Thermal pyrolysis of fresh and waste fishing nets

Kinetic tests on the pyrolysis of nylon-6 taken from fresh (new) fishing nets and waste fishing nets were conducted using thermogravimetric analysis at heating rates of 0.5, 1.0 and 2.0 degrees C/min. The main region of decomposition of both materials was between 340 and 440 degrees C at each heating rate. The region of decomposition for the nylon-6 from the waste fishing nets was slightly lower than that of the fresh fishing nets. The result shows that the value of activation energies increased from 128 to 433 kJ mol(-1) as the conversion of the pyrolysis reaction increased from 5% to 95%. Nylon-6 from the fresh fishing nets was pyrolyzed in a micro-scale tubing bomb reactor for 60, 80 and 100 min at 440 degrees C. The yield of pyrolyzed gases increased from 3.94 to 5.50 wt% with reaction time. The selectivity to specific hydrocarbons was not detected from the pyrolyzed oil and the carbon number distribution of the pyrolyzed oil was random.     

Influences of chemical activators on incinerator bottom ash

This research has applied different chemical activators to mechanically and thermally treated fine fraction (<14 mm) of incinerator bottom ash (IBA), in order to investigate the influences of chemical activators on this new pozzolanic material. IBA has been milled and thermally treated at 800 degrees C (TIBA). The TIBA produced was blended with Ca(OH)(2) and evaluated for setting time, reactivity and compressive strength after the addition of 0.0565 mole of Na(2)SO(4), K(2)SO(4), Na(2)CO(3), K(2)CO(3), NaOH, KOH and CaCl(2) into 100g of binder (TIBA+Ca(OH)(2)). The microstructures of activated IBA and hydrated samples have been characterized by X-ray diffraction (XRD) and thermogravimetry (TG) analysis. Thermal treatment is found to produce gehlenite (Ca(2)Al(2)SiO(7)), wollastonite (CaSiO(3)) and mayenite (Ca(12)Al(14)O(33)) phases. The thermally treated IBA samples are significantly more reactive than the milled IBA. The addition of Na(2)CO(3) can increase the compressive strength and calcium hydroxide consumption at 28-day curing ages. However, the addition of Na(2)SO(4), K(2)SO(4), K(2)CO(3), NaOH and KOH reduces the strength and hydration reaction. Moreover, these chemicals produce more porous samples due to increased generation of hydrogen gas. The addition of CaCl(2) has a negative effect on the hydration of TIBA samples. Calcium aluminium oxide carbonate sulphide hydrate (Ca(4)Al(2)O(6)(CO(3))(0.67)(SO(3))(0.33)(H(2)O)(11)) is the main hydration product in the samples with activated IBA, except for the sample containing CaCl(2).     

Recycling of organic materials and solder from waste printed circuit boards by vacuum pyrolysis-centrifugation coupling technology

Here, we focused on the recycling of waste printed circuit boards (WPCBs) using vacuum pyrolysis-centrifugation coupling technology (VPCT) aiming to obtain valuable feedstock and resolve environmental pollution. The two types of WPCBs were pyrolysed at 600°C for 30 min under vacuum condition. During the pyrolysis process, the solder of WPCBs was separated and recovered when the temperature range was 400-600°C, and the rotating drum was rotated at 1000 rpm for 10 min. The type-A of WPCBs pyrolysed to form an average of 67.91 wt.% residue, 27.84 wt.% oil, and 4.25 wt.% gas; and pyrolysis of the type-B of WPCBs led to an average mass balance of 72.22 wt.% residue, 21.57 wt.% oil, and 6.21 wt.% gas. The GC-MS and FT-IR analyses showed that the two pyrolysis oils consisted mainly of phenols and substituted phenols. The pyrolysis oil can be used for fuel or chemical feedstock for further processing. The recovered solder can be recycled directly and it can also be a good resource of lead and tin for refining. The pyrolysis residues contained various metals, glass fibers and other inorganic materials, which could be recovered after further treatment. The pyrolysis gases consisted mainly of CO, CO(2), CH(4), and H(2), which could be collected and recycled.     

Thermal cracking of oils from waste plastics

Thermal cracking of decomposed waste plastic oil produces a good yield of olefins. The solvent extraction of such waste plastic oil seems to be efficient for increasing gas yields and recycling monomers. To assess the potential of monomer recovery from municipal waste plastics, the oils were cracked using a laboratory-scale quartz-tube reactor. The waste plastic oils were provided by two commercial plants of the Sapporo Plastic Recycle Co. and the Dohoh Recycle Center Co. in Japan. A model waste plastic oil made in a laboratory was also examined. Yields of ethene, propene, and other products were measured at different temperatures. Two-step pyrolysis reduces coking compared with the direct thermal degradation of plastics. The raffinates from waste plastic oils extracted by sulfolane were also cracked. The primary products were almost the same as those from nontreated oils. The maximum total gas yield was 78wt%–85wt% at 750°C, an increase of about 20wt% compared with that of nonextracted oil. Solvent extraction removes stable aromatic hydrocarbons such as styrene, which is more coked than cracked.     

Pyrolysis of latex gloves in the presence of Y-zeolite

In this study we have investigated the possibility of processing waste rubber gloves using pyrolysis. Y-zeolite catalyst was employed to upgrade the pyrolysis products to give higher yields of valuable aromatic compounds such as toluene and xylenes. The composition of the pyrolysis products was determined using gas chromatography with linked mass spectrometry (GC-MS), gas chromatograph equipped with a flame ionization detector (GC-FID), gas chromatograph fitted with dual thermal conductivity detectors (GC-TCD), and Fourier Transform Infra-Red Spectrometry (FT-IR). It was found that when rubber gloves were pyrolysed in the absence of a catalyst, the pyrolysis oil consisted mainly of limonene and oligomers of polyisoprene. When Y-zeolite was added to the reaction system, the yields of toluene, xylene, methylbenzenes, ethylbenzenes, and naphthalenes increased dramatically. The Y-zeolite also catalysed the decomposition of limonene, which was absent from the catalytic pyrolysis products. The presence of the Y-zeolite catalyst also increased the yield of hydrocarbon gases. The tests were carried out at both 380 degrees C and 480 degrees C and it was found that the higher reaction temperature led to increased yields of all the major compounds, both in the presence and absence of the Y-zeolite catalyst.     

Pyrolysis kinetics of waste PVC pipe.

The pyrolysis kinetics of waste PVC pipe was investigated with a thermal gravimetric analysis system at heating rates of 5, 10, and 30 degrees C/min in a nitrogen atmosphere. Freeman-Carroll method was employed to evaluate kinetic parameters. Two dominant peaks were observed on derivative gravimetric curves, hypothetically suggesting a two-stage apparent reaction model. The first-stage reaction was likely to be represented by stoichiometric reaction to yield volatiles (mainly HCl) and intermediates. The second-stage reaction might be described by thermal degradation of intermediates competitively into gas, liquid, and solid by-products. Quasi-isothermal operations were introduced to verify the reaction types of the first and second reaction. The generation reaction of intermediates achieved at lower temperatures was carried out independently with their decomposition reaction at higher temperatures. The effects of additives on the pyrolysis kinetics of waste PVC pipe seem to be significant, especially on the first-stage reaction. The first-stage reaction was retarded. A merged peak at low temperatures was observed on the derivative thermogravimetry (DTG) curve instead of two peaks usually observed for that of pure PVC resin. The first peak on the DTG curve of pure PVC resin may shift more, resulting in the complete overlap of two peaks. The quantity of evolved HCl was likely to decrease because of interaction of metal components of stabilizers with either HCl or active chlorine atom or both. The final residual fraction increased as a result of pyrolysis of organic forms of additives to yield extra char. On the other hand, the second-stage reaction kinetics demonstrates a similar pattern to that of pure PVC resin, implying that the effects of additives may be less significant in comparison with that at the first-stage reaction.     

Pyrolysis of waste tyres: A review

Approximately 1.5 billion tyres are produced each year which will eventually enter the waste stream representing a major potential waste and environmental problem. However, there is growing interest in pyrolysis as a technology to treat tyres to produce valuable oil, char and gas products. The most common reactors used are fixed-bed (batch), screw kiln, rotary kiln, vacuum and fluidised-bed. The key influence on the product yield, and gas and oil composition, is the type of reactor used which in turn determines the temperature and heating rate. Tyre pyrolysis oil is chemically very complex containing aliphatic, aromatic, hetero-atom and polar fractions. The fuel characteristics of the tyre oil shows that it is similar to a gas oil or light fuel oil and has been successfully combusted in test furnaces and engines. The main gases produced from the pyrolysis of waste tyres are H₂, C₁–C₄ hydrocarbons, CO₂, CO and H₂S. Upgrading tyre pyrolysis products to high value products has concentrated on char upgrading to higher quality carbon black and to activated carbon. The use of catalysts to upgrade the oil to a aromatic-rich chemical feedstock or the production of hydrogen from waste tyres has also been reported. Examples of commercial and semi-commercial scale tyre pyrolysis systems show that small scale batch reactors and continuous rotary kiln reactors have been developed to commercial scale.     

The effect of clay catalyst on the chemical composition of bio-oil obtained by co-pyrolysis of cellulose and polyethylene

Cellulose/polyethylene (CPE) mixture 3:1, w/w with and without three clay catalysts (K10 – montmorillonite K10, KSF – montmorillonite KSF, B – Bentonite) addition were subjected to pyrolysis at temperatures 400, 450 and 500 °C with heating rate of 100 °C/s to produce bio-oil with high yield. The pyrolytic oil yield was in the range of 41.3–79.5 wt% depending on the temperature, the type and the amount of catalyst. The non-catalytic fast pyrolysis at 500 °C gives the highest yield of bio-oil (79.5 wt%). The higher temperature of catalytic pyrolysis of cellulose/polyethylene mixture the higher yield of bio-oil is. Contrarily, increasing amount of montmorillonite results in significant, almost linear decrease in bio-oil yield followed by a significant increase of gas yield. The addition of clay catalysts to CPE mixture has a various influence on the distribution of bio-oil components. The addition of montmorillonite K10 to cellulose/polyethylene mixture promotes the deepest conversion of polyethylene and cellulose. Additionally, more saturated than unsaturated hydrocarbons are present in resultant bio-oils. The proportion of liquid hydrocarbons is the highest when a montmorillonite K10 is acting as a catalyst.     

Characterization of MSWI bottom ashes towards utilization as glass raw material

The characterization of the bottom ashes produced by two Portuguese municipal solid waste incinerators (MSWI) was performed with the aim of assessing the feasibility of using this waste as raw material in the production of glass that can be further processed as glass-ceramics for application in construction. Density and particle size distribution measurements were carried out for physical characterization. Chemical characterization revealed that SiO(2), a network glass former oxide, was present in a relatively high content (52-58wt%), indicating the suitability for this waste to be employed in the development of vitreous materials. CaO, Na(2)O and K(2)O, which act as fluxing agents, were present in various amounts (2-17wt%) together with several other oxides normally present in ceramic and glass raw materials. Mineralogical characterization revealed that the main crystalline phases were quartz (SiO(2)) and calcite (CaCO(3)) and that minor amounts of different alkaline and alkaline-earth aluminosilicate phases were also present. Thermal characterization showed that the decomposition of the different compounds occurred up to 1100 degrees C and that total weight loss was <10wt%. Heating both bottom ashes at 1400 degrees C for 2h resulted in a melt with suitable viscosity to be poured into a mould, and homogeneous black-coloured glasses with a smooth shiny surface were obtained after cooling. The vitrified bottom ashes were totally amorphous as confirmed by X-ray diffraction. The results from the present experimental work indicate that the examined bottom ashes can be a potential material to melt and to obtain a glass that can be further processed as glass-ceramics to be applied in construction.     

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.     

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.     

Quality improvement of pyrolysis oil from waste rubber by adding sawdust

This work was aimed at improving the pyrolysis oil quality of waste rubber by adding larch sawdust. Using a 1 kg/h stainless pyrolysis reactor, the contents of sawdust in rubber were gradually increased from 0%, 50%, 100% and 200% (wt%) during the pyrolysis process. Using a thermo-gravimetric (TG) analyzer coupled with Fourier transform infrared (FTIR) analysis of evolving products (TG–FTIR), the weight loss characteristics of the heat under different mixtures of sawdust/rubber were observed. Using the pyrolysis–gas chromatography (GC)–mass spectrometry (Py–GC/MS), the vapors from the pyrolysis processes were collected and the compositions of the vapors were examined. During the pyrolysis process, the recovery of the pyrolysis gas and its composition were measured in-situ at a reaction temperature of 450 °C and a retaining time of 1.2 s. The results indicated that the efficiency of pyrolysis was increased and the residual carbon was reduced as the percentage of sawdust increased. The adding of sawdust significantly improved the pyrolysis oil quality by reducing the polycyclic aromatic hydrocarbons (PAHs) and nitrogen and sulfur compounds contents, resulting in an improvement in the combustion efficiency of the pyrolysis oil.     

Gasification of refuse derived fuel in a fixed bed reactor for syngas production

Steam gasification of two different refuse derived fuels (RDFs), differing slightly in composition as well as thermal stability, was carried out in a fixed-bed reactor at atmospheric pressure. The proximate and ultimate analyses reveal that carbon and hydrogen are the major components in RDFs. The thermal analysis indicates the presence of cellulose and plastic based materials in RDFs. H2 and CO are found to be the major products, along with CO2 and hydrocarbons resulting from gasification of RDFs. The effect of gasification temperature on H2 and CO selectivities was studied, and the optimum temperature for better H2 and CO selectivity was determined to be 725 degrees C. The calorific value of product gas produced at lower gasification temperature is significantly higher than that of gas produced at higher process temperature. Also, the composition of RDF plays an important role in distribution of products gas. The RDF with more C and H content is found to produce more amounts of CO and H2 under similar experimental conditions. The steam/waste ratio showed a notable effect on the selectivity of syngas as well as calorific value of the resulting product gas. The flow rate of carrier gas did not show any significant effect on products yield or their distribution.     

Pyrolysis characteristics of the mixture of printed circuit board scraps and coal powder

Thermogravimetric (TG) analysis and infrared spectroscopy were used to analyze the pyrolysis characteristics of printed circuit board scraps (PCBs), coal powder and their mixtures under nitrogen atmosphere. The experimental results show that there is a large difference between waste PCBs and coal powder in pyrolysis processing. The pyrolysis properties of the mixing samples are the result of interaction of the PCBs and coal powder, which is influenced by the content of mixture. The degree of pyrolysis and pyrolysis properties of the mixture are much better than that of the single component. The TG and the differential thermogravimetric (DTG) curves of the PCBs mixed with coal powder move towards the high-temperature zone with increasing amount of coal powder and subsequently the DTG peak also becomes wider. The Coats–Redfern integral method was used to determine the kinetic parameters of pyrolysis reaction mechanism with the different proportion of mixture. The gas of pyrolysis mainly composes of CO₂, CO, H₂O and some hydrocarbon. The bromide characteristic absorption peak has been detected obviously in the pyrolysis gas of PCBs. On the contrary, the absorption peak of the bromide is not obvious in pyrolysis gas of the PCBs samples adding 40% coal powder.     

Effect of some environmentally degradable materials on the pyrolysis of plastics II: influence of cellulose and lignin on the pyrolysis of complex mixtures

Pyrolysis of polymer mixtures with a composition similar to that of municipal plastic waste containing polyvinyl chloride (PVC) and of municipal plastic waste free of PVC was performed in the presence of components of biomass, namely lignin, cellulose, or both. The pyrolysis products were characterized by standard methods utilized in the petrochemical industry, i.e., paraffins-isoparaffinsolefins-naphthenes-aromatics analysis, proton nuclear magnetic resonance and infrared spectroscopy, and gas chromatography-mass spectrometry. Up to 3 wt% lignin, cellulose, or both in mixed polymers changed the material balance of pyrolysis by decreasing the amount of waxy products. The presence of both PVC and biomass components significantly changed the material balance by decreasing the waxy product yield and increasing the gas and coke yield. The composition of all pyrolysis products was also modified with the addition of PVC, components of biomass, or both.     

Tertiary recycling of PVC-containing plastic waste by copyrolysis with cattle manure

The corrosion from pyrolysis of PVC in plastic waste was reduced by copyrolysis of PVC with cattle manure. The optimization of pyrolysis conditions between PVC and cattle manure was studied via a statistical method, the Box-Behnken model. The pyrolysis reaction was operated in a tubular reactor. Heating rate, reaction temperature and the PVC:cattle manure ratio were optimized in the range of 1-5 degrees C/min, 250-450 degrees C and the ratio of 1:1-1:5, respectively. The suitable conditions which provided the highest HCl reduction efficiency were the lowest heating rate of 1 degrees C/min, the highest reaction temperature of 450 degrees C, and the PVC:cattle manure ratio of 1:5, with reliability of more than 90%. The copyrolysis of the mixture of PVC-containing plastic and cattle manure was operated at optimized conditions and the synergistic effect was studied on product yields. The presence of manure decreased the oil yield by about 17%. The distillation fractions of oil at various boiling points from both the presence and absence of manure were comparable. The BTX concentration decreased rapidly when manure was present and the chlorinated hydrocarbon was reduced by 45%. However, the octane number of the gasoline fraction was not affected by manure and was in the range of 99-100.     

Catalytic pyrolysis of car tire waste using expanded perlite

In this study, the non-catalytic and catalytic pyrolysis experiments were conducted on the sample of tire waste using expanded perlite as an additive material to determine especially the effect of temperature and catalyst-to-tire ratio on the products yields and the compositions and qualities of pyrolytic oils (NCPO and CPO). Non-catalytic studies, which were carried out under the certain conditions (a nitrogen flow of 100 mL/min and a heating rate of 10 °C/min), showed that the highest yield of pyrolytic oil (NCPO) was 60.02 wt.% at 425 °C. Then, the catalytic pyrolysis studies were carried out at catalyst-to-tire ratio range of 0.05-0.25 and the highest catalytic pyrolytic oil (CPO) yield was 65.11 wt.% at the ratio of 0.10 with the yield increase of 8.48 wt.% compared with the non-catalytic pyrolysis. Lastly, the pyrolytic oils were characterized with applying a various techniques such as elemental analyses and various chromatographic and spectroscopic techniques (GC-MS, ¹H NMR, FT-IR, etc.). The characterization results revealed that the pyrolytic oils which were complex mixtures of C₅-C₁₅ organic compounds (predominantly aromatic compounds) and also the CPO compared to the NCPO was more similar to conventional fuels in view of the certain fuel properties.     

Characterization of alkali-activated thermally treated incinerator bottom ash

The fine fraction (<14mm) of incinerator bottom ash (IBA) obtained from a UK energy from waste plant has been milled and thermally treated at 600, 700, 800 and 880 degrees C. Treated materials have been activated with Ca(OH)(2) (10wt%) and the setting times and compressive strengths at different curing times measured. In addition to decomposition of CaCO(3) to CaO, thermal treatment increases the content of gehlenite (Ca(2)Al(2)SiO(7)), wollastonite (CaSiO(3)) and mayenite (Ca(12)Al(14)O(33)). Thermally treated samples were significantly more reactive than milled IBA and heating to 700 degrees C produced a material which rapidly set. Silica, gehlenite and wollastonite were the main crystalline phases present in hydrated samples and a mixed sulphate-carbonate AFm-type phase (Ca(4)Al(2)O(6)(CO(3))(0.67)(SO(3))(0.33).11H(2)O) formed. Significant volumes of gas were generated during curing and this produced a macro-porous microstructure that limited strength to 2.8MPa. The new materials may have potential for use as controlled low-strength materials.     

Recovery of different waste vegetable oils for biodiesel production: A pilot experience in Bahia State,Brazil

In Brazil, and mainly in the State of Bahia, crude vegetable oils are widely used in the preparation of food. Street stalls, restaurants and canteens make a great use of palm oil and soybean oil. There is also some use of castor oil, which is widely cultivated in the Sertão Region (within the State of Bahia), and widely applied in industry. This massive use in food preparation leads to a huge amount of waste oil of different types, which needs either to be properly disposed of, or recovered. At the Laboratorio Energia e Gas-LEN (Energy & Gas lab.) of the Universidade Federal da Bahia, a cycle of experiments were carried out to evaluate the recovery of waste oils for biodiesel production. The experiences were carried out on a laboratory scale and, in a semi-industrial pilot plant using waste oils of different qualities. In the transesterification process, applied waste vegetable oils were reacted with methanol with the support of a basic catalyst, such as NaOH or KOH. The conversion rate settled at between 81% and 85% (in weight). The most suitable molar ratio of waste oils to alcohol was 1:6, and the amount of catalyst required was 0.5% (of the weight of the incoming oil), in the case of NaOH, and 1%, in case of KOH.The quality of the biodiesel produced was tested to determine the final product quality. The parameters analyzed were the acid value, kinematic viscosity, monoglycerides, diglycerides, triglycerides, free glycerine, total glycerine, clearness; the conversion yield of the process was also evaluated.     

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.