Development of a catalytic cracking process for converting waste plastics to petrochemicals

The catalytic degradation of polyolefin using H-gallosilicates was examined using a bench-scale reactor (0.8kg/h) with semicontinuous feeding and the following plastics: (1) low-density polyethylene (LDPE) pellets; (2) linear low-density polyethylene (L-LDPE) pellets; (3) high-density polyethylene (HDPE) pellets; (4) polypropylene (PP) pellets; (5) polyolefin obtained from pulverized industrial waste plastics. The yields of liquid compounds from these materials, which were aromatics in most cases, ranged from 55wt% to 68wt%. With an increase in the ratio of total reactant to catalyst, the liquid yield remained the same. Yields of benzene, toluene, and xylenes (BTXs) decreased rapidly to below 50wt% at a ratio of more than 30. Differences in this ratio for BTXs were always small and were independent of the material. Only about half of the gas product was propane with a fresh catalyst. When the experiments were repeated, propylene, isobutane, and isobutene were found to increase.     

废旧塑料的处理工艺

介绍了当前国内外几种处理和利用废旧塑料的方法,特别对废旧塑料掩埋、再生、回收、焚烧、热裂解制造燃料油和化学品的技术和存在的问题作了重点探讨.     

Utilization of red mud as catalyst in conversion of waste oil and waste plastics to fuel

The aim of this study was to investigate the possibilities of using a by-product (red mud) from alumina production as a catalyst for recovery of waste. The conversion of waste mineral oil (WMO) and waste mineral oil/municipal waste plastic (WMO/MWP) blends over red mud (RM), a commercial hydrocracking catalyst (silica–alumina), and a commercial hydrotreating catalyst (Ni–Mo/alumina) to fuel has been studied. The effect of the catalyst and the temperature on the product distribution (gas, liquid, and wax) and the properties of liquid products were investigated. In the case of hydrotreatment of WMO, the liquids obtained over RM at both 400° and 425°C had larger amounts of low-boiling hydrocarbons than that of thermal or catalytic treatment with hydrotreating catalyst. Gas chromatography and nuclear magnetic resonance analysis of the liquid products showed that RM had hydrogenation and cracking activity in hydrotreatment of WMO. In coprocessing of WMO with municipal waste plastics, temperature had an important effect as well as the amount of MWP in the blend and the catalyst type. The hydrocracking at 400°C produced no liquid product. In hydrocracking at 425°C, the product distribution varied with catalyst type and MWP amount. The commercial hydrocracking catalyst had more cracking ability in the conversion of WMO/MWP to liquid and gas fuel than RM. In the case of hydrocracking over RM, the largest amount of liquid having satisfactory quality was obtained only from the blend containing 20% MWP.     

Trends in waste plastics and recycling

Zero emission is an ambitious project aimed at the conversion of the conventional top-down or one-directional flow type production systems of modern society to those of a recycling type. The basic idea underlying this project is to understand in detail the material flow mechanism in a particular segment of society and to evaluate the transformability of the hitherto one-directional types of process into recycling types. The authors, members of the Zero-Emission Research Group of Japan, are investigating the material flow of plastics in Japan. The present work describes the features of this project, as well as the results obtained so far. Received: May 28, 1998 / Accepted: October 16, 1998     

Gasification of waste plastics by steam reforming in a fluidized bed

The process of producing synthetic gas from waste plastics by steam reforming was investigated. To evaluate this process, the steam reforming of the oils derived from low-density polyethylene and polystyrene were carried out using a laboratory-scale fluidized bed of Ni-Al₂O₃ catalysts. The performance of gasification in terms of carbon conversion, gas yield, and gas compositions was examined. Although oils derived from plastics contain many kinds of heavy hydrocarbons and aromatics, they were well gasified at temperatures above 1023 K with a steam/carbon ratio of 3.5 and a weight hourly space velocity of 1 h⁻¹. The hydrogen content of the product gas was very high at approximately 72 vol% for polyethylene-derived oil and 68 vol% for polystyrene-derived oil. These compositions agreed well with the values calculated from chemical equilibrium.     

Two-stage thermal gasification of polyolefins

Plastic pellets of polyethylene (PE), polypropylene (PP), and polystyrene (PS) were gasified in a two-stage thermal degradation process. The first stage is the conversion of polyolefins to distilled oils using a melting vessel. In the second stage, the oils from the first stage are gasified using a tubular reactor. The distilled oil yields of PE, PP, and PS in the first stage were 84, 89, 92 wt%, respectively, each at 470°C. The total gas yields of PE, PP, and PS in the second stage were 80, 74, and 6.2 wt%, respectively, each at 800°C. The main components of the product gas for PE and PP were methane and olefins such as ethene and propene. Some aromatic oils, including benzene, toluene, and xylene, were also produced as by-products. The amount of carbonaceous residue, or coke, was very low (less than 1 wt%). By dividing the process into two stages, the coking rate was considerably reduced compared with direct gasification of the polyolefins. Received: July 19, 2000 / Accepted: September 17, 2000     

Studies on the dechlorination and oil-production technology of waste plastics

 Recycle technology for waste plastics containing polyvinyl chloride (PVC) has been developed in the Hokkaido National Industrial Research Institute for the production of solid and liquid fuel, and has established a recycling process which includes a dechlorination process for PVC plastics, and a two-stage catalytic pyrolysis process for plastics using zeolite catalysts. The dechlorination equipment consists of a two-axis screw extruder with a heating element, which can remove chlorine up to 99.9 wt. % from PVC containing plastics as hydrogen chloride. The product had about 44 000 kJ/kg calorific value and was fed into the next oil production process, although it could also be used as a solid fuel. Natural and synthetic zeolite were used as catalysts for the two-stage catalytic process, which produced a light oil with a boiling point which was between those of kerosene and gasoline. The yield of this oil reached 82 wt. %. The chemical type was analyzed using liquid chromatography, and was found to have many aromatic compounds. These technologies make it possible to produce a nonpolluting, high-calorie solid fuel and a liquid fuel very efficiently. Received: July 19, 2000 / Accepted: September 21, 2000     

Formation of recycled plastics from depolymerized monomers derived from waste fiber-reinforced plastics

To develop a new method for the chemical recycling of plastics, we examined the formation of recycled polymers from the recovered monomeric materials of solubilized waste fiber-reinforced plastics (FRP) under supercritical alcoholic conditions. Treatment of waste FRP with supercritical MeOH resulted in the formation of monomeric organic compounds that mainly contained dimethyl phthalate (DMP) and propylene glycol. The presence of these materials was confirmed by gas chromatography and nuclear magnetic resonance analyses and they were mixed with new DMP and glycols in various ratios to form unsaturated polyesters. The polymerization progressed successfully for all mixing ratios of the recovered and new DMP. Hardness tests on these recycled polymers indicated that the polymer made from a 1:1 mixture of recovered and new dimethyl phthalate had almost the same level of hardness as the polymers made from new materials. We also examined the formation of recycled FRP by using glass fibers and monomeric materials recovered through the present depolymerization method. Chemical Feedstock Recycling & Other Innovative Recycling Techniques 6     

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.     

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.     

Toward maximizing the recycling rate in a Sapporo waste plastics liquefaction plant

Sapporo Plastics Recycling Co., Ltd., (SPR) started its commercial operation of waste plastics liquefaction in 2000. At first only hydrocarbon oil was reclaimed, this being derived from the waste plastics liquefaction process under the Japanese Containers and Packaging Recycling Law. Presently, thermal degradation residue and hydrochloric acid are being produced as by-products in addition to the hydrocarbon oil. As a result, the SPR plastics liquefaction plant has achieved a high reclamation rate of 96%, and 93% of the recycled products have been reused in Hokkaido, where SPR is located. The technical problems caused by corrosion and clogging have been solved. Chemical Feedstock Recycling & Other Innovative Recycling Techniques 6     

Waste plastics recycling process using coke ovens

The Japan Iron and Steel Federation (JISF), as its voluntary energy-saving action plan, proposed a 10% energy reduction by 2010 with 1990 as the basis. Further, it has suggested an additional 1.5% energy saving by the use of waste plastics as a metallurgical raw material. The amount of processing of waste plastics which corresponds to this amount of energy conversion is about 1 million t scale during 1 year. Conventional known methods for recycle-processing of waste plastics include, for example, the method of injection into a blast furnace to use waste plastics as an iron-ore reducing agent instead of coal. On the other hand, the coking process is considered to be suitable as a waste plastic recycling facility because the process involves coal carbonization in a high-temperature and reducing atmosphere. Carbonization tests with mixed waste plastics were conducted with laboratory equipment and in actual coke ovens. As a result, it was confirmed that the waste plastics recycling process using coke ovens is feasible. Therefore, a waste plastics recycling process using coke ovens was started as a chemical recycling technology at Nippon Steel.     

废旧塑料的再生及其在制管行业中的应用

总结了再生、降解、焚烧及填埋等几种废旧塑料处置方式的特点,指出对于品种单一、老化程度低的废旧塑料应优先选择再生利用.重点介绍了废旧聚氯乙烯塑料、聚乙烯塑料、聚丙烯塑料、氯化聚氯乙烯塑料的再生及其在制管行业中的利用情况进展.     

Boiling treatment of ABS and PS plastics for flotation separation

A new physical method, namely boiling treatment, was developed to aid flotation separation of acrylonitrile–butadiene–styrene (ABS) and polystyrene (PS) plastics. Boiling treatment was shown to be effective in producing a hydrophilic surface on ABS plastic. Fourier Transform Infrared analysis was conducted to investigate the mechanism of boiling treatment of ABS. Surface rearrangement of polymer may be responsible for surface change of boiling treated ABS, and the selective influence of boiling treatment on the floatability of boiling treated plastics may be attributed to the difference in the molecular mobility of polymer chains. The effects of flotation time, frother concentration and particle size on flotation behavior of simple plastic were investigated. Based on flotation behavior of simple plastic, flotation separation of boiling treatment ABS and PS with different particle sizes was achieved efficiently. The purity of ABS and PS was up to 99.78% and 95.80%, respectively; the recovery of ABS and PS was up to 95.81% and 99.82%, respectively. Boiling treatment promotes the industrial application of plastics flotation and facilitates plastic recycling.     

VOC气体检测仪在进口废塑料检验中的应用

针对挥发性有机化合物(VOC)气体在现实中的危害,对废物原料检验的标准进行了探讨,对废物原料检验中如何进行VOC检测进行分析并提出建议。     

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.     

Liquefaction process for a hydrothermally treated waste mixture containing plastics

Most landfilled plastic waste is a mixture or is in the form of composites with incombustible wastes such as glass, metals, and ceramics. After hydrothermal treatment, including a steam-explosion process, the separation of mixed waste (MW) into organic and inorganic substances becomes easy. However, the effect of hydrothermal pretreatment on the subsequent liquefaction of organic substances from MW is not obvious. In this study, the effects on the liquefaction of polystyrene and high-density polyethylene are discussed. Moreover, optimum conditions for the liquefaction of organic substances from hydrothermally treated MW are identified. By means of this hydrothermal pretreatment, including the steam-explosion process, polystyrene and high-density polyethylene can be significantly converted to oil by liquefaction at 300°–400°C. In comparison with liquefaction of hydrothermally pretreated mixed waste (HMW) at 300°–400°C with a batch type reactor, the yield of oil increases significantly on liquefaction using a semi-batch type reactor. It is considered that the radical chain and termination reactions among the radicals from HMW were inhibited in the semi-batch type reactor. On liquefaction of HMW in a semi-batch reactor, the conversion of HMW to oil was enhanced on increasing the liquefaction temperature to 350°C and the holding time to 60 min. Chemical Feedstock Recycling & Other Innovative Recycling Techniques 6     

Waste plastics recycling by an entrained-flow gasifier

We studied an entrained-flow gasification process which efficiently converts waste plastics to energy at a high energy recovery rate. Waste plastics, after being shredded to <8 mm or <14 mm, were fed into an entrained-flow gasifier with air and oxygen. In the gasifier, organic substances were pyrolyzed, partially combusted, and then converted into synthetic gas (CO, H₂) at a high temperature (over 1600 K). The clarified gasification characteristics were that the lower heat value (LHV) of the product gas was over 4.2 MJ/Nm³ and the cold gas efficiency was approximately 60%. Other inert substances in the wastes such as ashes and metals were melted into slag and condensed on bag filters. The bag filters and a water scrubber removed impurities such as dusts, heavy metals, and hydrogen halides from the product gases. Solid hydrocarbons, which include char and soot, were removed at a hot cyclone and on the bag filters. Received: July 19, 2000 / Accepted: October 3, 2000     

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.     

浅谈国际原油价格暴跌对进口废塑料行业的影响及建议

作为资源的重要补充,近年来国内塑料加工行业对进口废塑料的需求市场不断扩大,但作为原油的下游产品,因原油价格波动带来的经营影响和环保风险不容忽视。为有效规避风险,提升行业竞争力,在源头控制、行业转型、通关便利等方面提供可行性建议。