstocks. The syngas composition and the gasification conditions were simulated using a simple thermodynamic model. The waste feedstocks considered are: landfill gas, waste oil, municipal solid waste (MSW) typical of a low-income country, the same MSW blended with landfill gas, refuse derived fuel (RDF) made from the same MSW, the same RDF blended with waste oil and a MSW typical of a high-income country. Energy content, the sum of H2 and CO gas percentages, and the ratio of H2 to CO are considered as measures of syngas quality. The simulation shows that landfill gas gives the best results in terms of both H2+CO and H2/CO, and that the MSW of low-income countries can be expected to provide inferior syngas on all three quality measures. Co-gasification of the MSW from low-income countries with landfill gas, and the mixture of waste oil with RDF from low-income MSW are considered as options to improve gas quality.     

Water-soluble characteristics of chlorine in char derived from municipal solid wastes

Chlorine in char derived from municipal solid waste (MSW) was characterized and quantified based on its water solubility: easily water-soluble, hardly water-soluble, and non-water-soluble chlorine. For that, a four-cycle process of water-washing, heating or carbonation were carried out. In order to confirm the characteristics of non-water-soluble chlorine, additional thermal treatment and an alkali-acid washing process were applied to washed char. It was found that a large particle size of char (0.5-1.0 mm) significantly contributed to the amount of non-water-soluble chlorine. Pulverization and HNO3-HF digestion were performed to identify a factor to interfere chlorine release from char with a large particle size. Pulverization was proven ineffective for release of non-water-soluble chlorine, whereas approximately 32% of non-water-soluble chlorine was extracted by HNO3-HF digestion. Therefore, the presence of non-water-soluble chlorine is likely to originate from its chemical property rather than simply from its physical one.     

Removal of unburned carbon from municipal solid waste fly ash by column flotation

Unburned carbon (UC) is the major source of organic contaminants in municipal solid waste (MSW) fly ash. So most organic contaminants can be removed by the removal of the UC from the MSW fly ash. In this paper, we first used a technique of column flotation to remove UC from MSW fly ash. The influences of column flotation parameters on the recovery efficiency of UC were systematically studied. It was found that the UC recovery efficiency was greatly influenced by the gas flow rate, pH value, collector kerosene's concentration and the types of fly ash. By optimizing the above parameters, we have successfully removed 61.2% of the UC from MSW fly ash having 5.24% UC content. The removal mechanism was well accounted for the kinetic theory of column flotation and surface-chemistry theory. The results indicate that the column flotation technique is effective in removing the UC from MSW fly ash, and show that there is a strong possibility for practical application of this technique in removing the organic contaminants from MSW fly ash.     

Combustion studies of high moisture content waste in a fluidised bed

The combustion of three high moisture content waste materials in a fluidised bed combustor has been investigated and a comparison with co-firing of these materials with coal in the same combustor has been made. Waste materials burnt were olive oil waste, municipal solid waste and potato, which is representative of vegetable waste. Mixtures of up to 20% mass concentration water in the waste were fed to the combustor. Above that value the moisture content was too high to sustain combustion without addition of coal. Measurements of CO, NOx, SO2 temperatures were made and the carbon combustion efficiency evaluated. Co-firing with coal resulted in markedly higher combustion efficiencies with an increase of approximately 10-80% when burning the simulated MSW. However, this was much lower than the value of 93% when coal was burnt on its own. It was also much lower than the value obtained, average 90%, when co-firing potato and olive oil waste with coal and there was little difference in the combustion efficiency between the two types of waste and with increasing moisture content. It was concluded that the high ash content of the simulated MSW 26%, compared with 5% in the other two waste materials resulted in slower burning and consequently the char particles were elutriated from the bed without being fully burnt. In term of gaseous emissions during co-combustion, CO emission is relatively insensitive to change in waste fraction. While emission of SO2 can be reduced as the waste fraction increases as a result of fuel-S dilution. But in terms of percent fuel-S converted, it is actually increased by increasing waste fraction. Emissions of NO and N2O increase slightly with MSW fraction.     

Vacuum pyrolysis of waste tires with basic additives

Granules of waste tires were pyrolyzed under vacuum (3.5-10kPa) conditions, and the effects of temperature and basic additives (Na(2)CO(3), NaOH) on the properties of pyrolysis were thoroughly investigated. It was obvious that with or without basic additives, pyrolysis oil yield increased gradually to a maximum and subsequently decreased with a temperature increase from 450 degrees C to 600 degrees C, irrespective of the addition of basic additives to the reactor. The addition of NaOH facilitated pyrolysis dramatically, as a maximal pyrolysis oil yield of about 48wt% was achieved at 550 degrees C without the addition of basic additives, while a maximal pyrolysis oil yield of about 50wt% was achieved at 480 degrees C by adding 3wt% (w/w, powder/waste tire granules) of NaOH powder. The composition analysis of pyrolytic naphtha (i.b.p. (initial boiling point) approximately 205 degrees C) distilled from pyrolysis oil showed that more dl-limonene was obtained with basic additives and the maximal content of dl-limonene in pyrolysis oil was 12.39wt%, which is a valuable and widely-used fine chemical. However, no improvement in pyrolysis was observed with Na(2)CO(3) addition. Pyrolysis gas was mainly composed of H(2), CO, CH(4), CO(2), C(2)H(4) and C(2)H(6). Pyrolytic char had a surface area comparable to commercial carbon black, but its proportion of ash (above 11.5wt%) was much higher.     

Moisture retention of municipal solid waste mixed with sewage sludge and ash in a semi-arid climate.

Mechanisms involved in moisture storage in refuse are explored using data from four sets of experiments in a semi-arid climate. Two laboratory series of experiments contained municipal solid waste (MSW) amended with sewage sludge, one with higher proportions of ash in the MSW than the other. Outdoor experiments contained waste streams with different proportions of ash. Field cells compared moisture retention of refuse and MSW co-disposed with sewage sludge. Sewage sludge at high loads was found to increase the moisture storage relative to unamended MSW. Belt-pressed sludge retained water as bound water that was released by decay and changing pH. Sun-dried sludge also retained more moisture than MSW alone. In gravimetric terms, ash reduced the storage potential of MSW, in laboratory and outdoor experiments. However, outdoor experiments released less leachate from ash-rich refuse than middle-income waste with no ash fraction.     

Flow analysis of metals in a municipal solid waste management system

This study aimed to identify the metal flow in a municipal solid waste (MSW) management system. Outputs of a resource recovery facility, refuse derived fuel (RDF) production facility, carbonization facility, plastics liquefaction facility, composting facility, and bio-gasification facility were analyzed for metal content and leaching concentration. In terms of metal content, bulky and incombustible waste had the highest values. Char from a carbonization facility, which treats household waste, had a higher metal content than MSW incinerator bottom ash. A leaching test revealed that Cd and Pb in char and Pb in RDF production residue exceeded the Japanese regulatory criteria for landfilling, so special attention should be paid to final disposal of these substances. By multiplying metal content and the generation rate of outputs, the metal content of input waste to each facility was estimated. For most metals except Cr, the total contribution ratio of paper/textile/plastics, bulky waste, and incombustible waste was over 80%. Approximately 30% of Cr originated from plastic packaging. Finally, several MSW management scenarios showed that most metals are transferred to landfills and the leaching potential of metals to the environment is quite small.     

Physical-mechanical and environmental properties of sintered municipal incinerator fly ash

A step-wise treatment of Municipal Solid Waste (MSW) incinerator fly ash including washing, milling and sintering was investigated in order to manufacture ceramic materials with improved physical, mechanical and environmental properties and, possibly, to reduce the power input of the sintering process. An interpretation of the test results based on the microstructure of sintered products and sintering kinetic modeling was also attempted to identify the densification mechanisms. It was found that milling of washed fly ash represents a basic step for manufacturing high-density ceramic materials with very high compressive strengths (up to 500 N/mm2). A significant reduction in the power input of the sintering process (reduction of firing temperature from 1210 degrees C for washed fly ash to 1140 degrees C for milled-washed fly ash) is also achieved. A dense, well-sintered microstructure is formed through an intermediate-stage, liquid-phase sintering mechanism controlled by liquid-phase diffusion and grain shape accommodation. Such a microstructure is able to strongly immobilise heavy metals, thus giving good environmental properties to sintered product.     

On the ASR and ASR thermal residues characterization of full scale treatment plant

In order to obtain 85% recycling, several procedures on Automotive Shredder Residue (ASR) could be implemented, such as advanced metal and polymer recovery, mechanical recycling, pyrolysis, the direct use of ASR in the cement industry, and/or the direct use of ASR as a secondary raw material. However, many of these recovery options appear to be limited, due to the possible low acceptability of ASR based products on the market. The recovery of bottom ash and slag after an ASR thermal treatment is an option that is not usually considered in most countries (e.g. Italy) due to the excessive amount of contaminants, especially metals. The purpose of this paper is to provide information on the characteristics of ASR and its full-scale incineration residues. Experiments have been carried out, in two different experimental campaigns, in a full-scale tyre incineration plant specifically modified to treat ASR waste.Detailed analysis of ASR samples and combustion residues were carried out and compared with literature data. On the basis of the analytical results, the slag and bottom ash from the combustion process have been classified as non-hazardous wastes, according to the EU waste acceptance criteria (WAC), and therefore after further tests could be used in future in the construction industry. It has also been concluded that ASR bottom ash (EWC – European Waste Catalogue – code 19 01 12) could be landfilled in SNRHW (stabilized non-reactive hazardous waste) cells or used as raw material for road construction, with or without further treatment for the removal of heavy metals. In the case of fly ash from boiler or Air Pollution Control (APC) residues, it has been found that the Cd, Pb and Zn concentrations exceeded regulatory leaching test limits therefore their removal, or a stabilization process, would be essential prior to landfilling the use of these residues as construction material.     

Leachability of municipal solid waste ashes in simulated landfill conditions

In Japan the volume of municipal solid waste is reduced by incineration, with fly ash and bottom ash disposed in controlled landfills. The leachability of anions and heavy metal cations, Zn, Cu and Pb, from MSW fly ash and bottom ash at different pHs was examined using batch- and column-leaching tests. The MSW ashes had a high capacity for neutralizing acids. Behaviour during leaching depended on the pH of the solution. For the volumes applied, the leachabilities of MSW fly ash were very similar at pHs from 3 to 6. Due to its amphoteric nature, Pb is leachable at pHs of approximately 10 or more, with leachate concentrations of about 3 and 3-10mg/L for the fly ash and bottom ash, respectively, much higher than for Zn and Cu. Pb concentrations for most leaching solutions were 1 and 3mg/L for the fly ash and bottom ash, respectively. Zn, and Cu leached at low concentrations for solutions of pH 3-6. Na and K ions leached at high concentrations of approximately 5000 mg/L in the first batch leaching test, decreasing to 10mg/L by the fourth leach. Ca and Mg ions leached more gradually than Na and K. Cl(-) and SO(4)(2+) ions were the major anions in the MSW ash. The high pH and cation leaching are expected to have negative impacts on the performance of clay liners.     

Predicting the heating value of MSW with a feed forward neural network

The influence of the heating value of municipal solid waste (MSW) is very important on the combustion efficiency of MSW incinerators. The heating value of MSW is determined by the elementary chemical composition of its various components. Commonly, calorimetric measurement and empirical methods are available for this determination. In this analysis, the relationship between the physical composition and the low heating value (LHV) was studied. A feed forward neural network (FFNN) can be very helpful in predicting the heating value of MSW from its physical composition. The results of this analysis show that the prediction of LHV of MSW with FFNN is much better than conventional models.     

Investigation of MSWI fly ash melting characteristic by DSC-DTA

The melting process of MSWI (Municipal Solid Waste Incineration) fly ash has been studied by high-temperature DSC-DTA experiments. The experiments were performed at a temperature range of 20-1450 degrees C, and the considerable variables included atmosphere (O(2) and N(2)), heating rates (5 degrees C/min, 10 degrees C/min, 20 degrees C/min) and CaO addition. Three main transitions were observed during the melting process of fly ash: dehydration, polymorphic transition and fusion, occurring in the temperature range of 100-200 degrees C, 480-670 degrees C and 1101-1244 degrees C, respectively. The apparent heat capacity and heat requirement for melting of MSWI fly ash were obtained by DSC (Differential Scanning Calorimeter). A thermodynamic modeling to predict the heat requirements for melting process has been presented, and it agrees well with the experimental data. Finally, a zero-order kinetic model of fly ash melting transition was established. The apparent activation energy of MSWI fly ash melting transition was obtained.