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.     

废塑料热解聚乙烯蜡的羧基化改性和表征

以废弃聚乙烯塑料热解得到的粗蜡为原料,用溶液催化氧化法制备了羧基化改性的氧化聚乙烯蜡,考察了催化剂种类和用量、引发剂用量、反应时间、反应温度对产物酸值的影响。结果表明,在催化剂加入量为1%、引发剂用量为10%、反应时间为8 h、反应温度为90℃的条件下,可制得酸值为16.26 mg KOH/g和16.17 mg KOH/g的氧化蜡。利用红外光谱和热重分析对产品进行表征。     

PE废塑料溶剂裂解制备聚乙烯蜡

本文以废旧聚乙烯为原料,在溶剂水的作用下进行裂解制备聚乙烯蜡。实验过程中考察了温度、时间及溶剂加入量对产品性能的影响。结果表明:随裂解温度的升高和反应时间的延长都使得反应体系获得了更高的能量,容易使PE大分子发生断链从而得到低分子量PE,从而使产物收率逐渐降低,粘均分子量减少,熔程也随之下降。溶剂加入量对产品性质也有一定影响。当裂解温度为370℃,反应时间60min,溶剂加入量占原料总质量50%时,得到灰白色的聚乙烯蜡,其熔程在104~110℃之间,酸值为0.0143mg·g-1,粘均分子量为3426.4,且具有较高的热稳定性。通过溶剂裂解制得的聚乙烯蜡具有一定的工业应用前景。     

混合废塑料裂解液相产物的分析

通过SH/T 0558色谱模拟蒸馏技术和成分检测分析混合废塑料裂解得到的液相产物。详细介绍了SH/T 0558色谱模拟蒸馏技术快速测定裂解油馏程的方法,采用nC_9、nC_(10)混合物作为裂解油模拟蒸馏的内标物,使用常规峰面积归一分析方法,经过处理产生色谱模拟蒸馏的测定报告。该方法样品用量少,操作简便,分析速度快,结果精确,最大相对标准偏差为0.75%,能够较好的模拟裂解油馏程。混合废塑料热裂解和催化裂解得到的液相产物中汽油和柴油的含量较高,油品质量较好。对混合废塑料热裂解和催化裂解所获得的两种油样进行饱和烃、芳烃和烯烃成分检测,有催化剂参与后烯烃+芳烃的总量为85.2%,其汽油辛烷值很高,可作为高标号优质汽油组分。     

聚烯烃塑料的热解和催化热解研究进展

通过热解和催化热解技术将废塑料转化为高附加值产品是一种有前途的回收途径,可解决废塑料对环境的污染问题并促进环境的可持续化,这种方法同时具有经济效益和明显的环境优势,为塑料的回收行业确立了未来的发展趋势。本文以石蜡、轻质芳烃（BTX）、低碳烯烃和苯乙烯等产品为出发点,阐述了不同聚烯烃塑料的热解特性,详细介绍了温度和停留时间对产品分布和收率的影响,然后基于聚烯烃空间结构的差异,讨论了不同催化剂作用下的热解机理,并对催化剂的酸强度和孔结构等影响因素进行了着重分析,以改善产品选择性。此外,文章简述了聚氯乙烯脱氯的三类过程,即热解脱氯、催化热解脱氯和吸附脱氯。最后指出催化热解过程中催化剂成本高、重复使用活性低等潜在问题,今后的研究应致力于优化工艺路线、开发价格低廉的新型催化剂。     

Thermal and catalytic pyrolysis of a synthetic mixture representative of packaging plastics residue

A synthetic mixture of real waste packaging plastics representative of the residue from a material recovery facility (plasmix) was submitted to thermal and catalytic pyrolysis. Preliminary thermogravimetry experiments coupled with Fourier transform infrared spectroscopy were performed to evaluate the effects of the catalysts on the polymers’ degradation temperatures and to determine the main compounds produced during pyrolysis. The thermal and catalytic experiments were conducted at 370°C, 450°C and 650°C using a bench scale reactor. The oil, gas, and char yields were analyzed and the compositions of the reaction products were compared. The primary aim of this study was to understand the effects of zeolitic hydrogen ultra stable zeolite Y (HUSY) and hydrogen zeolite socony mobil-5 (HZSM5) catalysts with high silica content on the pyrolysis process and the products’ quality. Thermogravimetry showed that HUSY significantly reduces the degradation temperature of all the polymers—particularly the polyolefines. HZSM5 had a significant effect on the degradation of polyethylene due to its smaller pore size. Mass balance showed that oil is always the main product of pyrolysis, regardless of the process conditions. However, all pyrolysis runs performed at 370°C were incomplete. The use of either zeolites resulted in a decrease in the heavy oil fraction and the prevention of wax formation. HUSY has the best performance in terms of the total monoaromatic yield (29 wt-% at 450°C), while HZSM5 promoted the production of gases (41 wt-% at 650°C). Plasmix is a potential input material for pyrolysis that is positively affected by the presence of the two tested zeolites. A more effective separation of polyethylene terephthalate during the selection process could lead to higher quality pyrolysis products.     

The pyrolysis of individual plastics and a plastic mixture in a fixed bed reactor

Six thermoplastics, which represent more than two-thirds of all polymer production in western Europe, were pyrolysed in a static batch reactor in a nitrogen atmosphere. These were high density polyethylene (HDPE), low density polyethylene (LDPE), polystyrene (PS), polypropylene (PP), polyethylene terephthalate (PET) and polyvinyl chloride (PVC). The heating rate used was 25°C min⁻¹ to a final temperature of 700°C. These six plastics were then mixed together to simulate the plastic fraction of municipal solid waste found in Europe. The effect of mixing on the product yield and composition was examined. The results showed that the polymers studied did not react independently, but some interaction between samples was observed. The product yield for the mixture of plastics at 700°C was 9·63% gas, 75·11% oil, 2·87% char and 2·31% HCl. The gases identified were H₂, CH₄, C₂H₄, C₂H₆, C₃H₆, C₃H₈, C₄H₈, C₄H₁₀, CO₂ and CO. The composition of oils were determined using Fourier Transform infra-red spectrometry and size exclusion chromatography. Analysis showed the presence mainly of aliphatic compounds with small amounts of aromatic compounds. ©1997 SCI     

废旧橡塑制品的密封热解工艺

介绍了废旧橡塑制品密封热解工艺的流程,设备以及特点,采用该生产工艺,可通过调节加热裂解炉的炉腔温度对废旧橡胶和塑料制品进行热解回收,操作简单易行,回收效率高,无污染排放物,回收产品的市场前景广阔。     

Decomposition characteristics of residue from the pyrolysis of polystyrene waste in a fluidized-bed reactor

Effective treatment of residue generated from the pyrolysis of polystyrene wastes has been one of the important factors in the recovery of styrene monomer and oil from polystyrene wastes. Depending on the experimental conditions, the yields of oil and styrene monomer are considerably decreased in the presence of residue. Here the residue was decomposed effectively in a catalytic fluidized-bed reactor. Nitrogen and silica sand were used as a fluidizing gas and a bed material, respectively. Effects of catalyst, temperature and gas velocity on the characteristics of decomposition of the residue were examined. It was found that the residue could be decomposed to oil or chemicals effectively by means of a catalytic fluidized-bed reacting system. The yields of oil and individual chemicals and the composition of the products were dependent upon the operating variables such as reaction temperature, catalyst and gas velocity.     

Biofuels from waste fish oil pyrolysis: Continuous production in a pilot plant

Fast pyrolysis of waste fish oil was performed in a continuous pyrolysis pilot plant. The experiment was carried out under steady-state conditions in which 10 kg of biomass was added at a feed rate of 3.2 kg h⁻¹. A bio-oil yield of 72-73% was obtained with a controlled reaction temperature of 525 °C. The bio-oil was distilled to obtain purified products with boiling ranges corresponding to light bio-oil and heavy bio-oil. These biofuels were characterized according to their physico-chemical properties, and compared with the Brazilian-fuel specifications for conventional gasoline and diesel fuels. The results show that the fast pyrolysis process represents an alternative technique for the production of biofuels from waste fish oil with characteristics similar to petroleum fuels.     

Continuous pyrolysis of waste tyres in a conical spouted bed reactor

Continuous pyrolysis of scrap tyres has been carried out in a conical spouted bed reactor and the results (yields, composition of the volatile fraction and carbon black properties) have been compared with those obtained operating in batch mode in a previous study. Continuous operation in the 425-600 °C range gives way to a yield of 1.8-6.8 wt.% of gases, 44.5-55.0 wt.% of liquid fraction (C₅-C₁₀ range hydrocarbons, with a maximum yield of limonene of 19.3 wt.% at 425 °C), 9.2-11.5 wt.% of tar and 33.9-35.8 wt.% of char. The main differences between the continuous and batch processes are in the yield of light aromatics, which is higher in the continuous process, and in that of the heavy liquid fraction or tar, which is higher in the batch process. These are the advantages of the continuous process, although hydrogenation of the liquid fraction is required even in this case in order to use it as fuel. The high yield of limonene, the flexibility in the operating conditions and the capacity for a continuous removal of the residual carbon black from the reactor are the advantages of conical spouted bed technology. The excellent performance of the conical spouted bed reactor for the tyre pyrolysis process is due to the solid cyclic movement, the good contact between phases, the high heating rate and the reduced residence time of the volatile products.     

Conversion of waste plastics to single-cell protein by means of pyrolysis followed by fermentation

Waste plastics (e.g. polyethylene, polystyrene and polypropylene) have been converted to single-cell protein using pyrolysis followed by fermentation. Conversion efficiencies of plastics to pyrolysate were 75–90% for polyethylene, 10–56% for polystyrene and 40–50% for polypropylene. Unpyrolysed residues were formed with polystyrene (6–14%) and polypropylene (14–30%), but not with polyethylene. Polyvinyl chloride produced hydrogen chloride fumes, together with 33–39% unpyrolysed residue, no fermentable pyrolysis products being formed. Polyethylene pyrolysate was fermented by the yeast, Candida tropicalis. Batch fermentation was carried out at 31°C and pH 5.5 on polyethylene pyrolysate in shaken flasks (100 cm³ culture) and in an aerated fermenter (500 cm³ culture). Maximum growth rate was 0.168 h^?1, cell yield was 0.47 ± 0.02 g g^?1 pyrolysate used (n = 3) and doubling time was 4–5 h, after 72 h growth on 1.0g pyrolysate 100 cm^?3 culture. Continuous culture (dilution rate 0.10 h^?1) gave a dry cell yield of 0.39 g g^?1 pyrolysate utilised. Utilisation of pyrolysate was 49.0% in batch culture and 33.0% in continuous culture. The efficiency of conversion of polyethylene to biomass was 34–42% in batch culture. Emulsification and pristane-solubilisation were studied as a means of dispersing waxy pyrolysates in culture media. Pristane did not support growth whereas the emulsifier [lecithin, Tween 85 and sodium glycocholate (1:2:2 by weight)] could support up to 27% of the growth observed on polyethylene pyrolysate. Although growth would occur without either emulsifier or pristane, use of pristane increased both dry cell yield (g g^?1 pyrolysate used) and pyrolysate utilisation by 1.3 times in flask cultures. Crude protein content of cells cultured on polyethylene pyrolysate was 46.7 ± 2.4% (n = 3) for batch culture cells, and 43.8 ± 0.3% (n = 4) for continuous culture cells. The true protein content of Candida cells was about 17%. The protein had a favourable nutritional quality as judged by in-vitro chemical tests.     

PVC裂解过程中的形貌学特征参数及其对裂解过程的表征

研究了聚氯乙烯(PVC)裂解反应过程中的形貌学特征,利用高清红外摄像头记录PVC从常温升至500℃的裂解反应进程中的图像序列,并借助Image Pro Plus(v6.3)数字图像处理软件进行数字化处理,得到了能够表征反应进程的形貌学特征参数量化值:即考察区域(ROI)的总像素面积(PA)和泡率(BR)。同时研究了初始形态和杂质对该两项参数的影响。结果表明,PVC的裂解过程分为4个阶段:熔化,第一裂解段,准稳定段和第二裂解段。BR能够准确反映各阶段及反应快慢,PA则可以作为PVC脱氯结束的关键形貌信号。PVC初始形态对形貌学参数的影响仅体现在熔化段,杂质的引入促进了PVC的裂解,使得各形貌参数变化所对应的特征温度提前,BR峰值变大。研究得到的PVC裂解形貌学信息可为含PVC塑料预脱氯处理过程控制及裂解器的优化提供指导。     

典型杂质掺混对废塑料热解油特性的影响

以从4个典型的废弃物处理场取得的与废塑料掺混的杂质样品作为纯塑料热解过程中的添加剂,研究不可回收废塑料中掺混的杂质组分对塑料热解油品质的影响。研究内容包括4种杂质（I₁～I₄）对聚乙烯、聚丙烯、聚苯乙烯及混合塑料热解的影响以及杂质中的无机和有机组分在热解中分别起到的作用。结果表明,杂质的添加将塑料热解油中主要组分的富集度由65.5%提升到79.2%～90.3%;其中来源于废旧自行车拆解厂的杂质I₄对热解油组成的影响最为显著。I₄使得聚乙烯及聚丙烯热解油中的烯烃含量分别提高了25.0%及21.1%,但对聚苯乙烯的热解没有显著影响。I₄对塑料热解的影响可分为三个方面：无机灰分作为热载体起到的作用、特定活性灰分组分的催化作用以及杂质中有机组分参与热解的影响。灰分作为热载体促进了聚合物分子链的裂解;活性灰分组分能够催化加氢及氢转移等反应;而I₄中有机组分热解提高了油相产物中芳烃和烯烃的含量。该研究将为废塑料规模化热解过程中原料的预处理及热解油品质调控提供指导。     

Kinetics of the thermal degradation of wax materials obtained from pyrolysis of mixed waste plastics

We did a kinetic analysis of the thermal degradation of wax materials obtained from pyrolysis of mixed waste plastics using the nonisothermal weight loss technique with heating rates of 10, 20, 30 and 40 °C/min. The weight loss data according to degradation temperature were analyzed by using the integral method based on Arrhenius form to obtain the kinetic parameters. To verify the effectiveness of the proposed kinetic analysis method, the experimental values were compared with those of the numerical integration results using kinetic parameters obtained in this work. It was found that the proposed kinetic analysis method gave reliable kinetic parameters of the thermal degradation of wax materials obtained from pyrolysis of mixed waste plastics.     

The pyrolysis of waste mandarin residue using thermogravimetric analysis and a batch reactor

A study on the pyrolysis of waste mandarin residue, with the aim of producing bio-oil, is reported. To elucidate the thermodynamics and temperature-dependency of the pyrolysis reaction of waste mandarin residue, the activation energy was obtained by thermogravimetric analysis. Mass loss occurred within the temperature range 200–750 °C, and the average activation energy was calculated to be 205.5 kJ/mol. Pyrolysis experiments were performed using a batch reactor, under different conditions, by varying the carrier gas flow rate and temperature. When the carrier gas flow rate was increased from 15 to 30 and finally to 50ml/min, the oil yield slightly increased. Experiments performed within the temperature range 400–800 °C showed the highest oil yield (38.16 wt%) at 500 °C. The moisture content in the bio-oil increased from 35 to 45% as the temperature increased from 400 to 800 °C, which also resulted in reduction of the oxygenates content and increase in the phenolics and aromatics content, indicating that temperature is an important operating parameter influencing the yield and composition of bio-oil.     

Molten waste plastic pyrolysis in a vertical falling film reactor and the influence of temperature on the pyrolysis products

Molten plastics are characterised with high viscosity and low thermal conductivity. Applying falling film pyrolysis reactor to deal with waste plastics can not only improve heat transfer efficiency, but also solve the flow problem.In this work, the pyrolysis process of molten polypropylene(PP) in a vertical falling film reactor is experimentally studied, and the influence of heating temperature on pyrolysis products is discussed. It has been found that with the temperature increases from 550 ℃ to 625 ℃, the yield of pyrolysis oil decreases from 74.4 wt%(± 2.2 wt%) to53.5 wt%(±1.3 wt%). The major compositions of the pyrolysis oil are C_9, C_(12) and C_(18), and β-scission reactions are predominant. The content of the light fraction C_6-C_(12) of pyrolysis oil is 69.7 wt%. Compared with other pyrolysis reactors, the yield of oil from vertical falling film pyrolysis reactor is slightly higher than that from tubular reactor,equal to that from rotary kiln reactor, and slightly lower than that in medium fluidised-bed reactor.     

压力反应釜中低温热裂解废旧LLDPE塑料制备PE蜡

以废旧线性低密度聚乙烯（LLDPE）为原料,采用压力反应釜在封闭条件下通过热裂解方法制备聚乙烯蜡（PE蜡）,研究了裂解时间、温度和压力对产物的产率、分子量和滴熔点的影响,并通过红外光谱对产物的官能团进行了分析。实验结果表明,在裂解时间为15~60 min,裂解温度约为260℃的条件下,LLDPE裂解所得到的PE蜡性能较佳,其主要成分为直链烷烃和烯烃,滴熔点大于100℃,黏均分子量处于1400~4700;由动力学分析可知,由于封闭反应体系增加了反应压力,降低了裂解温度和活化能,促进了LLDPE裂解反应进行,同时抑制了气体分子的产生,有利于获得PE蜡。     

利用废杂塑料制备燃料油

为使废杂塑料的产物回归石油产品，介绍了废杂塑料制备燃料油工艺中原料的分离、原料的预处理、催化剂的使用以及热分解、裂解工艺条件。     

Engine fuel derived from waste plastics by thermal treatment

Two series of experiments of waste polymers cracking were carried out. The first series of polymer cracking experiments was carried out in a glass reactor of 0.5 dm³ volume at atmospheric pressure and in a temperature range 350-420°C, the second one in autoclaves under hydrogen pressure (∼3-5 MPa) in the temperature range 380-440°C. The influence of cracking parameters, i.e. reaction temperature, presence and amount of cracking catalysts and composition of the polymer feed on product yields and composition of gas and liquid fractions are discussed. It was stated that the proper selection of the process parameters makes it possible to control, in the limited range, the product composition distribution as well as yields and composition of gas, gasoline and diesel oil fractions. Basic physicochemical properties of gasoline and diesel fuels obtained in both type of processes were characterised and discussed.