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.     

Carbon materials-catalyzed hydroliquefaction of flame-retardant plastics in organic solvents

Flame-retardant plastics, such as desktop and laptop personal computer bodies, could be completely liquefied by carbon materials-catalyzed hydroliquefaction in tetralin without using H₂ as a hydrogen source. Active carbons with larger surface areas (1450–3450 m²/g) acted as superior catalysts in transferring tetralin hydrogens to plastics. On the other hand, carbon blacks and fullerene-rich soot were less active catalysts. Graphite and mesocarbon microbeads did not show any catalytic effects. Benzene, toluene, and ethylbenzene were obtained as recyclable hydrocarbons; their total amounts varied from 4 wt% to 12 wt% depending on the types of plastics and the carbon materials used. Organic bromides such as polybromodioxins were not contained in the gases and oils of the product. Received: July 19, 2000 / Accepted: September 17, 2000     

Decomposition of mixed plastics consisting of polypropylene and polyethylene terephthalate into oils over titania/silica catalysts

The catalytic decomposition of mixed plastics consisting of polypropylene (PP) and polyethylene terephthalate (PET) has been investigated over titania/silica catalysts at 698 K. The yield of oil produced was about 70%, and the large amounts of C₁₈₊ hydrocarbons this contained was from the aromatics in PET. Gas was also produced, including C₃–C₅ hydrocarbons. The carbon-number fractions in the oil was influenced by the PET/(PP + PET) ratios and the catalyst weight. The titania/silica catalysts could be used repeatedly, and after they had been fouled, could be regenerated. From the Fourier Transform Infrared (FT–IR) spectroscopic data of adsorbed pyridine on the catalyst surface, most of the acid sites of the titania/silica catalysts were found to be Lewis sites where the hydride abstracted from PP pyrolysates react with PET pyrolysates to form oil and gas. Received: July 19, 2000 / Accepted: October 20, 2000     

Study on dechlorination technology for municipal waste plastics containing polyvinyl chloride and polyethylene terephthalate

It is necessary to remove chlorine efficiently from municipal waste plastics (MWP) that contain polyvinyl chloride (PVC) and other plastics containing chlorine. In this article we consider thermal degradation liquefaction technology. In Japan, the chlorine content of reclamation oil products must be kept below 100 ppm owing to the quality standard for pyrolysis oil. Liquefaction dechlorination technology for MWP is still an important issue to study. The twin-screw extruder that has been developed as dechlorination technology for blast furnaces and coke ovens has a shorter residence time for dechlorination than other dechlorination technologies. In this article, we used a single-screw extruder for the dechlorination process because it also has a short residence time. Experiments on the dechlorination process were carried out by using a single-screw extruder to assess its dechlorination performance. Practical use of the single-screw was demonstrated by the operation of a commercial oil reclamation plant operated by Sapporo Plastic Recycle Co., Ltd. (SPR). Moreover, an investigation of cascade recycling was carried out in 2008 in which material recycle wastes were mixed with MWP and processed by chemical recycling (liquefaction). It was demonstrated that cascade recycling is an efficient recycling combination and contributes to local feedstock recycling. However, it was shown that MR wastes affect the quality of the reclamation oil when they make up more than 40% of the feed mix. If the quantity of MR wastes is kept below 40%, the reclamation oil is able to meet the quality standard. The SPR plant can be operated safely and in a stable manner.     

Upgrading of poly(vinyl chloride) by chemical modifications using sodium sulfide

The recycling of poly(vinyl chloride) (PVC) is one of the most important issues in the treatment of waste plastics. To improve PVC recycling, it is necessary to develop new recycling techniques, including new techniques for the dechlorination of chlorine-containing polymers. It has been established that wet dechlorination of PVC in NaOH/ethylene glycol solution is more effective than dry dechlorination. In this study, the wet process was used, and the chemical modification of PVC by nucleophilic substitution was considered for upgrading waste PVC. Chlorine was substituted in solution by several nucleophilic reagents, thus changing the properties of PVC. The reaction of PVC in Na2S/ethylene glycol solution at 170°C resulted in the formation of a mixture comprising 32% elimination and 26% substitution products. The scanning electron microscopy/energy dispersive X-ray spectroscopy mappings and elementary analysis of PVC indicated that this chlorine-substitution process led to cross-linking by sulfur.     

Influence of poly(bisphenol A carbonate) and poly(ethylene terephthalate) on poly(vinyl chloride) dehydrochlorination

Recycling of poly(vinyl chloride) (PVC) waste is a serious problem because of its high chlorine content. Dehydrochlorination of PVC-containing polymer waste produces solid residue char, for which conversion to pyrolysis oil in a petrochemical plant seems to be an attractive way of recycling PVC waste. Unfortunately, some polymer admixtures react with HCl and cause formation of chloroorganic compounds in a char. This article describes the influence of polycarbonates and poly(ethylene terephthalate) on thermal feedstock recycling of PVC wastes using a two-stage method. It was found that the presence of polycarbonate causes the formation of small amounts of benzyl chloride and other chloroaryl or chloroalkylaryl compounds. Poly(ethylene terephthalate) interacts with HCl forming significant amounts of various chlorocompounds – mainly chloroethyl esters of terephthalic and benzoic acids, but derivatives possessing chlorine directly connected to the aromatic ring are also formed.     

Behavior of bromine on the thermal decomposition of paper-based phenolic laminate wastes

We investigated the thermal properties and behavior of bromine on the thermal decomposition of paper-based phenolic laminate wastes containing polybrominated flame retardants. The thermal properties of the phenolic laminate wastes were measured with a thermogravimeter and a conduction-type scanning calorimeter (TG-CSC). The weight loss of the wastes on thermal decomposition was mainly in three phases between 40°C and 600°C. The enthalpy (ΔH) of the thermal decomposition was 104 cal/g. The material balance of the decomposition components was measured with batch-type thermal decomposition equipment. The ratios of carbon residue, liquid, and gas on decomposition at 800°C in a vacuum were 37 wt. %, 48 wt. %, and 15 wt. %, respectively. The bromine contents in the carbon residue and liquid were less than 0.02 wt. % and 10 wt. %, respectively. These results are useful both in the carbonization process of these wastes and in the application of carbon residue as carbon materials. Received: August 11, 2000 / Accepted: March 7, 2001     

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.     

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     

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.     

Relation between mechanochemical dechlorination rate of polyvinyl chloride and mill power consumption

A sample of polyvinyl chloride (PVC) powder was milled with CaO powder in a planetary mill for various mill operational parameters. The milled product consisted of dechlorinated hydrocarbon and water-soluble CaOHCl. The dechlorination rate of PVC was determined by the concentration of Cl⁻ ions measured in solution after dispersing the milled product in water. To evaluate the power consumption during PVC dechlorination, the mill power consumption was measured during each experimental run. In addition, media motion during planetary milling was simulated using the discrete element method (DEM), enabling calculation of the mill power consumption. The power consumption calculated by the DEM simulation compared well with the power consumption measured experimentally. The dechlorination rate correlated well with the specific mill power consumption, regardless of the sample weight. The dechlorination rate of PVC when milled with oyster shells (CaCO₃) was observed to be faster than that of the PVC/CaO system, and oyster shells could be used as a reactant for the treatment of PVC wastes. This work should be useful for the design of a reactor for the dechlorination of PVC. Chemical Feedstock Recycling & Other Innovative Recycling Techniques 6     

Waste plastics recycling by an entrained-flow gasifier

We studied an entrained-flow gasification process which efficiently converts waste plastics to energy at a high energy recovery rate. Waste plastics, after being shredded to <8 mm or <14 mm, were fed into an entrained-flow gasifier with air and oxygen. In the gasifier, organic substances were pyrolyzed, partially combusted, and then converted into synthetic gas (CO, H₂) at a high temperature (over 1600 K). The clarified gasification characteristics were that the lower heat value (LHV) of the product gas was over 4.2 MJ/Nm³ and the cold gas efficiency was approximately 60%. Other inert substances in the wastes such as ashes and metals were melted into slag and condensed on bag filters. The bag filters and a water scrubber removed impurities such as dusts, heavy metals, and hydrogen halides from the product gases. Solid hydrocarbons, which include char and soot, were removed at a hot cyclone and on the bag filters. Received: July 19, 2000 / Accepted: October 3, 2000     

Mechanical treatment of automobile shredder residue for its application as a fuel

Enforcement of the Automobile Recycling Law in Japan requires utilization of automobile shredder residue (ASR). However, the high contents of copper (∼5%) and chlorine (∼1%) in ASR stand in the way of practical application. We studied methods for the removal of copper and chlorine from ASR so that it could be utilized as a fuel. By compression of the ASR for solidification with an extruder, the polyvinylchloride (PVC) that covered electrical cables was softened and stripped from the copper wire. The solidified ASR was comminuted with cutter mills and classified by dry density separation. The copper content of the obtained light products was 0.2%–0.5%. Furthermore, we studied the possibility of dechlorination of the ASR by mechanochemical (MC) activation. The light product of the ASR was milled with CaO or CaCO₃. The chlorine content decreased to about one-tenth of the original value after MC activation over 8 h. Therefore, the combined processing of softening–stripping and comminution liberated the PVC-covered cables and decreased the copper content of the ASR. In addition, dechlorination of the ASR was also possible by MC activation with the addition of calcium compounds.     

Investigation on thermal dechlorination and catalytic pyrolysis in a continuous process for liquid fuel recovery from mixed plastic wastes

A continuous system (feeding rate >1 kg/h) consisting of thermal dechlorination pre-treatment and catalytic pyrolysis with Fe-restructured clay (Fe-RC) catalyst was developed for feedstock recycling of PVC-containing mixed plastic waste. The vented screw conveyor which was specially designed for continuous dechlorination was able to achieve dechlorination efficiency of over 90 % with a feedstock retention time longer than 35.5 min. The chlorine content of the pyrolytic oil obtained after dechlorination was in the range of 6.08–39.50 ppm, which meet the specification for reclamation pyrolytic oil in Japan. Fe-RC was found to significantly improve the yield of pyrolytic oil (achieved to 83.73 wt%) at the optimized pyrolysis temperature of 450 °C and catalyst dosage of 60 g. With the optimized parameters, Fe-RC showed high selectivity for the C₉–C₁₂ and C₁₃–C₁₉ oil fraction, which are the major constituents of kerosene and diesel fuel, demonstrating that this catalyst can be applied in the pyrolysis of mixed plastic wastes for the production of kerosene and diesel fuel. Overall, the continuous process exhibited high stability and consistently high-oil yield upon reaching steady state, indicating its potential up-scaling application in the industry.     

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     

High efficiency chlorine removal from polyvinyl chloride (PVC) pyrolysis with a gas–liquid fluidized bed reactor

In this research a gas–liquid fluidized bed reactor was developed for removing chlorine (Cl) from polyvinyl chloride (PVC) to favor its pyrolysis treatment. In order to efficiently remove Cl within a limited time before extensive generation of hydrocarbon products, the gas–liquid fluidized bed reactor was running at 280–320 °C, where hot N₂ was used as fluidizing gas to fluidize the molten polymer, letting the molten polymer contact well with N₂ to release Cl in form of HCl. Experimental results showed that dechlorination efficiency is mainly temperature dependent and 300 °C is a proper reaction temperature for efficient dechlorination within a limited time duration and for prevention of extensive pyrolysis; under this temperature 99.5% of Cl removal efficiency can be obtained within reaction time around 1 min after melting is completed as the flow rate of N₂ gas was set around 0.47–0.85 Nm³ kg^?1 for the molten PVC. Larger N₂ flow rate and additives in PVC would enhance HCl release but did not change the final dechlorination efficiency; and excessive N₂ flow rate should be avoided for prevention of polymer entrainment. HCl is emitted from PVC granules or scraps at the mean time they started to melt and the melting stage should be taken into consideration when design the gas–liquid fluidized bed reactor for dechlorination.     

Catalytic conversion of waste tyres into valuable hydrocarbons

Tyre recycling has become a necessity because of the huge piles of tyres that represent a threat to the environment. The used tyres represent a source of energy and valuable chemical products. Waste tyres were pyrolysed catalytically in a batch reactor under atmospheric pressure. Calcium carbide was used as a catalyst to explore its effect on pyrolysis product distribution. The effect of temperature, amount of catalyst and time on the yields of the pyrolysed products was investigated. Char yield decreased with increase of pyrolysis temperature while total gas and liquid yields increased. The liquid fraction was obtained with boiling point up to 320 °C. The physical and chemical properties of the pyrolysed products obtained were characterized. The catalytic pyrolysis produced 45 wt.% aromatic, 35 wt.% aliphatic and 20 wt.% of polar hydrocarbons. The distillation data showed that ∼80% of oil has boiling point below 270 °C which is the boiling point for 50% of distilled product in commercial diesel oil. The oil fraction was found to have high gross calorific value; GCV (42.8 MJ kg⁻¹). Its Specific gravity, viscosity, Kinematic viscosity, freezing point and diesel index were also within the limits of diesel fuel. The char residues were studied to investigate their characteristics for use as a possible adsorbent. Surface area of char before and after acid demineralization was determined to determine the adsorptive features for waste water treatment.     

Improved quartz furnace method for chlorine and sulfur determination in municipal solid waste

 A method of determining the chlorine (Cl) and sulfur (S) in municipal solid waste (MSW) was studied. The quartz furnace method was improved in two ways: recovery from ash by hot extraction with dilute nitric acid, and avoidance of the volatilization of alkali (earth) metal chlorides by setting the sample combustion temperature at 600°C. In a comparison with the bomb method, using nine sets of kitchen garbage and waste plastics, the bomb method yielded a 15%–25% lower value than the improved quartz furnace method. Combustion in the bomb was frequently incomplete, resulting in recovery losses of Cl and S. The average kitchen garbage involved 5.2 mg Cl/g, of which at least 24.1% would be converted to HCl. Plastics contained 23 mg Cl/g generating 88.1% HCl on average. In the same way, kitchen garbage contained 3.0 mg S/g, generating 52.3% SO _x , whereas plastics contained 1.1 mg S/g with 55.1% SO _x formation. Received: March 20, 2002 / Accepted: October 13, 2002     

Mechanochemical dechlorination of polyvinyl chloride with calcium sulfates

Polyvinyl chloride (PVC) was milled with hydrated or unhydrated calcium sulfates (CaSO₄·2H₂O or CaSO₄) in air by using a planetary mill to investigate mechanochemical dechlorination behavior. The milling process resulted in size reduction and in the breaking of bonds leading to mechanically induced solid state reaction, forming CaCl₂ and dechlorinated hydrocarbon with C=C double bonds in the product. Washing the milled mixtures with water at room temperature allowed removal of the chloride formed during milling, and more than 95% of the chlorine in PVC was removed from a mixture milled for 4 h. This process could offer a potential route for the handling and disposal of both PVC and gypsum wastes. H₂S gas was generated during milling; more H₂S was released from the unhydrated sample than from the hydrated sample.     

锌粉对聚氯乙烯的机械化学还原脱氯

以锌粉为还原剂进行了聚氯乙烯（PVC）的机械化学还原脱氯（简称脱氯）探索研究，考察了球磨转速、球料比（磨球与试样的质量比）、锌粉与PVC质量比等对脱氯率的影响，并对脱氯产物进行了X射线衍射、红外光谱等分析。实验结果表明，最佳工艺条件为球料比33、球磨转速528r／min、锌粉与PVC质量比9；产物中未形成结晶性氯化锌，且锌粉被氧化成ZnO；行星球磨比搅拌球磨对PVC的脱氯效果好，球磨时间超过3h，PVC的脱氯率可接近100％。