Pyrolysis of mixed plastics for the recovery of useful products

Thermal and catalytic pyrolysis of polystyrene (PS) with low-density polyethylene (LDPE), high-density polyethylene (HDPE), polypropylene (PP), poly-ethylene terephthalate (PET) plastics were carried out in a 25 cm³ stainless steel micro reactor at around 430–440 °C under 5.5–6.0 MPa of N₂ gas pressure for 1 h. Three reactions of each plastic with PS were conducted in the ratio of 1:1, 1:2 and 1:3. The amount of PS was varied to explore its role and reactivity. In all coprocessing reactions, ratio 1:1 afforded the best yields in the form pyrolytic oils. SIM distillation of hexane soluble portion showed that the low boiling fractions were not found and fractions were obtained only after 96 °C + boiling point. It could be due to the vaporization of high volatile components. In most of the binary pyrolysis, light cycle oil (LCO) fractions have low recovery than heavy cycle oil (HCO). GC identified some very important chemical compounds present in the liquid products obtained from the pyrolysis of mixed plastics. The results obtained from this study have shown usefulness and feasibility of the pyrolysis process of the mixed plastics as an alternative approach to feedstock recycling.     

Evaluation of pyrolysis residue of oil sludge for recycling as bed material

Pyrolysis is an appealing technique to convert oil sludge into valuable products such as gaseous and liquid fuels, however, there is lack of research on the use of solid residue after sludge pyrolysis. This work investigated the possibility of recycling solid residue as bed material for the pyrolysis process. The thermogravimetric analysis of the raw sludge in both the pyrolysis condition and combustion condition found that part of the heavy organic compounds in the oil sludge was difficult to recover by pyrolysis, though could be combusted easily in the presence of oxygen. Therefore, by leaving the heavy compound in the solid residue, the solid residue can be self-heated by combustion and cycled to the pyrolysis process to enhance heat transfer and catalysis. A series of pyrolysis residues at varies temperatures and holding times were collected after pyrolyzing oil sludge in this study. To examine whether there is sufficient potential heat remaining in the pyrolytic residue, the residue was further investigated by FTIR, proximate, ultimate analysis, and TGA in air to study the combustion characteristics and combustion kinetics. Higher pyrolysis temperature and longer pyrolysis time resulted in more ash and fixed carbon in the residue, though less volatile matter. Residue pyrolyzed at a lower temperature was easier to combust and showed lower combustion activation energy, though the recovery of organic fuel was not significant. Pyrolysis time had very minor effect on the solid residue combustion behaviour. It is more appropriate to control the residue property by governing the pyrolysis temperature.     

Development of a Separation Sequence for the Integration of a Styrene Recyclate into Polystyrene Production

This work addresses the processing of a polystyrene recyclate stream into polystyrene synthesis on an industrial scale. Evaluating the energetic demand of the separation process with the following reintegration of the recyclate stream shows a significantly reduced specific energy input compared to conventional polystyrene synthesis. Therefore, recycling polystyrene by pyrolysis and thermal separation shows a considerable potential as a tool for industrial circular production in the plastics sector.     

含油污泥热解技术研究进展

含油污泥是石油工业的主要污染物之一,其处理一直是油田以及石油企业的难题,如果处置不当,将造成严重的环境污染。热解技术是一种在无氧或缺氧的条件下,将油泥中的重质组分转化为轻质组分,并加以回收的新的含油污泥处理技术,可以更为彻底地处理含油污泥,且具有二次污染程度小、能量可回收利用的特点,是一种应用前景较广的处理方法。本文对国内外含油污泥热解技术的研究进展进行了总结,并重点介绍了温度、加热速率、停留时间、热解催化剂对于含油污泥热解效果及产物的影响,同时还阐述了热解动力学模型的拟合方法,分析了热解能量流动过程以及目前工业中应用比较广泛的热解设备,并指出未来含油污泥热解技术可能的发展方向,以期对含油污泥热解技术的发展提供参考。     

碳中和背景下国内外废塑料裂解法回收进展

人类生产生活对塑料制品日益增长的需求使得塑料废弃物迅速增加,由此引起的环境问题和社会问题亟待解决。本文综述了碳中和背景下国内外废塑料裂解法回收进展,从废塑料裂解催化剂、废塑料裂解反应器、废塑料与其他固废共裂解三个方面对废塑料裂解技术进展进行总结,归纳了国内外塑料回收企业和石油石化企业在废塑料裂解回收方面的进展,分为裂解法制油和裂解法制化学品两个方面。阐明了废塑料回收在节约能源、碳减排和经济性方面的意义,指出国内废塑料裂解法回收存在法规缺失、废塑料分类不清晰、产业链条不完善、相关学术研究不深入等问题,提出国内石油石化企业应从全生命周期角度出发对废塑料进行裂解法回收处理,结合上下游产业链,分阶段实施废塑料裂解产油品路线和产化学品路线。     

废旧轮胎裂解炭黑的改性及其应用进展

废旧轮胎作为对环境有害的固体废弃物，其组成包括炭黑、白炭黑和胶粉等多种有价值的资源。在现有回收技术中，废轮胎热裂解技术可有效回收裂解油、炭黑和钢丝等，在国内获得了广泛应用。相对于已经普遍利用的热解油和钢丝来说，热解炭黑含有质量分数14-21%的灰分和胶质层，它的高价值利用是实现废旧轮胎循环回用的关键。很多研究者开展了热解炭黑不同的改性处理工艺研究，改性后的热解炭黑可被应用于多个领域。该文主要概括了热解改性炭黑在橡胶生产中的补强作用、改性活性炭吸附剂、电池材料、以及沥青和油墨填料等方面的应用，综述了上述应用领域内热解炭黑的处理和改性方法，并指出今后热解炭黑高价值回用的方向和改性方法。     

重质有机质热解过程中挥发物的产出与逸出气体分析研究进展

煤、重质油、生物质等重质有机质富含碳氢共价结构,其轻质化和定向化学品转化是加工利用的主要目标。热解是重质有机质加工过程中最直接、最基础的反应过程,挥发物作为重要的热解产物,其组成分布及在热解过程的演变规律解析是研究的关键和热点问题。本文综述了重质有机质热解过程中挥发物的生成过程,总结了反应类型及产物组成随温度升高的阶段性变化,并以煤、油砂、油页岩、生物质、含油污泥、市政污泥以及废橡胶为例,对比了不同种类的重质有机质热解挥发物产出的异同。针对重质有机质挥发物逸出特性分析方法,本文重点介绍了质谱、傅里叶变换红外光谱逸出气体分析技术,举例说明了各方法在重质有机质有机结构解析、热解工艺条件优化、污染物控制、催化剂设计等研究上的应用,并且就现阶段热解过程逸出气体的定量分析方法和应用进行了概述。最后,本文还就重质有机质热解逸出气体分析技术提出了建议和展望,以期为重质有机质的热解研究提供参考和借鉴。     

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。     

中国石化废旧塑料化学回收与化学循环技术探索

废旧塑料化学回收是实现塑料资源可持续发展的技术之一,特别是废旧塑料热解技术备受关注。中国石油化工股份有限公司（简称：中国石化）结合自身优势,对废旧塑料化学回收及化学循环技术进行了全面设计规划,开发了几种不同途径的化学回收及化学循环技术。其中,废旧塑料生产低杂质油品（SPWO）技术,通过物理法脱杂、溶剂热解的有机耦合实现了最大量生产低杂质油品的目的,为废旧塑料的全循环利用奠定了基础;开发了废旧塑料微波辅助热解技术,可实现一步法制备低碳烯烃。废旧塑料热解油加氢生产柴油调和组分技术所得柴油馏分十六烷值可达到61.2;所开发的催化裂化技术生产汽油时,汽油产率可达50 %,而同时生产汽油和低碳烯烃产品时,汽油收率可达30 %,乙烯和丙烯产率总产率18 %以上;设计开发了废旧塑料热解油加氢?蒸汽裂解制备烯烃技术,经深度加氢预处理耦合蒸汽裂解处理后,三烯收率可达41.9 %。对不同的废旧塑料化学回收技术路线进行碳足迹分析并与石油基炼厂及废旧塑料焚烧发电技术的碳排放进行对比,废旧塑料化学回收技术具有良好的碳减排竞争力。     

Chemical recycling of polymers from Waste Electric and Electronic Equipment

This research is focused on the recycling of three types of polymers, namely polycarbonate (PC), poly(acrylonitrile‐butadiene‐styrene) (PABS), and polystyrene (PS) from Waste Electric and Electronic Equipment (WEEE). Initially, the chemical structure of each polymeric material in a variety of WEEE was identified by Fourier Transform Infra Red (FTIR) spectroscopy and Differential Scanning Calorimetry (DSC). The potential recycling of these polymers from these wastes was examined by employing two different approaches, the dissolution/reprecipitation method and the more challenging technique of pyrolysis. During the first, the polymer is separated and recycled through a solvent/non‐solvent system. It is a simple and economic technique leading to high recovery of pure polymer. Both, model polymers and plastic parts from WEEEs were studied and optimum experimental conditions, including dissolution temperature and time, polymer concentration and type of solvent were proposed to achieve significant recovery of the polymer (>90 wt %). Furthermore, pyrolysis of waste Compact Disks (CD) was investigated and compared with model poly(bisphenol A carbonate) (PC) through a laboratory‐scale fixed bed reactor. The appropriate pyrolysis temperature was selected after measuring the thermal degradation of model PC by Thermogravimetric analysis (TGA). A large amount of oil was measured, together with a smaller amount of gaseous product, leaving also a solid residue. For both samples, the gaseous fraction consisted mainly of CO₂ and CO whereas in the liquid fraction a large amount of different phenolic compounds, including the monomer bisphenol A, was measured. It seems that recycling of used CDs by pyrolysis is a very promising technique having the potential of producing useful high‐value chemicals, which may find applications in the petrochemical industry. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

注蒸汽条件下供氢催化改质稠油及其沥青质热分解性质

利用CWYF-Ⅰ型高压反应釜模拟热采条件下,以甲酸作为供氢体.以自制的油溶性有机镍盐为催化剂进行的稠油水热裂解反应.考察了供氢体的加入对催化水热裂解反应前后稠油黏度、族组成及硫含量的影响,并采用TG-DTA分析法对供氢催化改质反应前后稠油中沥青质的热转化行为进行了分析.结果表明,随着加入供氢体质量分数增加,供氢催化水热裂解后稠油降黏率增大,饱和烃、芳香烃含量增加,胶质,沥青质含量降低,同时硫含量下降.供氢催化水热裂解反应后的稠油中沥青质TG-DTA曲线分析表明,供氢催化水热裂解反应后稠油中沥青质失重量高于催化水热裂解反应前稠油中含有的沥青质的失重量.经过供氢催化水热裂解反应,稠油中沥青质的稳定性下降.     

Distribution and characteristics of pyrolysis products from automobile shredder residue using an experimental semi-batch reactor

Automobile shredder residue (ASR) generated by end-of-life vehicles, comprises more than 20% of a new vehicle by weight. Significant amounts of polymers in ASR, such as Poly Propylene (PP), Poly Ethylene (PE), Acrylonitrile Butadiene Styrene (ABS), Ethylene Propylene Ethylidene Nobomene (EPDM), rubber, Polyethylene Terephthalate (PET), Poly Amide (PA), and Poly Vinyl Chloride (PVC), can be used as energy or chemical sources, whereas other components, such as tires, rubber, glass, wood, sand/dust, and heavy metals inhibit the recycling of ASR. In many countries, landfill use of ASR is regulated, so landfill costs have increased, as has inappropriate disposal; sending ASR to landfills will be needed to be regulated in Korea. Pyrolysis has been suggested as an economically feasible recycling and recovery technique for ASR in Korea and other advanced countries. Before such technology is implemented, the characteristics of pyrolyzed products should be investigated. Shredded samples from the facility were collected, and calorific value, elemental analysis, and leaching tests were performed to determine ASR characteristics. Pyrolysis experiments were conducted at five different temperatures, 400, 500, 600, 700, and 800 °C, and the product distributions of gas, tar, and char were investigated. The optimal temperature for ASR pyrolysis, in terms of yield efficiency, was found to be 600 °C. The mean calorific value was also found to be higher in this case; thus, ASR can be treated as an auxiliary fuel. During pyrolysis, there were high ignition losses of light and heavy fluff, due to the presence of organic materials. The leaching concentrations of all tested heavy metals were found to be within the Korean guideline values. In terms of carbon number distributions, pyrolysis of ASR at 600 °C was optimal. For further utilization of pyrolysis products as fuel, the characteristics of char, oil, and gas were investigated with an experimental batch reactor.     

Influence of Molecular Characteristics and Size Effects in Polystyrene Pyrolysis

Understanding the structure-property-process relationships in pyrolysis-based recycling of polymers offers new possibilities, like, energy-efficient process designs and tailored products. With the consideration of sample size as well as thermal rate effects, the influence of the molecular weight distribution of polystyrene on the pyrolysis kinetics is investigated. It is shown that molecular weight distribution significantly impacts pyrolysis kinetics. Thermal rate and sample weight affect the material conversion rate and are decisive for determining the thermal processing window.     

烃类裂解制乙烯催化剂研究进展

阐述了烃类催化热裂解的机理，国外轻油催化热裂解催化剂的科研成果及国内重油催化热裂解催化剂的研究成果及进展，根据上述研究成果提出了自主开发轻油热裂解制乙烯的催化剂研究方向。     

催化裂解制低碳烯烃技术研究进展

综述了目前国内外以轻烃到重油范围内为原料的催化裂解工艺技术,着重介绍了我国有代表性的研究成果DCC、CPP及HCC工艺。而重油催化裂解更适合于我国国情,并指出在研制与工艺技术相匹配的高效新型催化剂方面,找到催化剂酸强度、孔道分布、金属含量和活性组分含量与催化裂解活性之间的关系,为催化裂解制低碳烯烃工艺技术能够全面实行工业化奠定更坚实的基础。     

Demetallization of heavy oil through pyrolysis: A reaction kinetics analysis

By tracking the transfer of vanadium and nickel in pyrolysis products, a seven-lump reaction kinetic model for pyrolysis-based demetallization of heavy oil was established. During pyrolysis, the demetallization of heavy oil is achieved by condensing metal-rich resins and asphaltenes to coke. The condensation of oil components originally contained in heavy oil differs greatly in reaction behavior, having the activation energy between 167 and 361 kJ/mol. As the pyrolysis progresses, the newly formed heavy components show a condensation behavior close to that of the light components. Limited by high activation energy and low initial fraction, the condensation of asphaltenes to coke and the resulting removal of metals contained in asphaltenes are hindered. Meanwhile, the condensation of light components has a major contribution to coke formation. An increase in reaction temperature accelerates the demetallization, but hardly changes the yield and component distribution of liquid products at the same metal removal rate.     

废塑料热解油中杂质硅、氯的影响及应对策略探讨

废旧塑料化学法回收是应对白色污染,同时实现高值化回收利用的有效方法之一,尤其是利用废塑料热解油进一步生产燃料油或化工产品的技术路线备受关注。但塑料垃圾杂质较多、成份复杂,其中杂质硅、氯对反应器、产物、催化剂或反应本身的影响均不可忽视。本文对塑料热解油中硅、氯杂质的来源、形态、生成机制及催化转化规律进行了分析,并根据杂质可能产生的不利影响提出了有效的应对策略。     

废橡胶热裂解技术现状及发展方向

废橡胶是继白色污染之后又一大污染——黑色污染,是世界性的又一大难题,其中比重最大的就是废轮胎,世界各国尤其是发达国家纷纷致力于轮胎的回收利用研究.特别是其回收产品的再利用:一方面解决资源的短缺;另一方面获取较高的经济价值.经长期的探究,人们发现与翻新、制造胶粉和再生胶、作沥青填料、直接作为燃料焚烧等处理方法相比,热裂解...     

YN-1型镍系催化剂在裂解重C_9~+馏分一段加氢装置上长周期运行

介绍了中国石化催化剂北京燕山分公司的裂解重C+9馏分一段加氢工况,采用了低压、低空速、高氢油比和高循环比的加氢工艺。依据工业装置原料性质、反应温度和反应器进、出口压力变化情况,统计分析了使用YN-1型镍系催化剂没有经过再生进行一段加氢产品的溴价和双烯含量变化,工业应用结果表明,YN-1型镍系催化剂具有优异的加氢活性和长周期运行的稳定性。     

Recycling polymeric wastes by means of pyrolysis

Different polymeric wastes, which include materials from the automobile industry, such as tyres, automobile shredder residues (ASR) and sheet moulding compound (SMC), and materials from municipal solid wastes (MSW), such as cardboard, tetrabrik and plastics (LDPE, PP, PS, PET and PVC), pure and mixed, have been pyrolysed in a 3.5 dm³ autoclave at 500 °C for 30 min in a nitrogen atmosphere. The amount and characteristics of the solid, liquids and gases obtained are presented. The suitability of the different materials for the pyrolysis recycling process is discussed. It is concluded that pyrolysis is a very promising technique for recycling tyres, SMC, one type of ASR (heavy ASR), and LDPE, PP and PS, either pure or mixed; with all of them valuable solid, liquid and gaseous products are obtained in pyrolysis. On the contrary, light ASR, tetrabrik and cardboard do not yield valuable products in the pyrolysis process and therefore their recycling by pyrolysis is not of interest, except as a way of volume reduction. PET and PVC turned out to be troublesome in the pyrolysis experiments; for a proper study of their recycling by pyrolysis other operating conditions and installations are required. © 2002 Society of Chemical Industry