Pyrolysis-gasification of plastics, mixed plastics and real-world plastic waste with and without Ni-Mg-Al catalyst

Polypropylene, polystyrene, high density polyethylene and their mixtures and real-world plastic waste were investigated for the production of hydrogen in a two-stage pyrolysis-gasification reactor. The experiments were carried out at gasification temperatures of 800 or 850 °C with or without a Ni-Mg-Al catalyst. The influence of plastic type on the product distribution and hydrogen production in relation to process conditions were investigated. The reacted Ni-Mg-Al catalysts were analyzed by temperature-programmed oxidation and scanning electron microscopy. The results showed that lower gas yield (11.2 wt.% related to the mass of plastic) was obtained for the non-catalytic non-steam pyrolysis-gasification of polystyrene at the gasification temperature of 800 °C, compared with the polypropylene (59.6 wt.%) and high density polyethylene (53.5 wt.%) and waste plastic (45.5 wt.%). In addition, the largest oil product was observed for the non-catalytic pyrolysis-gasification of polystyrene. The presence of the Ni-Mg-Al catalyst greatly improved the steam pyrolysis-gasification of plastics for hydrogen production. The steam catalytic pyrolysis-gasification of polystyrene presented the lowest hydrogen production of 0.155 and 0.196 (g H₂/g polystyrene) at the gasification temperatures of 800 and 850 °C, respectively. More coke was deposited on the catalyst for the pyrolysis-gasification of polypropylene and waste plastic compared with steam catalytic pyrolysis-gasification of polystyrene and high density polyethylene. Filamentous carbons were observed for the used Ni-Mg-Al catalysts from the pyrolysis-gasification of polypropylene, high density polyethylene, waste plastic and mixed plastics. However, the formation of filamentous carbons on the coked catalyst from the pyrolysis-gasification of polystyrene was low.     

废旧汽车门内饰板聚丙烯塑料同等性能再利用

以乘用车废旧门内饰板聚丙烯塑料为研究对象,通过共混改性研究其性能变化规律、机理,实现回收料的同等性能再利用。采用聚丙烯新料(VPP)、乙烯–辛烯共聚物(POE)对回收PP(RPP)进行共混改性,研究VPP和POE的添加量对复合体系力学性能的影响规律及改善机理。结果表明,VPP的加入可以显著提高RPP/VPP复合体系的拉伸性能、弯曲性能和流动性能;POE含量越高,RPP/VPP/POE复合体系的冲击强度越大;当RPP/VPP/POE=54/36/10时,复合体系的综合性能满足汽车门内饰板的性能要求,实现废旧材料的同等性能再利用。     

Hydrocarbon fuels produced by catalytic pyrolysis of hospital plastic wastes in a fluidizing cracking process

A mixture of post-consumer polyethylene/polypropylene/polystyrene (PE/PP/PS) with polyvinyl chloride (PVC) waste was pyrolyzed over cracking catalysts using a fluidizing reaction system operating isothermally at ambient pressure. The influences of catalyst types and reaction conditions including reaction temperatures, ratios of catalyst to plastic feed, flow rates of fluidizing gas and catalyst particle sizes were examined. Experiments carried out with various catalysts gave good yields of valuable hydrocarbons with differing selectivity in the final products dependent on reaction conditions. A model based on kinetic and mechanistic considerations associated with chemical reactions and catalyst deactivation in the acid-catalyzed degradation of plastics has been developed. The model gives a good representation of experimental results from the degradation of commingled plastic waste. The results of this study are useful for determining the effects of catalyst types and reaction conditions on both the product distribution and selectivity from hospital plastic waste, and especially for the utilization of post-use commercial FCC catalysts for producing valuable hydrocarbons in a fluidizing cracking process.     

Pyrolysis kinetics of olive residue/plastic mixtures by non-isothermal thermogravimetry

The TGA studies of a pyrolytic decomposition of mixtures of olive residue/plastic were carried out. The investigation was made at the temperature ranging from 300 to 1273 K) in the nitrogen atmosphere at four heating rates β = 2, 10, 20 and 50 K min^− 1. High density polyethylene (HDPE), low density polyethylene (LDPE), polypropylene (PP) and polystyrene (PS) were selected as plastic samples. Based on the results obtained, three thermal stages were identified during the thermal degradation. The first two were dominated by the olive residue pyrolysis, while the third was linked to the plastics pyrolysis, which occurred at much higher temperatures. Discrepancies between the experimental and calculated TG/DTG profiles were considered as a measurement of the extent of interactions occurring on pyrolysis olive residue/plastic mixtures. The maximum degradation temperatures of each component in the mixture were higher than those of the individual components. These experimental results indicate a significant synergistic effect during olive residue and plastic co-pyrolysis at the high temperature region. In addition, a kinetic analysis was performed to fit thermogravimetric data. A reasonable fit to the experimental data was obtained for all materials and their mixtures.     

The effect of plastic addition on coal caking properties during carbonization

The recycling process of waste plastics using coke ovens is now being studied. The effect of plastic addition on coal caking property was investigated. It was revealed that thermal decomposition products of plastics interacted with bituminous coal during carbonization in coke ovens. The effect of plastic addition on coal caking property varied with types of plastics. The addition of aliphatic polymers such as polyethylene (PE), polypropylene (PP) and poly(vinyl chloride) (PVC) had only a small effect on coal caking property and coke strength and in some cases PE addition increased coke strength. On the other hand, the addition of polystyrene (PS), poly(ethylene terephthalate) (PET) and terephtalic acid (TFA) inhibited coal expansion and fusion, decreased maximum fluidity and total dilatation, and deteriorated the coke strength. These differences were discussed from the viewpoint of the interaction between thermal decomposition products of plastics and hydrogen in coal. It was suggested that the radical formed as a result of PS or PET thermal decomposition abstracted hydrogen from coal, which resulted in the decrease in coal caking property.     

Basic study on separate charge of coal and waste plastics in coke oven chamber

Nippon Steel Corporation started to operate a waste plastic recycling process using coke ovens at Nagoya and Kimitsu Works in 2000 and at Yawata and Muroran Works in 2002. Now the total capacity is 120,000 tons per year and the recycling process is operating smoothly. In this process, coals and added plastics are carbonized and changed into coke, tar, oil and coke oven gas in a coke oven chamber. At present, upper limit of the addition rate of waste plastics to blended coals is 1% so that the plastic addition does not affect coke strength. However, the amount of waste plastics in Japan is as much as about 10 million tons per year and there is a real need for increasing the amount of waste plastics treated by the waste plastic recycling process using coke ovens. We investigated a method of increasing the addition rate of waste plastics without affecting coke strength by charging coal and plastic separately in a coke oven chamber. In the case of the same plastic addition rate, charging the plastic in the bottom or the top part of the coke oven chamber can decrease the deterioration of coke strength compared with charging a homogeneous mixture of coal and plastic. Charging the plastic in the bottom decreases the coke strength to a greater extent than charging the plastic in the top. This is because the decomposition of the plastic charged in the bottom decreases the bulk density of the upper coal layer. The results suggest that charging the coal and waste plastics separately increases the amount of waste plastics treated in the waste plastic recycling process using coke ovens. In order to commercialize this method, further studies are necessary concerning the charging method, device and the effect of this method on the coke oven operation.     

Rheological and mechanical properties of polypropylene/thermoplastic starch blend

Starch as an inexpensive and renewable source has been used as a filler for environmentally friendly plastics for about two decades. In order to improve the compatibility between hydrophilic starch granules and hydrophobic polypropylene (PP), glycerol used as a plasticizer for starch to enhance the dispersion and the interfacial affinity in thermoplastic starch (TPS)/PP blend. In this study, PP was melt blended with thermoplastic starch (TPS) using a single screw extrusion process and molded using injection molding process to investigate the rheological and mechanical properties of these blends. TPS viscosity measurements were performed on the single screw extruder. Rheological properties were studied using a capillary rheometer and the Bagley’s correction was performed. Mechanical analysis (stress–strain) was performed using Testometric M350-10KN. The rheological properties showed that the viscosity of TPS decreases with increasing glycerol content in TPS. Also, it was found that PP/TPS blends are pseudo plastic in nature and the flow activation energy of the blends is greater than that of PP. Mechanical results showed that strain at break of the blends is lower than that of PP, whereas the Young’s modulus of the blends is higher than that of PP.     

Triboelectrostatic separation of pvc materials from mixed plastics for waste plastic recycling

This study covers the triboelectrostatic separation of Polyvinylchloride (PVC) materials from mixed plastics such as polyethylene terephthalate (PET), polyethylene (PE), polypropylene (PP), and polystyrene (PS). The PVC material generates hazardous hydrogen chloride gas resulting from the combustion in the incinerators. The laboratory scale triboelectrostatic separation system consists of a fluidized-bed tribocharger, a separation chamber, a collection chamber and a controller. Negative and positive surface charges can be imparted to the PVC and PET particles, respectively, due to the difference of triboelectric charging series between the particles in the fluidized-bed tribocharger. They can be separated by passing through an external electric field. A highly concentrated PVC (91.9%) can be recovered with a yield of about 96.1% from the mixture of PVC and PET materials in a single stage of processing. For the removal of PVC from the two-component mixed plastics such as PVC/PET, PVC/PP, PVC/PE or PVC/PS, separation results show the recovery of 96–99% with the pure extract content in excess of 90%. The triboelectrostatic separation system using the fluidized-bed tribocharger shows the potential to be an effective method for removing PVC from mixed plastics for waste plastic recycling.     

废塑料配煤炼焦实验研究Ⅱ-焦炭质量分析

利用焦炭反应性装置对在2kg焦炉上实验所得的废塑料配煤炼焦焦炭进行热强度分析,结果表明:废塑料的配入量为1%～5%时,各配煤样品所得的焦炭的反应性和反应后强度均呈现下降趋势。用废塑料代替3%以内的瘦煤炼焦,所得焦炭的反应性和反应后强度指标均有所改善,但是废塑料代替其他煤种炼焦所得焦炭的热性能指标均有所降低。     

Mechanical properties of composites from sawdust and recycled plastics

Mechanical properties of wood plastic composites (WPCs) manufactured from sawdust and virgin and/or recycled plastics, namely high density polyethylene (HDPE) and polypropylene (PP), were studied. Sawdust was prepared from beech industrial sawdust by screening to the desired particle size and was mixed with different virgin or recycled plastics at 50% by weight fiber loading. The mixed materials were then compression molded into panels. Flexural and tensile properties and impact strength of the manufactured WPCs were determined according to the relevant standard specifications. Although composites containing PP (virgin and recycled) exhibited higher stiffness and strength than those made from HDPE (virgin and recycled), they had lower unnotched impact strengths. Mechanical properties of specimens containing recycled plastics (HDPE and PP) were statistically similar and comparable to those of composites made from virgin plastics. This was considered as a possibility to expand the use of recycled plastics in the manufacture of WPCs. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3641–3645, 2006     

Pyrolytische Rohstoff-Rückgewinnung aus Sonderabfällen

Pyrolytic recovery of raw materials from special wastes . The pyrolytic techniques developed especially for producing smelting coke from coal and in petroleum refining can be applied to the thermal decomposition of waste materials having a high organic content. Fluidized bed reactors and rotary kilns are particularly suitable as universally applicable pyrolysis units for continuous operation. Highly aromatic pyrolysis oils for use as chemical raw material, heating gases for the autothermic operation of the pyrolysis unit, and carbon and solids containing nonferrous metals are obtained from plastics waste, used tires, old cable, shredder wastes, and acid resins at reactor temperatures of about 700°C. Largescale applicability and economics of the process have yet to be proved.     

Co-pyrolysis characteristics of typical components of waste plastics in a falling film pyrolysis reactor

Waste plastics mainly come from MSW and usually exist in the form of mixed plastics. During the co-pyrolysis process of mixed plastics, various plastic components have different physicochemical properties and reaction mechanisms. Considering the high viscosity and low thermal conductivity of molten plastics, a falling film pyrolysis reactor was selected to explore the rapid co-pyrolysis process of typical plastic components (PP, PE and PS). The oil and gas yields and the compositions of pyrolysis products of the three components under different ratios at pyrolysis temperatures were analyzed to explore the co-pyrolysis characteristics of PP, PE, and PS. The study is of great significance to the recycling of waste plastics.     

聚丙烯等离子体热解与管式炉热解对比研究

叙述了等离子体热解技术的特点及相对普通热解的优越性,并以聚丙烯为实验物料,对比了等离子体热解与管式炉热解的转化率、产物分布、成分等,实验结果显示等离子体热解转化率高,所得产物易于分离,气体产物中H2体积分数高,表明等离子热解是一种颇具发展潜力的固体废弃物处理技术。     

废旧塑料的回收与利用

综述了利用区块链技术进行废旧塑料的回收。使用区块链技术建立的塑料银行可以激励人们自发地回收废旧塑料。废旧塑料的回收流程大多是线下的,监管困难,使用区块链技术可以使用户在区块链上查询全流程的回收数据,便于监管。在废旧塑料的分选和利用方面,介绍了聚乙烯和聚丙烯的分选,聚对苯二甲酸乙二酯与聚氯乙烯混合固体塑料的分选。废旧塑料可以通过加入不同的改性剂转化为高附加值的有用材料。     

Fracture behavior of polypropylene/ ethylene- diene-terpolymer blends : Effect of temperatures,notch radius and rubber content

The mechanical fracture and ductile-brittle transition (DBT) behavior, hysteresis phenomenon and the plastic zone size of polypropylene (PP) / ethylene-propylene-diene terpolymer (PP/EPDM) blends were investigated by varying EPDM content and notch radius under different temperatures. An increase in test temperature or rubber content in the PP/EPDM blend results in lower yield stress and Young's modulus. The ductile-brittle transition temperature (DBTT) of the notched impact strength decreases with the increase of the EPDM content. However, the DBTT is fairly independent of the notch radius. SEM morphologies of the fracture surfaces indicate that two separate modes, localized and mass shear yielding, work simultaneously in these blends. The plane-strain localized shear yielding dominates the brittle failure at lower temperatures, whereas the plane stress mass shear yielding dominates the ductile fracture at higher temperatures. The presence of EPDM rubber decreases the yield stress of the PP/EPDM blend due to the overlapping stress fields of adjacent particles, resulting in higher hysteresis energy. The relationships among the test temperature, hysteresis loss energy and the size of plastic zone are discussed in detail.     

The effect of plastic size on coke quality and coking pressure in the co-carbonization of coal/plastic in coke oven

In the recycling process of waste plastics using coke ovens, coals and added plastics are carbonized and changed into coke, tar, oil and coke oven gas in a coke oven chamber. In this study, the effect of added plastic size on coke quality and the effect of plastic addition on coking pressure was investigated. In the case of a plastic addition rate of 2%, the coke strength reached a minimum at the particle size of 10 mm for polyethylene (PE) and 3 mm for polystyrene (PS). The mechanism was attributed to the weak coke structure formed on the interface between plastic and coal. The result indicates that large or small plastic particles are favorable in order to add waste plastics to blended coals for coke making without affecting coke strength . Furthermore, it was also shown that a 1% addition of large size agglomerated waste plastics to blended coals did not increase coking pressure. Based on this fundamental study, and considering the ease of handling plastics, we have determined that the size of waste plastic used in a commercial-scale recycling process of waste plastics using coke ovens is about 25 mm. Nippon Steel Corporation started to operate a waste plastic recycling process using coke ovens at Nagoya and Kimitsu works in 2000 and at Yawata and Muroran works in 2002. Now the total capacity is 120,000 tons per year as of 2003 and this process is operating smoothly.     

Rheological characteristics of coal tar and petroleum pitches with and without additives

An extensive study of rheological characteristics of coal tar and petroleum pitches with and without additives, namely, petroleum coke, natural graphite and carbon black has been made. It is found that all pitches, pure or mixed with a carbon additive are not Newtonian as reported in the literature, but behave Theologically as Bingham plastics with certain yield stress and plastic viscosity at all temperatures of measurement between 85–180°C. The yield stress and plastic viscosity both decrease with increase in temperature of the pitch. A pure petroleum pitch having the same softening point as that of a coal tar pitch is found to have a lower viscosity compared to that of the latter at all temperatures of measurement. This suggests that the criterion of softening point as a measure of suitability of a coal tar pitch binder in the manufacture of artificial carbon is not sufficient for petroleum pitches. Addition of ten parts of carbon black by weight of pitch results in a considerable decrease in viscosity change with temperature of the coal tar pitch compared to almost insignificant change in the case of the petroleum pitch of the same softening point. However, the addition of petroleum coke or natural graphite makes the pitch more viscous but does not change the temperature dependence of viscosity of either of the two types of pitches. The implications are discussed.     

废塑料裂解催化剂研究进

废塑料造成的环境污染日趋严重,处理回收废塑料已成为全球关注的问题。催化裂解作为一种新的塑料回收方法,具有高效、环保、无二次污染和产物油品质高等特点。综述了国内外废塑料裂解制油催化剂如分子筛、氧化物、黏土和过渡金属负载型双功能催化剂的研究进展。分子筛类、黏土类和无定形氧化铝-二氧化硅催化剂属酸性催化剂,其裂解废塑料机理为碳正离子机理;碱金属氧化物催化剂裂解废塑料机理为碳负离子机理;过渡金属负载型催化剂具有双功能,其中,金属活性位起加氢-脱氢作用,载体酸性位起异构化作用;而粉煤灰催化剂可同时实现废塑料与粉煤灰两种废弃物的综合回收利用。今后应注意在催化机理指导下,进一步提高催化剂性能,并研究对复杂废塑料混合物的催化裂解效果。     

Creep and recovery behavior of kenaf/polypropylene nonwoven composites

This article reports an exploratory study on the creep and recovery behavior of kenaf/polypropylene nonwoven composites (KPNCs), serving as a bio‐based substitution for polypropylene (PP) plastics in the automotive industry due to the environmental concern. The creep and recovery behavior of KPNC and solid virgin PP were performed by dynamic mechanical analyzer (DMA) which allowed it to be studied extensively. The linear viscoelastic limit (LVL) was found at 1 MPa. Two popular creep models, the four‐element Burgers (FEB) model and the Findley power law (FPL) model, were used to model the creep behavior in this study. The FEB model was found only appropriate for characterizing short‐term creep behavior. In contrast, the FPL model was satisfactory for predicting the long‐term creep performance. The long‐term creep behavior of KPNC in comparison to virgin PP plastic was predicted using the time‐temperature superposition (TTS) principle. The 1‐year creep strains were estimated to be 0.32% for KPNC and 1.00% for virgin PP at 40°C. A three‐day creep test was conducted to validate the effectiveness of the TTS prediction. KPNC showed a better creep resistance and higher recoverability than the virgin PP, especially in a high‐temperature environment. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40726.