Pyrolysis technologies for municipal solid waste: A review

Pyrolysis has been examined as an attractive alternative to incineration for municipal solid waste (MSW) disposal that allows energy and resource recovery; however, it has seldom been applied independently with the output of pyrolysis products as end products. This review addresses the state-of-the-art of MSW pyrolysis in regards to its technologies and reactors, products and environmental impacts. In this review, first, the influence of important operating parameters such as final temperature, heating rate (HR) and residence time in the reaction zone on the pyrolysis behaviours and products is reviewed; then the pyrolysis technologies and reactors adopted in literatures and scale-up plants are evaluated. Third, the yields and main properties of the pyrolytic products from individual MSW components, refuse-derived fuel (RDF) made from MSW, and MSW are summarised. In the fourth section, in addition to emissions from pyrolysis processes, such as HCl, SO₂ and NH₃, contaminants in the products, including PCDD/F and heavy metals, are also reviewed, and available measures for improving the environmental impacts of pyrolysis are surveyed. It can be concluded that the single pyrolysis process is an effective waste-to-energy convertor but is not a guaranteed clean solution for MSW disposal. Based on this information, the prospects of applying pyrolysis technologies to dealing with MSW are evaluated and suggested.     

Kinetics of scrap tyre pyrolysis under vacuum conditions

Scrap tyre pyrolysis under vacuum is attractive because it allows easier product condensation and control of composition (gas, liquid and solid). With the aim of determining the effect of vacuum on the pyrolysis kinetics, a study has been carried out in thermobalance. Two data analysis methods have been used in the kinetic study: (i) the treatment of experimental data of weight loss and (ii) the deconvolution of DTG (differential thermogravimetry) curve. The former allows for distinguishing the pyrolysis of the three main components (volatile components, natural rubber and styrene–butadiene rubber) according to three successive steps. The latter method identifies the kinetics for the pyrolysis of individual components by means of DTG curve deconvolution. The effect of vacuum in the process is significant. The values of activation energy for the pyrolysis of individual components of easier devolatilization (volatiles and NR) are lower for pyrolysis under vacuum with a reduction of 12 K in the reaction starting temperature. The kinetic constant at 503 K for devolatilization of volatile additives at 0.25 atm is 1.7 times higher than that at 1 atm, and that corresponding to styrene–butadiene rubber at 723 K is 2.8 times higher. Vacuum enhances the volatilization and internal diffusion of products in the pyrolysis process, which contributes to attenuating the secondary reactions of the repolymerization and carbonization of these products on the surface of the char (carbon black). The higher quality of carbon black is interesting for process viability.The large-scale implementation of this process in continuous mode requires a comparison to be made between the economic advantages of using a vacuum and the energy costs, which will be lower when the technologies used for pyrolysis require a lower ratio between reactor volume and scrap tyre flow rate.     

Studies of the thermal degradation of waste rubber

One kind of Chinese waste tire's sample was pyrolyzed under an inert atmosphere by using thermo-gravimetric apparatus (TGA) and differential thermal analysis (DTA). Different pyrolysis temperature ranges were determined according to the reaction transition temperature obtained by TGA and DTA. Then, at each temperature range, the pyrolysis gaseous products were analyzed by gas chromatography (GC). The influence of the temperature range on the relative yields of the major decomposition products is studied, and a mechanism for the formation of the main components was also investigated. The results indicate that pyrolysis of waste rubber follows the radical mechanism, and the major products are not seriously affected by increasing the temperature from room temperature to 420 degrees C and from 421 to 600 degrees C, but the degradation of blend rubber is different for each of the compositional elastomer.     

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.     

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

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

Studies on the pyrolysis behavior of gasification and melting systems for municipal solid waste

 It is important to investigate the pyrolysis processes of municipal solid waste (MSW) in the same way as for any mixture comprised of multiple substances. In this article, a two-reaction model for a variety of MSW mixtures is proposed to predict mass changes due to pyrolysis. In order to formulate the model based on pyrolysis kinetics, we conducted experiments to determine the kinetic model parameters. By thermal analysis of the typical components of MSW, mass changes attributable to the pyrolysis reaction were found at about 350°C for paper, 400°–500°C for plastics, and 200°–400°C for garbage (dry condition). Activation energies were obtained by the Ozawa method based on the mass changes in pyrolysis. Thus, the pyrolysis behavior is formulated as a function of temperature. Then the pyrolysis mass change of the mixture can be predicted by using a weighted sum of the individual components. The model proved useful in experiments with real waste (refuse-derived fuels). Furthermore, the weight yields (pyrolysis gas, tars, solid residues) of the mixture can be calculated by their additive property after measuring the mass balance of each component. Received: May 11, 2001 / Accepted: November 16, 2001     

Pyrolysis of polyethylene mixed with paper and wood: Interaction effects on tar, char and gas yields

In the present study the interactions between the main constituents of the refuse derived fuel (plastics, paper, and wood) during pyrolysis were studied. Binary mixtures of polyethylene-paper and polyethylene/sawdust have been transformed into pellets and pyrolyzed. Various mixtures with different composition were analyzed and pyrolysis products (tar, gas, and char) were collected. The mixtures of wood/PE and paper/PE have a different behavior. The wood/PE mixtures showed a much reduced interaction of the various compounds because the yields of pyrolysis products of the mixture can be predicted as linear combination of those of the pure components. On the contrary, a strong char yield increase was found at a low heating rate for paper/PE mixtures. In order to explain the results, the ability of wood and paper char to adsorb and convert the products of PE pyrolysis into was studied. Adsorption and desorption tests were performed on the char obtained by paper and wood by using n-hexadecane as a model compound for the heavy products of PE pyrolysis.     

生态修复植物蜈蚣草中砷的回收

采用管式炉高温热解-NaOH-Na₂CO₃混合液碱浸-CuSO₄·5H₂O沉淀的方法回收生态修复植物蜈蚣草中的砷,最终得到产品砷酸铜。该方法的最佳工艺条件为：热解温度600 ℃,热解时间30 min,CaO加入量（CaO与蜈蚣草的质量比）8%; m（NaOH）∶m（Na₂CO₃）=1∶3,碱浸温度70 ℃, 碱浸时间2 h, 固液比1∶10; 沉淀反应pH 5, 沉淀反应温度70 ℃。采用该方法处理生态修复植物蜈蚣草,得到产品砷酸铜的纯度为93%,砷回收率达88%。     

Enhanced styrene recovery from waste polystyrene pyrolysis using response surface methodology coupled with Box–Behnken design

A work applied response surface methodology coupled with Box–Behnken design (RSM-BBD) has been developed to enhance styrene recovery from waste polystyrene (WPS) through pyrolysis. The relationship between styrene yield and three selected operating parameters (i.e., temperature, heating rate, and carrier gas flow rate) was investigated. A second order polynomial equation was successfully built to describe the process and predict styrene yield under the study conditions. The factors identified as statistically significant to styrene production were: temperature, with a quadratic effect; heating rate, with a linear effect; carrier gas flow rate, with a quadratic effect; interaction between temperature and carrier gas flow rate; and interaction between heating rate and carrier gas flow rate. The optimum conditions for the current system were determined to be at a temperature range of 470–505 °C, a heating rate of 40 °C/min, and a carrier gas flow rate range of 115–140 mL/min. Under such conditions, 64.52% WPS was recovered as styrene, which was 12% more than the highest reported yield for reactors of similar size. It is concluded that RSM-BBD is an effective approach for yield optimization of styrene recovery from WPS pyrolysis.     

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.     

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.     

The pyrolysis of sawdust and polyethylene in TG and U-shape tube reactor

The co-pyrolysis of sawdust and polyethylene was carried out in a TG-DTG system and a U-shape tube reactor. This research was focused on the interaction between sawdust and polyethylene during the pyrolysis process. The results showed that the interaction between the sawdust particles and polyethylene particles could be ignored during the devolatile process, but there was interaction among the volatile components in the co-pyrolysis process.     

土壤残留塑料的热降解脱附研究

针对土壤的塑料污染问题,提出一种采用热脱附降解技术修复污染土壤的方法.选取4种土壤中常见的残留塑料(聚乙烯(PE)、聚氯乙烯(PVC)、聚对苯二甲酸乙二酯(PET)、聚丙烯(PP))为研究对象,通过控制热解温度和土壤含水率对各污染土壤的修复效果进行探究.实验结果表明:在500℃的最佳热解温度下处理60 min,PE、P...     

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.     

水稻秸秆生物炭-过硫酸盐去除水中p-硝基酚

以水稻秸秆为原料制备了多种生物炭,运用BET和FTIR等技术对其进行了表征,研究了生物炭-过硫酸盐体系对水中p-硝基酚的去除效果。与热解温度和时间相比,供氧量对生物炭活化过硫酸盐性能的影响更为显著,足氧条件下的活化性能显著降低;500℃缺氧条件下热解1 h制备的生物炭(RS500-1)对过硫酸盐具有良好的活化性能,可以实现p-硝基酚的高效去除,生物炭与过硫酸盐之间存在显著的协同作用。初始溶液pH和反应温度对p-硝基酚的去除效果影响很小;在RS500-1投加量1.0 g/L、过硫酸盐投加量5 mmol/L、反应温度25℃、不调节初始溶液pH的优化条件下,240 min时p-硝基酚的去除率可达70%以上。     

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.     

利用农药含钾废渣制备氯化钾

利用热解及钙盐沉淀法对农药含钾废渣进行处理,制得高纯度的KCl.通过管式炉反应器对农药含钾废渣中有机物的去除进行了研究,探讨了升温速率、热解终温、终温保持时间及空气流量对热解过程的影响,并对钙盐沉淀法除氟过程的溶液pH及m(Ca2+)∶m(F-)进行了确定.实验结果表明:当升温速率为20℃/min、热解终温为600℃、终温保持时间为90 min、空气流量为3.0m3/min时,废渣中的有机物完全分解;钙盐沉淀法除氟的最佳条件为溶液pH 8,m(Ca2+)∶m(F-)=3.0,氟离子的去除率达到98％;最终得到KCl的产率为70.6％,产品纯度为98.2％,符合国家Ⅰ级优等品标准.     

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.     

The important role of microwave receptors in bio-fuel production by microwave-induced pyrolysis of sewage sludge

Microwave receptor plays an important role in the microwave pyrolysis of sewage sludge in view of its significant influence on the yield and property of bio-fuel products. The yield and the chemical compositions of bio-fuels (gases and oils) obtained from sewage sludge mixed with different receptors (graphite, residue char, active carbon or silicon carbide) were investigated in this study by Gas Chromatography (GC), Gas Chromatography-Mass Spectrometry (GC-MS), and Fourier Transform Infrared Spectroscopy (FTIR). The results showed that the use of silicon carbide gave rise to the highest final temperature of 1130 °C, resulting in the highest yield of gas fraction (up to 63.2 wt.%). The low heating rate (200 °C/min) which was attributed to the addition of residue char promoted condensation reactions and resulted in an increase in solid yield. The existence of active carbon could prolong the resistance time of volatiles in the hot zone owing to its porous structure, generating the maximum concentration of H₂ + CO (60%) in the pyrolysis gas. When graphite was used, the final low temperature favoured the cyclization of the alkenes, giving rise to a higher concentration of mononuclear aromatics in the pyrolysis oils. The model established in this study revealed that the quantity and quality of the products obtained from the microwave pyrolysis highly depended on the process conditions, which were influenced by the receptor significantly.     

Thermogravimetric analysis and kinetic study on pyrolysis of representative medical waste composition

To obtain detailed information on the pyrolysis characteristics, a thermogravimetric study on the pyrolysis of 14 typical medical waste compositions was carried out in thermogravimetric analysis (TGA) equipment using dynamic techniques in a stream of N(2). An index representing pyrolysis reactivity of waste was presented. Kinetic parameters were obtained by Coats-Redfern method and used to model the TG curve. The results showed that: (a) Plastic, protein, cellulosic material, synthetic fibre, and rubber entered pyrolysis process in succession. (b) There was one decomposition stage in the pyrolysis of one-off medical glove, operating glove, cellulosic waste, absorbable catgut suture and adhesive plaster, while other components had two obvious weight loss stages. (c) The obtained apparent activation energy for second stage pyrolysis was comparably higher than that for first stage. (d) Each stage was controlled by only one kinetic mechanism, in which kinetic parameters were constant. (e) The degradation kinetics of medical waste may be affected by special physical and chemical treatment in the product manufacturing process. (f) Among 13 waste samples, the pyrolysis index of cellulosic matter was the highest, which indicated cellulosic matter had strong pyrolysis reactivity. (g) With increasing heating rate, TG curve and DTG peak shifted to high temperatures and main reaction interval of the sample became longer.