Toward maximizing the recycling rate in a Sapporo waste plastics liquefaction plant

Sapporo Plastics Recycling Co., Ltd., (SPR) started its commercial operation of waste plastics liquefaction in 2000. At first only hydrocarbon oil was reclaimed, this being derived from the waste plastics liquefaction process under the Japanese Containers and Packaging Recycling Law. Presently, thermal degradation residue and hydrochloric acid are being produced as by-products in addition to the hydrocarbon oil. As a result, the SPR plastics liquefaction plant has achieved a high reclamation rate of 96%, and 93% of the recycled products have been reused in Hokkaido, where SPR is located. The technical problems caused by corrosion and clogging have been solved. Chemical Feedstock Recycling & Other Innovative Recycling Techniques 6     

Pyrolysis of plastic packaging waste: A comparison of plastic residuals from material recovery facilities with simulated plastic waste

Pyrolysis may be an alternative for the reclamation of rejected streams of waste from sorting plants where packing and packaging plastic waste is separated and classified. These rejected streams consist of many different materials (e.g., polyethylene (PE), polypropylene (PP), polystyrene (PS), polyvinyl chloride (PVC), polyethylene terephthalate (PET), acrylonitrile butadiene styrene (ABS), aluminum, tetra-brik, and film) for which an attempt at complete separation is not technically possible or economically viable, and they are typically sent to landfills or incinerators. For this study, a simulated plastic mixture and a real waste sample from a sorting plant were pyrolyzed using a non-stirred semi-batch reactor. Red mud, a byproduct of the aluminum industry, was used as a catalyst. Despite the fact that the samples had a similar volume of material, there were noteworthy differences in the pyrolysis yields. The real waste sample resulted, after pyrolysis, in higher gas and solid yields and consequently produced less liquid. There were also significant differences noted in the compositions of the compared pyrolysis products.     

Development of a catalytic dehalogenation (Cl,Br) process for municipal waste plastic-derived oil

Dehalogenation is a key technology in the feedstock recycling of mixed halogenated waste plastics. In this study, two different methods were used to clarify the effectiveness of our proposed catalytic dehalogenation process using various carbon composites of iron oxides and calcium carbonate as the catalyst/sorbent. The first approach (a two-step process) was to develop a process for the thermal degradation of mixed halogenated waste plastics, and also develop dehalogenation catalysts for the catalytic dehydrochlorination of organic chlorine compounds from mixed plastic-derived oil containing polyvinyl chloride (PVC) using a fixed-bed flow-type reactor. The second approach (a single-step process) was the simultaneous degradation and dehalogenation of chlorinated (PVC) and brominated (plastic containing brominated flame retardant, HIPS–Br) mixed plastics into halogen-free liquid products. We report on a catalytic dehalogenation process for the chlorinated and brominated organic compounds formed by the pyrolysis of PVC and brominated flame retardant (HIPS–Br) mixed waste plastics [(polyethylene (PE), polypropylene (PP), and polystyrene (PS)], and also other plastics. During dehydrohalogenation, the iron- and calcium-based catalysts were transformed into their corresponding halides, which are also very active in the dehydrohalogenation of organic halogenated compounds. The halogen-free plastic-derived oil (PDO) can be used as a fuel oil or feedstock in refineries.     

Noncatalytic liquefaction of tar with low-temperature hydrothermal treatment

Water at hydrothermal and supercritical conditions is considered a promising solvent for the degradation of hazardous waste into harmless compounds. Tar liquefaction experiments were conducted using a batch-type reactor at temperatures between 623 K and 673 K and at pressures between 25 and 40 MPa. A reaction mechanism for tar liquefaction is proposed. Moreover, on the basis of the experimental results, this method could become an efficient method for tar liquefaction, producing high yields of valuable chemical intermediates.     

Hydrothermal treatment and characterization of model food garbage,focusing on the effect of additional foreign matter on internal temperature,pressure and products

Hydrothermal treatment of model food garbage focusing on the effects of additional foreign matter has been performed in subcritical conditions as a pretreatment for the next step, i.e., the bio-processing and production of liquid feed or fertilizer. Using the hydrothermal technique, we studied the temporal change in internal temperature and pressure in a reactor on the elapsed heating time to check the equipment safety in terms of temperature and pressure. The gaseous and water-soluble liquid was also characterized to investigate the feasibility of retrieving valuable chemicals and emitting environmentally hazardous substances. From the changes in the internal temperature and pressure curve, the maximum temperature and pressure were 196 °C and 1.42 MPa for 30-min elapsed heating time, which was below the predefined temperature limits of 200 °C and pressure of 1.55 MPa. No such irregular behavior was observed in the temperature and pressure curve except that it was a little different for the foreign matter detergent, which also was within the limits. The qualitative and quantitative analysis of end products showed that the emitted malodorous substances and chemicals were further below the threshold levels for Japan.     

废塑料催化裂解制燃料油

用自制的L不列催化剂对聚乙烯，聚丙烯，聚苯乙烯及其按不同比例混合的3种废塑料催化裂解制燃料油进行了研究。试验结果表明：混合废塑料料经过催化解制得的90^#汽油和0^#柴油的质量均达到国家标准。油品品质的好坏主要由废塑料的种类，催化剂和催化改质温度3个因素决定。     

Effect of aerobic pretreatment of waste on the rate of anaerobic treatment processes

The efficiency of waste degradation can be expressed by the rate of waste decomposition in individual phases. This article presents the durations of degradation phases of pretreated and untreated waste stabilized in anaerobic laboratory reactors. In this investigation, the quantities of organic and nitrogen contaminants emitted from the waste during the study are presented. The study confirmed the beneficial effects of aerobic pretreatment of waste before landfilling on reducing the duration of hydrolysis and acid phases, and speeding up the start of the stable methane phase. In the pretreated waste reactor, the stable methane phase began about 19 weeks earlier than in the untreated waste. The total amounts of contaminants removed from the aerobic pretreatment waste were lower than from untreated waste, with values of COD, TOC, BOD₅, and VFA corresponding to 21, 18, 6, and 23 %, respectively, and values of TKN and NH₄ of 7 and 50 %, respectively.     

Characteristics of liquid product from the pyrolysis of waste plastic mixture at low and high temperatures: influence of lapse time of reaction

Pyrolysis of a waste plastic mixture (high-density polyethylene: low-density polyethylene: polypropylene: polystyrene = 3:2:3:1) into a liquid product was carried out in a stirred semi-batch reactor at low (350 degrees C) and high (400 degrees C) temperatures. The effect of lapse time of reaction in the reactor and also degradation temperature on the characteristics of the liquid product from pyrolysis of the mixture was investigated. Liquid products were described by cumulative amount distribution, paraffin, olefin, naphthene and aromatic (PONA) distribution and molecular weight distribution. Their characteristic was quite differed with a lapse time of reaction and also at a low and high degradation temperatures, because of the different physicochemical properties of the plastic types in the mixture. With increase of lapse time of reaction, the order for the main products in PONA components obtained at 350 degrees C was firstly aromatic products and then olefin products, while at 400 degrees C the order was firstly aromatic products, then olefin products and finally paraffin products. The experiments also showed from the molecular weight distribution of liquid PONA components that the paraffin and olefin products had a wide distribution by mainly random scission of polymer, but in the case of olefin products were produced by an end-chain scission mechanism as well as random scission mechanism, as evidenced by much more light olefin products. This phenomenon was evident at a higher degradation temperature. Also, both the light olefin and naphthene products with a molecular weight of around 120, as a main product, showed a similar trend as a function of lapse time, which had a maximum fraction at 343 min (at 350 degrees C) and 83 min (at 400 degrees C). Among PONA components, the highest concentrations of aromatic products were obtained with a molecular weight of around 100 at the fastest lapse time of reaction, regardless of degradation temperature. It was concluded that the characteristics of liquid product on the pyrolysis of plastic mixtures were strongly influenced by lapse time of reaction and degradation temperature.     

Effect of heating rate on the pyrolysis of high-impact polystyrene containing brominated flame retardants: fate of brominated flame retardants

In the case of plastics containing brominated flame retardants, various brominated organic compounds, including polybrominated dibenzodioxins and dibenzofurans, are yielded when they are degraded. In order to reduce the hazard that might be generated during after-live treatment, the behaviour of flame retarded high-impact polystyrene containing decabromo diphenylether and antimony oxide (Sb₂O₃), was investigated using several heating programs. It was found that the separation of the thermal process into two steps divided at 330?°C makes it possible to obtain an oil fraction rich in brominated compounds at low temperatures and an oil fraction depleted in brominated compounds at high temperatures. The low temperature oil contained a high concentration of SbBr₃ and dibromodibenzofurans. Various brominated compounds with a low volatility and 1-bromo-1-phenylethane from the reaction of HBr with styrene were among the substances in the high temperature oil. The concentration of brominated compounds was reduced from 6?wt% for degradation in a single step to below 1?wt% in the high temperature oil in the two step process.     

Two-stage thermal gasification of polyolefins

Plastic pellets of polyethylene (PE), polypropylene (PP), and polystyrene (PS) were gasified in a two-stage thermal degradation process. The first stage is the conversion of polyolefins to distilled oils using a melting vessel. In the second stage, the oils from the first stage are gasified using a tubular reactor. The distilled oil yields of PE, PP, and PS in the first stage were 84, 89, 92 wt%, respectively, each at 470°C. The total gas yields of PE, PP, and PS in the second stage were 80, 74, and 6.2 wt%, respectively, each at 800°C. The main components of the product gas for PE and PP were methane and olefins such as ethene and propene. Some aromatic oils, including benzene, toluene, and xylene, were also produced as by-products. The amount of carbonaceous residue, or coke, was very low (less than 1 wt%). By dividing the process into two stages, the coking rate was considerably reduced compared with direct gasification of the polyolefins. Received: July 19, 2000 / Accepted: September 17, 2000     

In-situ emission characteristics of odorous gases from two food waste processing plants

Odorous gas emission is the main environmental concern of food waste treatment. Two typical food waste processing plants, one for animal feed production by hydrothermal hydrolysis + aerobic fermentation (Plant A), and the other for biogas production by anaerobic digestion (Plant B), were selected to conduct in situ monitoring of fugitive odorous gas emission for five consecutive days, and the emission characteristics of NH₃ and total volatile organic compounds (TVOC) were compared in this paper. The results showed that the two processes had different emission characteristics of odorous gases. Closed-operated hydrothermal hydrolysis had positive effects on overall fugitive odor control in plant A. Meanwhile, more fugitive odor gases may be released into the environment during the pretreatment with high-temperature and seemingly-open facilities in plant B. The emission strength of odor gases at night was generally lower than that in the day since more fresh food waste was received in the day and the higher temperature and lower air pressure in the day were favorable to gas emission. In general, the process of hydrothermal hydrolysis + aerobic fermentation was more advantageous in controlling odor than the process of anaerobic digestion.     

Study on the conversion of waste plastics/petroleum resid mixtures to transportation fuels

Catalytic coprocessing of model and waste plastics with light Arabian crude oil residue was investigated using NiMo/Al₂O₃, ZSM-5, FCC, and hydrocracking catalysts. Reaction systems that were studied included low density polyethylene (LDPE), high density polyethylene (HDPE), polystyrene (PS), and polypropylene (PP). A series of single (plastic/catalyst) and binary (plastic/resid/catalyst) reactions were carried out in a 25-cm³ micro autoclave reactor under different conditions of weight and type of catalyst, duration, pressure, and temperature. The optimum conditions selected for our work were: 1% catalyst by weight of total feedstock weight, 60min reaction time, 8.3Mpa of H₂, and 430°C. The product distribution for the binary system using plastic and petroleum residue provided some encouraging results. High yields of liquid fuels in the boiling range of 100°–480°C and gases were obtained along with a small amount of heavy oils and insoluble material such as gums and coke. In general, this study helps to demonstrate the technical feasibility of upgrading both waste plastics and petroleum resid, as well as an alternative approach to feedstock recycling.     

Chemical recycling of polycarbonate in dilute aqueous ammonia solution under hydrothermal conditions

Polycarbonate (PC) pellets were subjected to dilute aqueous ammonia solution under hydrothermal conditions in a semi-batch reactor at temperatures ranging from 433 to 463 K and at a pressure of 10 MPa. The PC pellets were almost completely converted to bisphenol A (BPA). During an initial certain period, referred to as an induction time, neither BPA nor total organic carbon in solution were detected, and the BPA yield increased with time. The monomer yield was well represented by a surface reaction model, two-thirds-order reaction with respect to the mass of unreacted PC. The overall rate constant of the reaction in 0.6 mol/kg aqueous ammonia solution at 433 K was about 15 times greater than that in 0.6 mol/kg NaOH solution. The rate constant at 433 K was proportional to the ammonia or NaOH concentration. There was a correlation between the induction time and temperature, as well as the ammonia or NaOH concentration. By carrying out the reaction in aqueous mixtures of (NH₄)₂SO₄ and NaOH at various concentrations of NaOH, ammonia was confirmed not to function as an alkaline reagent, but as a nucleophile reagent.     

Production of hydrogen by steam gasification of dehydrochlorinated poly(vinyl chloride) or activated carbon in the presence of various alkali compounds

Steam gasification of dehydrochlorinated poly(vinyl chloride) (PVC) or activated carbon was carried out in the presence of various alkali compounds at 3.0 MPa and 560°C–660°C in a batch reactor or in a semi-batch reactor with a flow of nitrogen and steam. Hydrogen and sodium carbonate were the main products, and methane and carbon dioxide were the minor products. Yields of hydrogen were high in the presence of sodium hydroxide and potassium hydroxide. The acceleration effect of the alkali compounds on the gasification reaction was as follows: KOH > NaOH > Ca(OH)₂ > Na₂CO₃. The rate of gasification increased with increasing partial steam pressure and NaOH/C molar ratio. However, the rate became saturated at a molar ratio of NaOH/C greater than 2.0.     

Dechlorination and decomposition of Aroclor 1242 in real waste transformer oil using a nucleophilic material with a modified domestic microwave oven

This research was done to assess the dechlorination and decomposition of polychlorinated biphenyls (PCBs) in real waste transformer oil through a modified domestic microwave oven (MDMW). The influence of microwave power (200–1000 W), reaction time (30–600 s), polyethylene glycol (PEG) (1.5–7.5 g), iron powder (0.3–1.5 g), NaOH (0.3–1.5 g), and H₂O (0.4–2 ml) were investigated on the decomposition efficiency of PCBs existing in real waste transformer oil with MDMW. Obtained data indicate that PEG and NaOH have the greatest influence on decomposition of PCBs; while, iron did not influence, and H₂O decreased, the decomposition efficiency of PCBs. Experimental data also indicated that with the optimum amount of variables through a central composites design method (PEG = 5.34 g, NaOH = 1.17 g, Fe = 0.6 g, H₂O = 0.8 ml and microwave power 800 W), 78 % of PCBs was degraded at a reaction time of about 6 min. In addition, the PCBs decomposition without using water increased up to 100 % in the reactor with the MDMW at 6 min. Accordingly, results showed that MDMW was a very efficient factor for PCBs decomposition from waste transformer oil. Also, using microwave irradiation, availability and inexpensive materials (PEG, NaOH), and iron suggest this method as a fast, effective, and cheap method for PCB decomposition of waste oils.     

Hydrolysis of organic matter during autoclaving of commingled household waste

Commingled household waste (HW) that had a controlled composition was autoclaved at elevated pressures in the presence of saturated steam for one hour at the nominal temperature levels of 130 °C, 160 °C and 200 °C. The focus of this study was the impact of temperature/pressure on hydrolysis of organic matter during autoclaving and the extent of its hydrolysis. The pH decreased with autoclaving temperature with which it had a linear relationship, and ranged from 7.4 and 6 in floc, and 6.7 and 3.6 in steam condensate. Overall, organic matter solubilisation, as indicated by dissolved organic carbon, biological and chemical oxygen demands, and total dissolved solids, increased with temperature. Lignin did not appear to hydrolyse. Hemicellulose hydrolysed and degraded the most, followed by cellulose. The highest recoveries of hemicellulose and cellulose in solution were achieved at 160 °C, although the latter could be due to experimental error. The largest losses of hemicellulose and cellulose were recorded at 200 °C. The performance of the system in respect to hydrolysis was inferior compared to other hydrothermal systems, particularly those employing wet oxidation.     

Pyrolysis of lemon peel waste in a fixed-bed reactor and characterization of innovative pyrolytic products

Journal of Material Cycles and Waste Management - Lemon peel waste (LPW) were pyrolysed in a laboratory fixed-bed reactor at final temperature of 300 °C, 400 °C and...     

Effect of polyethylene addition to coal on hydrogasification enhancement

Hydrogasification of a coal/polyethylene mixture was carried out using a low concentration of polyethylene in the samples with the aim of industrial application. Coal/polyethylene mixtures in the ratio of 90:10 and 75:25 were used in this study. A hydrogasification experiment was conducted using a unique batch reactor at 1073 K under a 7.1 MPa hydrogen atmosphere. The reaction time varied from 1 to 80 s. The results revealed a methane yield from the mixtures that was noticeably greater than the values calculated from experimental results obtained from coal and polyethylene respectively, assuming no mutual influences. A significant synergistic effect was observed even when the polyethylene content was as low as 10 %. It is suggested that there might be an advantage in hydrogasification processes if waste plastics are mixed with coal, such content being practically assumed.     

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.     

Recycling extruded polystyrene by dissolution with suitable solvents

The amount of extruded polystyrene (XPS) waste has increased in recent years due to the increase of its use in the thermal insulation of buildings, transport vehicles, and refrigerators, among others. Dissolution with suitable solvents to achieve a volume reduction of more than 100 times without degradation of polymer chains is one of the cheapest and most efficient methods of recycling XPS. Several environmentally friendly solvents have been tested as dissolution agents for XPS volume reduction; the action of these solvents does not produce any degradation of polymer chains. The solubility of the polymer in such solvents at different temperatures was investigated. The solvent can be easily recycled by distillation, obtaining a high-quality recycled polymer. Chemical Feedstock Recycling & Other Innovative Recycling Techniques 6