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.     

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.     

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.     

Determination of the Burning Characteristics of a Slick of Oil on Water

The burning rate of a slick of oil on a water bed is characterized by three distinct processes, ignition, flame spread and burning rate. Although all three processes are important, ignition and burning rate are critical. The former, because it defines the potential to burn and the latter because of the inherent possibility of boilover. Burning rate is calculated by a simple expression derived from a one-dimensional heat conduction equation. Heat feedback from the flame to the surface is assumed to be a constant fraction of the total energy released by the combustion reaction. The constant fraction (χ) is named the burning efficiency and represents an important tool in assessing the potential of in situ burning as a counter-measure to an oil spill. By matching the characteristic thermal penetration length scale for the fuel/water system and an equivalent single layer system, a combined thermal diffusivity can be calculated and used to obtain an analytical solution for the burning rate. Theoretical expressions were correlated with crude oil and heating oil, for a number of pool diameters and initial fuel layer thickness. Experiments were also conducted with emulsified and weathered crude oil. The simple analytical expression describes well the effects of pool diameter and initial fuel layer thickness permitting a better observation of the effects of weathering, emulsification and net heat feedback to the fuel surface. Experiments showed that only a small fraction of the heat released by the flame is retained by the fuel layer and water bed (of the order of 1%). Ignition has been studied to provide a tool that will serve to assess a fuels ease to ignite under conditions that are representative of oil spills. Two different techniques are used, piloted ignition when the fuel is exposed to a radiant heat flux and flash point as measured by the ASTM D56 Tag Closed Cup Test. Two different crude oils were used for these experiments, ANS and Cook Inlet. Crude oils were tested in their natural state and at different levels of weathering, showing that piloted ignition and flash point are strong functions of weathering level.     

Pyrolysis of tyres. Influence of the final temperature of the process on emissions and the calorific value of the products recovered

A study was made of the pyrolysis of tyre particles, with the aim of determining the possibilities of using the products resulting from the process as fuel. Three final temperatures were used, determined from thermogravimetric data. The design of the experiment was a horizontal oven containing a reactor into which particles of the original tyre were placed. After the process, a solid fraction (char) remained in the reactor, while the gases generated went through a set of scrubbers where most of the condensable fraction (oils) was retained. Finally, once free of this fraction, the gases were collected in glass ampoules. Solid and liquids fractions were subjected to thermogravimetric analyses in order to study their combustibility. The gas fraction was analysed by means of gas chromatography to establish the content of CO, CO2, H2 and hydrocarbons present in the samples (mainly components of gases produced in the pyrolysis process). A special study was made of the sulphur and chlorine content of all the fractions, as the presence of these elements could be problematic if the products are used as fuel. Tyre pyrolysis engenders a solid carbon residue that concentrates sulphur and chorine, with a relatively high calorific value, although not so high as that of the original tyre. The liquid fraction produced by the process has a high calorific value, which rises with the final temperature, up to 40 MJ/kg. The chlorine content of this fraction is negligible. Over 95% of the gas fraction, regardless of the final temperature, is composed of hydrocarbons of a low molecular weight and hydrogen, this fraction also appearing to be free of chlorine.     

Ignition and burning rates of segregated waste combustion in packed beds

Recent developments in national recycling and re-use programmes for municipal waste have led to segregation of an increasing proportion of waste to enhance material recovery. Several of the segregated streams contain materials that can not viably be re-used or recycled but can be used for energy recovery. In this study, the combustion of cardboard and waste wood was investigated in a small-scale packed bed reactor in order to provide fundamental data for the design/operation of moving bed furnaces. Key parameters of combustion including the ignition and burning rates were evaluated for various air flowrates and compared to the modelling results. Two successive stages of combustion were identified for both samples: the propagation of ignition front into the bed and combustion of the fuel above the ignition front. The burning rate of cardboard reached a peak of about 300 kg/m(2)h at the air flowrate of 936 kg/m(2)h and decreased at higher air flowrates. For waste wood, both the ignition and burning rates increased in the tested range of the air flowrate up to 702 kg/m(2)h, of which the values were very close to those for the cardboard. The model prediction was in good agreement with the test results for waste wood. However, the burning rate for cardboard was under-predicted due to strongly irregular shapes of the fuel.     

等离子点火燃烧技术在电厂节能和环保方面的应用

介绍了等离子点火技术在浙江长兴电厂3号炉上的应用.自电厂进行等离子点火装置改造并正式投运以来,取得了良好的经济效益和节能效果,环境效益也十分显著,实现了低负荷断油燃烧,节油率达90%左右,1台300 MW机组可节约燃油成本180 万元/a.     

Removal potential of toxic 2378-substituted PCDD/F from incinerator flue gases by waste-derived activated carbons

The application of activated carbons has become a commonly used emission control protocol for the removal or adsorption of persistent organic pollutants from the flue gas streams of waste incinerators. In this study, the 2378-substituted PCDD/F removal efficiency of three types of activated carbons derived from the pyrolysis of refuse derived fuel, textile waste and scrap tyre was investigated and compared with that of a commercial carbon. Experiments were carried out in a laboratory scale fixed-bed reactor under a simulated flue gas at 275 °C with a reaction period of four days. The PCDD/F in the solid matrices and exhaust gas, were analyzed using gas chromatography coupled with a triple quadrupole mass spectrometer. In the absence of activated carbon adsorbent, there was a significant increase in the concentration of toxic PCDD/F produced in the reacted flyash, reaching up to 6.6 times higher than in the raw flyash. In addition, there was a substantial release of PCDD/F into the gas phase, which was found in the flue gas trapping system. By application of the different commercial, refuse derived fuel, textile and tyre activated carbons the total PCDD/F toxic equivalent removal efficiencies in the exhaust gas stream were 58%, 57%, 64% and 52%, respectively. In general, the removal of the PCDDs was much higher with an average of 85% compared to PCDFs at 41%. Analysis of the reacted activated carbons showed that there was some formation of PCDD/F, for instance, a total of 60.6 μg I-TEQ kg⁻¹ toxic PCDD/F was formed in the refuse derived fuel activated carbon compared to 34 μg I-TEQ kg⁻¹ in the commercial activated carbon. The activated carbons derived from the pyrolysis of waste, therefore, showed good potential as a control material for PCDD/F emissions in waste incinerator flue gases.     

Emissions from US waste collection vehicles

This research is an in-depth environmental analysis of potential alternative fuel technologies for waste collection vehicles. Life-cycle emissions, cost, fuel and energy consumption were evaluated for a wide range of fossil and bio-fuel technologies. Emission factors were calculated for a typical waste collection driving cycle as well as constant speed. In brief, natural gas waste collection vehicles (compressed and liquid) fueled with North-American natural gas had 6–10% higher well-to-wheel (WTW) greenhouse gas (GHG) emissions relative to diesel-fueled vehicles; however the pump-to-wheel (PTW) GHG emissions of natural gas waste collection vehicles averaged 6% less than diesel-fueled vehicles. Landfill gas had about 80% lower WTW GHG emissions relative to diesel. Biodiesel waste collection vehicles had between 12% and 75% lower WTW GHG emissions relative to diesel depending on the fuel source and the blend. In 2011, natural gas waste collection vehicles had the lowest fuel cost per collection vehicle kilometer travel. Finally, the actual driving cycle of waste collection vehicles consists of repetitive stops and starts during waste collection; this generates more emissions than constant speed driving.     

Performance and emission study of biodiesel from leather industry pre-fleshings

The possible use of pre-fleshing wastes from tanneries in the production of biodiesel fuel was examimed in our previous study in 2005. In this study, engine performance and emission values of biodiesel obtained from these wastes have been investigated and compared to petrodiesel fuel. The test results demonstrated that although the wheel force and power of biodiesel fuel is slightly lower than petrodiesel and the acceleration periods are accordingly longer, the emission values of hydrocarbons and particulate matter were found to be considerably lower with biodiesel. Thus, it has been shown that a waste byproduct can be utilized in the production of an environmentally friendly fuel, which can be used in some diesel engines without a need for major adjustment, providing economic and ecological benefits.     

Experimental investigation of wood combustion in a fixed bed with hot air

Waste combustion on a grate with energy recovery is an important pillar of municipal solid waste (MSW) management in the Netherlands. In MSW incinerators fresh waste stacked on a grate enters the combustion chamber, heats up by radiation from the flame above the layer and ignition occurs. Typically, the reaction zone starts at the top of the waste layer and propagates downwards, producing heat for drying and devolatilization of the fresh waste below it until the ignition front reaches the grate. The control of this process is mainly based on empiricism.MSW is a highly inhomogeneous fuel with continuous fluctuating moisture content, heating value and chemical composition. The resulting process fluctuations may cause process control difficulties, fouling and corrosion issues, extra maintenance, and unplanned stops. In the new concept the fuel layer is ignited by means of preheated air (T > 220 °C) from below without any external ignition source. As a result a combustion front will be formed close to the grate and will propagate upwards. That is why this approach is denoted by upward combustion.Experimental research has been carried out in a batch reactor with height of 4.55 m, an inner diameter of 200 mm and a fuel layer height up to 1 m. Due to a high quality two-layer insulation adiabatic conditions can be assumed. The primary air can be preheated up to 350 °C, and the secondary air is distributed via nozzles above the waste layer. During the experiments, temperatures along the height of the reactor, gas composition and total weight decrease are continuously monitored. The influence of the primary air speed, fuel moisture and inert content on the combustion characteristics (ignition rate, combustion rate, ignition front speed and temperature of the reaction zone) is evaluated.The upward combustion concept decouples the drying, devolatilization and burnout phase. In this way the moisture and inert content of the waste have almost no influence on the combustion process. In this paper an experimental comparison between conventional and reversed combustion is presented.     

Smoldering Combustion (STAR) for the Treatment of Contaminated Soils: Examining Limitations and Defining Success

Smoldering combustion, commercially available as the Self‐sustaining Treatment for Active Remediation (STAR) technology, is an innovative technique that has shown promise for the remediation of contaminant source zones. Smoldering combustion is an exothermic reaction (net energy producing) converting carbon compounds and an oxidant (e.g., oxygen in air) to carbon dioxide, water, and energy. Thus, following ignition, the smoldering combustion reaction can continue in a self‐sustaining manner (i.e., no external energy or added fuel input following ignition) as the heat generated by the reacting contaminants is used to preheat and initiate combustion of contaminants in adjacent areas, propagating a combustion front through the contaminated zone provided a sufficient flux of air is supplied. The STAR technology has applicability across a wide‐range of hydrocarbons in a variety of hydrogeologic settings; however, there are limitations to its use. Impacted soils must be permeable enough to allow a sufficient flux of air to the combustion front and there exists a minimum required concentration of contaminants such that the soils contain sufficient fuel for the reaction to proceed in a self‐sustaining manner. Further limitations, as well as lessons learned and methods to mitigate these limitations, are presented through a series of case studies. In summary, the successful implementation of STAR will result in >99 percent reduction in contaminant concentrations in treated areas, limited residual contaminant mass, reduced groundwater contaminant mass flux which can be addressed through monitored natural attenuation; and an enhanced site exit strategy, reduced lifecycle costs, and reduced risk. ©2016 Wiley Periodicals, Inc.     

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.     

Toxicity and source assignment of polycyclic aromatic hydrocarbons in road dust from urban residential and industrial areas in a typical industrial city in Korea

This study analyzed the toxicity and sources of polycyclic aromatic hydrocarbons (PAHs) in road dust from six representative areas (three urban residential areas and three industrial areas) from a typical industrial city in Korea. The concentrations and the toxicity equivalent concentrations (TEQs) in road dust varied by area, depending on the type of traffic and industrial activities and the PAHs identified. High correlations between the total concentration and the TEQ of PAHs in road dust were found in road dust from both the urban and industrial areas. To identify the sources of PAHs, this study utilized a factor loading method in a principal component analysis, the ratio of PAHs from combustion sources to total PAHs (ΣCOMB to ΣPAH), and bivariate plots of phenanthrene/anthracene (PA/Ant) versus fluoranthene/pyrene (FL/Pyr), and ΣCOMB/ΣPAH versus FL/Pyr in road dust. The identified origin of the PAHs was fuel combustion, including gasoline, diesel, oil, and coal, used in urban and industrial areas.     

Co-combustion of waste from olive oil production with coal in a fluidised bed

Waste from olive oil production was co-fired with coal in a fluidised bed combustor to study the feasibility of using this waste as an energy source. The combustion efficiency and CO emission were investigated and compared to those of burning 100% of coal. Olive oil waste with up to 20% mass concentration can be co-fired with coal in a fluidised bed combustor designed for coal combustion with a maximum drop of efficiency of 5%. A 10% olive oil waste concentration gave a lower CO emission than 100% coal firing due to improved combustion in the freeboard region. A 20% olive oil waste mixture gave a higher CO emission than both 100% coal firing and 10% olive oil waste mixture, but the combustion efficiency was higher than the 10% olive oil waste mixture due to lower elutriation from the bed.     

Fundamental study of the behavior of chlorine during the combustion of single RDF

A fundamental study of the combustion characteristics and the de-HCl behavior of a single refuse-derived fuel (RDF) pellet was carried out to explain the de-HCl phenomena of RDF during fluidized bed combustion and to provide data for the development of high efficiency power generation technology using RDF. In this research, combustion and pyrolysis experiments were carried out in an electrical furnace using a series of model and actual RDF samples. The de-HCl capability of Ca(OH)2 in RDF was evaluated by measuring the emission fraction of HCl in the flue gas and the capture fraction of Cl in the residue. It was found that the capture fraction of Cl components in the residue increased from 0 to nearly 70% when the molar ratio of Ca/Cl was changed from 0 to around 13. Apparently, the capture fraction also decreased with increasing oxygen concentration in the feed gas. The devolatilization process of RDF was confirmed to be a very important part of de-HCl process. The effect of temperature profile of the RDF pellet on the de-HCl process, as it varies with the heating rate of RDF and the oxygen concentration in the vicinity of the sample, is discussed.     

Valorisation of waste tyre by pyrolysis in a moving bed reactor

The aim of this work is to assess the behaviour of a moving bed reactor, based on a screw transporter design, in waste tyre pyrolysis under several experimental conditions. Waste tyre represents a significant problem in developed countries and it is necessary to develop new technology that could easily process big amounts of this potentially raw material. In this work, the influence of the main pyrolysis process variables (temperature, solid residence time, mass flow rate and inert gas flow) has been studied by a thorough analysis of product yields and properties. It has been found that regardless the process operational parameters, a total waste tyre devolatilisation is achieved, producing a pyrolytic carbon black with a volatile matter content under 5 wt.%. In addition, it has been proven that, in the range studied, the most influencing process variables are temperature and solid mass flow rate, mainly because both variables modify the gas residence time inside the reactor. In addition, it has been found that the modification of these variables affects to the chemical properties of the products. This fact is mainly associated to the different cracking reaction of the primary pyrolysis products.     

Thermal-behavior study of chlorine released from composite refuse derived fuel

In order to reduce secondary pollution during the incineration of composite refuse derived fuel (CRDF), the combustion features and the emission behavior of chlorine in CRDF containing coal were analyzed. The former was analyzed using thermo-gravimetric and the latter by gas chromatography–mass spectrometry. The release rate of inorganic chlorine during combustion reached 90 mass% at temperature between 773.15 and 873.15 K. On the other hand, approximately 84 mass% release rates was resulting from pyrolysis at 723.15 K. When temperature reached above 1073.15 K, it was noticed that higher concentration of organic chlorine in different organic compounds were produced in the processing of pyrolysis compared with those released from the combustion processing. From the thermo-gravimetric analysis using a self-designed system, three distinct phases were detected in the thermal process of CRDF. The first phase occurred at temperature between 473 and 573 K and its mass loss was about 38.50%. The second phase between temperature regions of 673–773 K with a mass loss of 20.35%. The third phase was observed at the temperature between 873 and 1073 K with 22.25% mass loss.     

Vacuum pyrolysis process for remediation of hydrocarbon-contaminated soils

A vacuum pyrolysis process was used for the remediation of hydrocarbon–contaminated soils from “Les Vidangeurs de Montréal” site in Mascouche in the province of Québec, near Montréal. Ten samples were tested on a laboratory scale batch reactor, and one sample was tested on a prototype process development unit. The process is simple, efficient, reliable, and economically competitive with other existing technologies. The vacuum pyrolysis process efficiently treated soils contaminated with a variety of pollution levels and types, irrespective of the soil matrix, providing treated soils meeting the A criterion (noncontaminated, residential level) of the Ministry of Environment Québec (MENVIQ). The pyrolytic oil and the noncondensable pyrolytic gases can be used as makeup fuel in the process, because they have a high calorific value and their combustion should not pose any emission problems. The waterphase effluent must be treated before discharge.     

废印制线路板真空热解产物分析

在自行设计的间歇式固定床真空热解装置中热解废印制线路板(PCB),对热解产物进行了分析.在热解温度为550 ℃、热解压力为20 kPa、恒温时间为60 min的条件下,得到的热解产物质量分数为:热解渣70%;热解油3%～4%;不可冷凝热解气26%～27%.经气相色谱-质谱联用(GC-MS)分析,热解油经常压蒸馏后得到的低沸点液态油中含有29种化合物,主要有苯酚、对异丙基酚、3-乙基酚、4-甲酚及2-溴苯酚,还含有少量含溴化合物和含氯化合物.热解油经简单的蒸馏就可达到回收酚类化合物的目的.热解渣经风选可实现铜与黏附有碳黑的玻璃纤维的分离,其中铜质量分数约30%,黏附有碳黑的玻璃纤维质量分数约70%.