Kinetics of thermal de-chlorination of PVC under pyrolytic conditions

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

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.     

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

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

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.     

Energy from gasification of solid wastes

Gasification technology is by no means new: in the 1850s, most of the city of London was illuminated by "town gas" produced from the gasification of coal. Nowadays, gasification is the main technology for biomass conversion to energy and an attractive alternative for the thermal treatment of solid waste. The number of different uses of gas shows the flexibility of gasification and therefore allows it to be integrated with several industrial processes, as well as power generation systems. The use of a waste-biomass energy production system in a rural community is very interesting too. This paper describes the current state of gasification technology, energy recovery systems, pre-treatments and prospective in syngas use with particular attention to the different process cycles and environmental impacts of solid wastes gasification.     

Energy recovery from solid waste fuels using advanced gasification technology

Since the mid-1980s, TPS Termiska Processer AB has been working on the development of an atmospheric-pressure gasification process. A major aim at the start of this work was the generation of fuel gas from indigenous fuels to Sweden (i.e. biomass). As the economic climate changed and awareness of the damage to the environment caused by the use of fossil fuels in power generation equipment increased, the aim of the development work at TPS was changed to applying the process to heat and power generation from feedstocks such as biomass and solid wastes. Compared with modern waste incineration with heat recovery, the gasification process will permit an increase in electricity output of up to 50%. The gasification process being developed is based on an atmospheric-pressure circulating fluidised bed gasifier coupled to a tar-cracking vessel. The gas produced from this process is then cooled and cleaned in conventional equipment. The energy-rich gas produced is clean enough to be fired in a gas boiler (and, in the longer term, in an engine or gas turbine) without requiring extensive flue gas cleaning, as is normally required in conventional waste incineration plants. Producing clean fuel gas in this manner, which facilitates the use of efficient gas-fired boilers, means that overall plant electrical efficiencies of close to 30% can be achieved. TPS has performed a considerable amount of pilot plant testing on waste fuels in their gasification/gas cleaning pilot plant in Sweden. Two gasifiers of TPS design have been in operation in Grève-in-Chianti, Italy since 1992. This plant processes 200 tonnes of RDF (refuse-derived fuel) per day. It is planned that the complete TPS gasification process (including the complete fuel gas cleaning system) be demonstrated in several gas turbine-based biomass-fuelled power generating plants in different parts of the world. It is the aim of TPS to prove, at commercial scale, the technical feasibility and economic advantages of the gasification process when it is applied to solid waste fuels. This aim shall be achieved, in the short-term, by employing the cold clean product gas in a gas boiler and, in the longer-term, by firing the gas in engines and gas turbines. A study for a 90 MWth waste-fuelled co-generation plant in Sweden has shown that, already today, gasification of solid waste can compete economically with conventional incineration technologies.     

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.     

Studies on the dechlorination and oil-production technology of waste plastics

 Recycle technology for waste plastics containing polyvinyl chloride (PVC) has been developed in the Hokkaido National Industrial Research Institute for the production of solid and liquid fuel, and has established a recycling process which includes a dechlorination process for PVC plastics, and a two-stage catalytic pyrolysis process for plastics using zeolite catalysts. The dechlorination equipment consists of a two-axis screw extruder with a heating element, which can remove chlorine up to 99.9 wt. % from PVC containing plastics as hydrogen chloride. The product had about 44 000 kJ/kg calorific value and was fed into the next oil production process, although it could also be used as a solid fuel. Natural and synthetic zeolite were used as catalysts for the two-stage catalytic process, which produced a light oil with a boiling point which was between those of kerosene and gasoline. The yield of this oil reached 82 wt. %. The chemical type was analyzed using liquid chromatography, and was found to have many aromatic compounds. These technologies make it possible to produce a nonpolluting, high-calorie solid fuel and a liquid fuel very efficiently. Received: July 19, 2000 / Accepted: September 21, 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.     

Hydrogen-rich synthesis gas production from waste wood via gasification and reforming technology for fuel cell application

The purpose of this study was to establish a fuel process for an advanced power generation system in which hydrogen-rich synthesis gas, as the fuel for the molten carbonate fuel cell (MCFC), can be extracted from biomass via gasification and reforming technologies. Experiments on waste wood gasification were performed using a bench-scale gasification system. The main factors influencing hydrogen generation in the noncatalytic process and in the catalytic process were investigated, and temperature was identified as the most important factor. At 950°C, without employing a catalyst, hydrogen-rich synthesis gas containing about 54 vol% hydrogen was extracted from feedstock with appropriately designed operation parameters for the steam/carbon ratio and the equivalence ratio. However, by employing a commercial steam reforming catalyst in the reforming process, similar results were obtained at 750°C.     

Energy recovery from grass using two-phase anaerobic digestion

Municipal solid wastes are major sources of air, water and soil contamination. There is a need for alternative waste management techniques to better utilize the waste and minimize its adverse environmental impact. A two-phase pilot-scale bio-fermentation system was used to evaluate the feasibility of producing methane from grass waste, a major constituent of solid wastes. The bi-phasic system consists of a solid phase and a methane phase. Leachate is re-circulated through the solid phase until a desired level of volatile fatty acid (VFA) is accumulated in the leachate. The leachate is then transferred to the methane reactor where the VFA is converted to methane. The results showed that 67% of the volatile solids in the waste can be converted into soluble chemical oxygen demand in a period of six months. The system produced an average of 0.15 m3 of methane per kg of grass. The average methane concentration in the produced gas was 71%. A mathematical model was developed to estimate the methane and carbon dioxide concentrations in the gas phase as a function of reactor properties.     

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.     

Thermal valorization of post-consumer film waste in a bubbling bed gasifier

The use of plastic bags and film packaging is very frequent in manifold sectors and film waste is usually present in different sources of municipal and industrial wastes. A significant part of it is not suitable for mechanical recycling but could be safely transformed into a valuable gas by means of thermal valorization. In this research, the gasification of film wastes has been experimentally investigated through experiments in a fluidized bed reactor of two reference polymers, polyethylene and polypropylene, and actual post-consumer film waste. After a complete experimental characterization of the three materials, several gasification experiments have been performed to analyze the influence of the fuel and of equivalence ratio on gas production and composition, on tar generation and on efficiency. The experiments prove that film waste and analogue polymer derived wastes can be successfully gasified in a fluidized bed reactor, yielding a gas with a higher heating value in a range from 3.6 to 5.6 MJ/m³ and cold gas efficiencies up to 60%.     

Co-gasification of solid waste and lignite - a case study for Western Macedonia

Co-gasification of solid waste and coal is a very attractive and efficient way of generating power, but also an alternative way, apart from conventional technologies such as incineration and landfill, of treating waste materials. The technology of co-gasification can result in very clean power plants using a wide range of solid fuels but there are considerable economic and environmental challenges. The aim of this study is to present the available existing co-gasification techniques and projects for coal and solid wastes and to investigate the techno-economic feasibility, concerning the installation and operation of a 30MW(e) co-gasification power plant based on integrated gasification combined cycle (IGCC) technology, using lignite and refuse derived fuel (RDF), in the region of Western Macedonia prefecture (WMP), Greece. The gasification block was based on the British Gas-Lurgi (BGL) gasifier, while the gas clean-up block was based on cold gas purification. The competitive advantages of co-gasification systems can be defined both by the fuel feedstock and production flexibility but also by their environmentally sound operation. It also offers the benefit of commercial application of the process by-products, gasification slag and elemental sulphur. Co-gasification of coal and waste can be performed through parallel or direct gasification. Direct gasification constitutes a viable choice for installations with capacities of more than 350MW(e). Parallel gasification, without extensive treatment of produced gas, is recommended for gasifiers of small to medium size installed in regions where coal-fired power plants operate. The preliminary cost estimation indicated that the establishment of an IGCC RDF/lignite plant in the region of WMP is not profitable, due to high specific capital investment and in spite of the lower fuel supply cost. The technology of co-gasification is not mature enough and therefore high capital requirements are needed in order to set up a direct co-gasification plant. The cost of electricity estimated was not competitive, compared to the prices dominating the Greek electricity market and thus further economic evaluation is required. The project would be acceptable if modular construction of the unit was first adopted near operating power plants, based on parallel co-gasification, and gradually incorporating the remaining process steps (gas purification, power generation) with the aim of eventually establishing a true direct co-gasification plant.     

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     

Production of high quality syngas from argon/water plasma gasification of biomass and waste

Extremely hot thermal plasma was used for the gasification of biomass (spruce sawdust, wood pellets) and waste (waste plastics, pyrolysis oil). The plasma was produced by a plasma torch with DC electric arc using unique hybrid stabilization. The torch input power of 100–110 kW and the mass flow rate of the gasified materials of tens kg/h was set up during experiments. Produced synthetic gas featured very high content of hydrogen and carbon monoxide (together approximately 90%) that is in a good agreement with theory. High quality of the produced gas is given by extreme parameters of used plasma – composition, very high temperature and low mass flow rate.     

Decreased PCDD/F formation when co-firing a waste fuel and biomass in a CFB boiler by addition of sulphates or municipal sewage sludge

Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) are formed during waste incineration and in waste-to-energy boilers. Incomplete combustion, too short residence times at low combustion temperatures (<700 °C), incineration of electronic waste and plastic waste containing chlorine are all factors influencing the formation of PCDD/Fs in boilers. The impact of chlorine and catalysing metals (such as copper and iron) in the fuel on PCDD/F formation was studied in a 12 MW_th circulating fluidised bed (CFB) boiler. The PCDD/F concentrations in the raw gas after the convection pass of the boiler and in the fly ashes were compared. The fuel types were a so-called clean biomass with low content of chlorine, biomass with enhanced content of chlorine from supply of PVC, and solid recovered fuel (SRF) which is a waste fuel containing higher concentrations of both chlorine, and catalysing metals. The PCDD/F formation increased for the biomass with enhanced chlorine content and it was significantly reduced in the raw gas as well as in the fly ashes by injection of ammonium sulphate. A link, the alkali chloride track, is demonstrated between the level of alkali chlorides in the gas phase, the chlorine content in the deposits in the convection pass and finally the PCDD/F formation. The formation of PCDD/Fs was also significantly reduced during co-combustion of SRF with municipal sewage sludge (MSS) compared to when SRF was fired without MSS as additional fuel.     

Study on chlorine removal from mixture of waste plastics

The recycling of waste plastics that include plastics that contain chlorine, such as polyvinyl chloride, is difficult because the chlorine leads to the corrosion of equipment. Then, the dechlorination method of waste plastics containing chlorine (CCWP) that consists of a series of melt process and hot water process was examined. CCWP was put into the melt process with coal tar (HOB) and converter dust (CD) to inhibit the diffusion of the chlorine-containing gas. The results indicated that iron oxide of the principal element of CD combines with chlorine eliminated from CCWP, and forms water-soluble iron chloride on the melt process. HOB dissolves or adsorbs a part of the chlorine during the melt process, and inhibits the diffusion of the chlorine-containing gas. Approximately 98% of the chlorine in the CCWP reacts with CD and forms iron chloride, which can be extracted on the hot water process.     

氟化工“三废”的资源化利用

结合我国氟化工行业发展现状,分析了含氟"三废"产生情况及处置方法的最新研究进展,并通过实际工程案例进行论述。氟化工生产过程污染物主要有含氟废气及副产氯化氢、含氟高沸物及含氟污泥等。通过将氯化氢用于工业清洗及制备氯化钙、氯化铝等化学品能够合理消耗副产盐酸。焚烧处理含氟有机废气产生的氟化氢气体经水洗后副产氢氟酸。含氟高沸物通过精馏分离出高沸物组分生产高附加值产品。含氟污泥可制成建筑材料,最优工业化利用途径仍在积极研究中。     

Laboratory study on the behaviour of spent AA household alkaline batteries in incineration

The quantitative evaluation of emissions from incineration is essential when Life Cycle Assessment (LCA) studies consider this process as an end-of-life solution for some wastes. Thus, the objective of this work is to quantify the main gaseous emissions produced when spent AA alkaline batteries are incinerated. With this aim, batteries were kept for 1h at 1273K in a refractory steel tube hold in a horizontal electric furnace with temperature control. At one end of the refractory steel tube, a constant air flow input assures the presence of oxygen in the atmosphere and guides the gaseous emissions to a filter system followed by a set of two bubbler flasks having an aqueous solution of 10% (v/v) nitric acid. After each set of experiments, sulphur, chlorides and metals (As, Cd, Co, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Sb, Tl and Zn) were analyzed in both the solutions obtained from the steel tube washing and from the bubblers. Sulphur, chlorides and metals were quantified, respectively, using barium sulfate gravimetry, the Volhard method and atomic absorption spectrometry (AAS). The emissions of zinc, the most emitted metal, represent about 6.5% of the zinc content in the batteries. Emissions of manganese (whose oxide is the main component of the cathode) and iron (from the cathode collector) are negligible when compared with their amount in AA alkaline batteries. Mercury is the metal with higher volatility in the composition of the batteries and was collected even in the second bubbler flask. The amount of chlorides collected corresponds to about 36% of the chlorine in the battery sleeve that is made from PVC. A considerable part of the HCl formed in PVC plastic sleeve incineration is neutralized with KOH, zinc and manganese oxides and, thus, it is not totally released in the gas. Some of the emissions are predictable through a thermodynamic data analysis at temperatures in the range of 1200-1300K taking into account the composition of the batteries. This analysis was done for most of potential reactions between components in the batteries as well as between them and the surrounding atmosphere and it reasonably agrees the experimental results. The results obtained show the role of alkaline batteries at the acid gases cleaning process, through the neutralization reactions of some of their components. Therefore, LCA of spent AA alkaline batteries at the municipal solid waste (MSW) incineration process must consider this contribution.