Pyrolysis of municipal plastic wastes: Influence of raw material composition

The objective of this work is the study of pyrolysis as a feedstock recycling process, for valorizing the rejected streams that come from industrial plants, where packing and packaging wastes are classified and separated for their subsequent mechanical recycling. Four real samples collected from an industrial plant at four different times of the year, have been pyrolysed under nitrogen in a 3.5 dm³ autoclave at 500 °C for 30 min. Pyrolysis liquids are a complex mixture of organic compounds containing valuable chemicals as styrene, ethyl-benzene, toluene, etc. Pyrolysis solids are composed of the inorganic material contained in the raw materials, as well as of some char formed in the pyrolysis process, and pyrolysis gases are mainly composed of hydrocarbons together with some CO and CO₂, and have very high gross calorific values (GCV).It has been proved by the authors that the composition of the raw material (paper, film, and metals contents) plays a significant role in the characteristics of pyrolysis products. High paper content yields water in the pyrolysis liquids, and CO and CO₂ in the gases, high PE film content gives rise to high viscosity liquids, and high metals content yields more aromatics in the liquid products, which may be attributed to the metals catalytic effect.     

Deactivation and regeneration of ZSM-5 zeolite in catalytic pyrolysis of plastic wastes

In this work, a study of the regeneration and reuse of ZSM-5 zeolite in the pyrolysis of a plastic mixture has been carried out in a semi-batch reactor at 440 °C. The results have been compared with those obtained with fresh-catalyst and in non-catalytic experiments with the same conditions. The use of fresh catalyst produces a significant change in both the pyrolysis yields and the properties of the liquids and gases obtained. Gases more rich in C3-C4 and H₂ are produced, as well as lower quantities of aromatic liquids if compared with those obtained in thermal decomposition. The authors have proved that after one pyrolysis experiment the zeolite loses quite a lot of its activity, which is reflected in both the yields and the products quality; however, this deactivation was found to be reversible since after regeneration heating at 550 °C in oxygen atmosphere, this catalyst recovered its initial activity, generating similar products and in equivalent proportions as those obtained with fresh catalyst.     

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.     

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.     

Pyrolysis behavior of different type of materials contained in the rejects of packaging waste sorting plants

In this paper rejected streams coming from a waste packaging material recovery facility have been characterized and separated into families of products of similar nature in order to determine the influence of different types of ingredients in the products obtained in the pyrolysis process. The pyrolysis experiments have been carried out in a non-stirred batch 3.5 dm³ reactor, swept with 1 L min^?1 N₂, at 500 °C for 30 min. Pyrolysis liquids are composed of an organic phase and an aqueous phase. The aqueous phase is greater as higher is the cellulosic material content in the sample. The organic phase contains valuable chemicals as styrene, ethylbenzene and toluene, and has high heating value (HHV) (33–40 MJ kg^?1). Therefore they could be used as alternative fuels for heat and power generation and as a source of valuable chemicals. Pyrolysis gases are mainly composed of hydrocarbons but contain high amounts of CO and CO₂; their HHV is in the range of 18–46 MJ kg^?1. The amount of COCO₂ increases, and consequently HHV decreases as higher is the cellulosic content of the waste. Pyrolysis solids are mainly composed of inorganics and char formed in the process. The cellulosic materials lower the quality of the pyrolysis liquids and gases, and increase the production of char.     

Pyrolysis and catalytic pyrolysis as a recycling method of waste CDs originating from polycarbonate and HIPS

Pyrolysis appears to be a promising recycling process since it could convert the disposed polymers to hydrocarbon based fuels or various useful chemicals. In the current study, two model polymers found in WEEEs, namely polycarbonate (PC) and high impact polystyrene (HIPS) and their counterparts found in waste commercial Compact Discs (CDs) were pyrolysed in a bench scale reactor. Both, thermal pyrolysis and pyrolysis in the presence of two catalytic materials (basic MgO and acidic ZSM-5 zeolite) was performed for all four types of polymers. Results have shown significant recovery of the monomers and valuable chemicals (phenols in the case of PC and aromatic hydrocarbons in the case of HIPS), while catalysts seem to decrease the selectivity towards the monomers and enhance the selectivity towards other desirable compounds.     

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.     

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.     

Pyrolysis of mixtures of sewage sludge and manure: a comparison of the results obtained in the laboratory (semi-pilot) and in a pilot plant

A pilot-scale pyrolysis process was carried out for the treatment of a mixture of two types of waste, sewage sludge and cattle manure, comparing the results with others obtained under laboratory conditions (semi-pilot scale). The aim of this study was to obtain the energetic valorization of the products. Owing to the specific characteristics of the plant, two products were obtained from the process: gas and carbonized solid. As no liquid fraction was obtained, the gas fraction is a greater percentage made up of both condensable and non-condensable compounds, which were obtained separately at the laboratory scale. The pilot plant was designed so that the gases produced by thermolysis were burnt continuously in a combustion chamber, while the carbonized fraction was fed in batches for co-combustion. To determine composition and combustion ability, the gas and solid products from the pilot process were characterized by chromatographic analysis of the gaseous fraction and chemical analysis and programmed-temperature combustion of the carbonized solid. The composition of the combustion gases, rich in light hydrocarbons, and the carbon present in the carbonized fraction enable the energetic valorization of these products. The combustion gases were subjected to a cleaning process and their composition analysed twice: before and after the gas cleaning treatment. The study led to a positive assessment of the possible use of the process products as fuel, provided that the combustion gases are treated. As most of the sulphur and chlorine from the original waste are mainly concentrated in the solid fraction, the use of char as a fuel will depend on the effectiveness of clean-up techniques for combustion gases. During gas cleansing, neutralizing with sodium bicarbonate proved effective, especially for the acidic compounds HCl, HF and SO(2).     

Pyrolysis of the tetra pak

This study deals with pyrolysis of tetra pak which is widely used as an aseptic beverage packaging material. Pyrolysis experiments were carried out under inert atmosphere in a batch reactor at different temperatures and by different pyrolysis modes (one- and two-step). The yields of char, liquid and gas were quantified. Pyrolysis liquids produced were collected as three separate phases; aqueous phase, tar and polyethylene wax. Characterization of wax and the determination of the total amount of phenols in aqueous phase were performed. Chemical compositions of gas and char products relevant to fuel applications were determined. Pure aluminum can be also recovered by pyrolysis.     

Utilization of amorphous rice husk ash for the synthesis of ZSM-5 zeolite under low temperature

The present study deals with the production and characterization of ZSM-5 zeolite under low temperature using amorphous rice husk ash as an alternative cheap silica source. Rice husk was combusted at various temperatures for the production of amorphous silica. The resulted amorphous silica ash was then utilized without any other treatment as a starting material for the synthesis of ZSM-5 zeolite using low temperature and under atmospheric pressure. For comparison, the high-temperature synthetic approach, the hydrothermal treatment under high temperature and autogenous pressure with the autoclave process, was also applied for the synthesis of ZSM-5 zeolite. The low-temperature method led successfully to the synthesis of highly siliceous zeolite of type ZSM-5. The produced materials were characterized using a variety of analytical techniques, including X-ray diffraction, Fourier transformation infrared spectroscopy, thermogravimetry–differential thermogravimetry analyses, scanning electron microscopy, electron dispersion X-ray analysis and nitrogen porosimetry. The results show that the utilization of an industrial by-product in abundance as a starting material can lead through a simple inexpensive technique to the synthesis of a high value added microporous material with many potential applications.     

Characterization of products obtained from pyrolysis and steam gasification of wood waste,RDF, and RPF

Pyrolysis and steam gasification of woody biomass chip (WBC) obtained from construction and demolition wastes, refuse-derived fuel (RDF), and refuse paper and plastic fuel (RPF) were performed at various temperatures using a lab-scale instrument. The gas, liquid, and solid products were examined to determine their generation amounts, properties, and the carbon balance between raw material and products.The amount of product gas and its hydrogen concentration showed a considerable difference depending on pyrolysis and steam gasification at higher temperature. The reaction of steam and solid product, char, contributed to an increase in gas amount and hydrogen concentration. The amount of liquid products generated greatly depended on temperature rather than pyrolysis or steam gasification. The compositions of liquid product varied relying on raw materials used at 500 °C but the polycyclic aromatic hydrocarbons became the major compounds at 900 °C irrespective of the raw materials used. Almost fixed carbon (FC) of raw materials remained as solid products under pyrolysis condition whereas FC started to decompose at 700 °C under steam gasification condition.For WBC, both char utilization by pyrolysis at low temperature (500 °C) and syngas recovery by steam gasification at higher temperature (900 °C) might be practical options. From the results of carbon balance of RDF and RPF, it was confirmed that the carbon conversion to liquid products conspicuously increased as the amount of plastic increased in the raw material. To recover feedstock from RPF, pyrolysis for oil recovery at low temperature (500 °C) might be one of viable options. Steam gasification at 900 °C could be an option but the method of tar reforming (e.g. catalyst utilization) should be considered.     

NiO-CuO/ZSM-5催化剂对催化裂化烟气的脱硫脱硝性能

采用浸渍法制备了不同NiO和CuO质量分数的NiO-CuO/ZSM-5催化剂,并以CH4为还原剂研究了NiO-CuO/ZSM-5催化剂对催化裂化烟气的脱硫脱硝活性。XRD分析结果表明,NiO质量分数为4%、CuO质量分数为6%的催化剂4%NiO-6%CuO/ZSM-5中的ZSM-5结构完好,CuO和NiO高度分散在ZSM-5骨架中,表明具有较好的催化活性。4%NiO-6%CuO/ZSM-5的脱硫脱硝起活温度均较低,无氧条件下最高NO转化率和SO2转化率分别为94.7%和95.9%,O2体积分数为1.0%时的NO转化率和SO2转化率分别为97.7%和89.0%。     

Thermocatalytic Degradation of High Density Polyethylene into Liquid Product

Thermocatalytic degradation of high density polyethylene (HDPE) was carried out using acid activated fire clay catalyst in a semi batch reactor. Thermal pyrolysis was performed in the temperature range of 420–500 °C. The liquid and gaseous yields were increased with increase in temperature. The liquid yield was obtained 30.1 wt% with thermal pyrolysis at temperature of 450 °C, which increased to 41.4 wt% with catalytic pyrolysis using acid activated fire clay catalyst at 10 wt% of catalyst loading. The composition of liquid products obtained by thermal and catalytic pyrolysis was analyzed by gas chromatography-mass spectrometry and compounds identified for catalytic pyrolysis were mainly paraffins and olefins with carbon number range of C₆–C₁₈. The boiling point was found in the range of commercial fuels (gasoline, diesel) and the calorific value was calculated to be 42 MJ/kg.     

改性Y沸石催化降解聚苯乙烯的研究

用热重分析方法研究了HY沸石与改性Y沸石(UHY)作为催化降解聚苯乙烯的催化剂对聚苯乙烯催化降解的作用及影响,对聚苯乙烯的催化降解与热降解反应产物进行了比较。结果表明,催化剂的存在能显著地降低聚苯乙烯的降解温度,催化剂的酸量和孔结构对聚苯乙烯的降解温度、活化能、积炭的生成量及裂解产物有很大的影响。     

Distribution of copper,silver and gold during thermal treatment with brominated flame retardants

The growing consumption of electric and electronic equipment results in creating an increasing amount of electronic waste. The most economically and environmentally advantageous methods for the treatment and recycling of waste electric and electronic equipment (WEEE) are the thermal techniques such as direct combustion, co-combustion with plastic wastes, pyrolysis and gasification. Nowadays, this kind of waste is mainly thermally treated in incinerators (e.g. rotary kilns) to decompose the plastics present, and to concentrate metals in bottom ash. The concentrated metals (e.g. copper, precious metals) can be supplied as a secondary raw material to metal smelters, while the pyrolysis of plastics allows the recovery of fuel gases, volatilising agents and, eventually, energy. Indeed, WEEE, such as a printed circuit boards (PCBs) usually contains brominated flame retardants (BFRs). From these materials, hydrobromic acid (HBr) is formed as a product of their thermal decomposition.In the present work, the bromination was studied of copper, silver and gold by HBr, originating from BFRs, such as Tetrabromobisphenol A (TBBPA) and Tetrabromobisphenol A-Tetrabromobisophenol A diglycidyl ether (TTDE) polymer; possible volatilization of the bromides formed was monitored using a thermo-gravimetric analyzer (TGA) and a laboratory-scale furnace for treating samples of metals and BFRs under an inert atmosphere and at a wide range of temperatures. The results obtained indicate that up to about 50% of copper and silver can evolve from sample residues in the form of volatile CuBr and AgBr above 600 and 1000 °C, respectively. The reactions occur in the molten resin phase simultaneously with the decomposition of the brominated resin. Gold is resistant to HBr and remains unchanged in the residue.     

Study on the conversion of waste plastics/petroleum resid mixtures to transportation fuels

Catalytic coprocessing of model and waste plastics with light Arabian crude oil residue was investigated using NiMo/Al₂O₃, ZSM-5, FCC, and hydrocracking catalysts. Reaction systems that were studied included low density polyethylene (LDPE), high density polyethylene (HDPE), polystyrene (PS), and polypropylene (PP). A series of single (plastic/catalyst) and binary (plastic/resid/catalyst) reactions were carried out in a 25-cm³ micro autoclave reactor under different conditions of weight and type of catalyst, duration, pressure, and temperature. The optimum conditions selected for our work were: 1% catalyst by weight of total feedstock weight, 60min reaction time, 8.3Mpa of H₂, and 430°C. The product distribution for the binary system using plastic and petroleum residue provided some encouraging results. High yields of liquid fuels in the boiling range of 100°–480°C and gases were obtained along with a small amount of heavy oils and insoluble material such as gums and coke. In general, this study helps to demonstrate the technical feasibility of upgrading both waste plastics and petroleum resid, as well as an alternative approach to feedstock recycling.     

淬火油泥的热解动力学分析及协同作用研究

采用热重差热分析法和傅里叶变换红外光谱分析联用的方法（TG-FTIR）研究淬火油泥（QOS）的热解过程,解析了热解过程的动力学特性,分析了其中的矿物油（MO）和残渣（SR）在QOS热解过程中的相互作用。实验结果表明：QOS热解过程包含油分热解阶段和矿物质分解阶段;低温段热解温度为150~520 ℃,高温段热解温度为800~980 ℃;SR的热解过程分为油分热解反应和残渣中Fe₂O₃的还原反应;MO的热解过程只有轻质油分的挥发和重质油分的热解。FTIR表征结果显示：QOS热解过程析出的气体主要为CO₂、CO和有机化合物;SR热解过程中CO₂的特征峰强度高于其他气体的特征峰强度;MO热解过程中烷烃的特征峰强度高于其他气体的特征峰强度,且MO主要以轻质油分为主。在QOS的热解过程中,初温~480 ℃时,SR所含的Fe₂O₃对MO的热解起促进作用,300 ℃左右时促进效果最明显。     

聚乙烯副产物聚乙烯蜡的热解及轻质馏分的GC-MS分析

采用高温模拟蒸馏、红外光谱和热重分析等方法对聚乙烯副产物聚乙烯蜡进行了表征。在间歇高压反应釜中对聚乙烯副产物聚乙烯蜡进行了热解,并通过正交实验考察了热解温度、停留时间和初始压力对液相产物收率的影响。利用GC-MS技术对液相产物轻质馏分(低于200℃)进行了分析。结果表明:聚乙烯副产物聚乙烯蜡主要由长链脂肪烃(C_(14)~C_(70))组成;热解发生的温度范围为175~490℃;热解温度和停留时间是影响液相产物收率的主要因素;液相产物轻质馏分的碳数分布在C_9~C_(20),主要为α-烯烃(占比32.79%)和正构烷烃,其中单体烃含量最高的是1-癸烯(占比8.46%),它是制备高级合成润滑油聚α-烯烃的优质原料。     

Recovery of glass fibers from glass fiber reinforced plastics by pyrolysis

Fiber-reinforced plastic sheets containing unsaturated polyester cross-linked with styrene, CaCO₃ and glass fibers as fillers were pyrolyzed in a helium and steam atmosphere in order to recover glass fibers and valuable organic pyrolysis products. Glass fibers were separated from CaCO₃ and CaO by dissolving calcium salts in hydrochloric acid. Residual organic material was burnt afterwards. Best results were obtained at a pyrolysis temperature of 600 and 700 °C, resulting in a large liquid fraction high in styrene, leaving little residual organic material on the surface of the glass fibers. At a pyrolysis temperature of 500 °C, the degradation of the polymer matrix was incomplete, and at 900 °C, glass fibers were destroyed in the presence of CaO, leaving CaSiO₃ as a product.