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。     

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     

热裂解回收利用废弃聚氯乙烯及其混合塑料

综述了以热裂解工艺(包括热裂解与化学处理相结合的工艺)回收利用废弃PVC及PVC混合塑料的近期进展,讨论了PVC热裂解的工艺过程、工艺条件、动力学参数、存在问题及改进方向。认为PVC的热裂解必须解决的首要问题是分离回收所产生的HCl及控制液态产品的卤代烃含量,而降低热裂解温度和提高热裂解效率则是其改进重点。     

不同类型分子筛催化热解陈腐垃圾性能研究

选用3种不同类型的分子筛催化剂HZSM-5、HY和HBeta,以垃圾填埋场陈腐垃圾为原料,进行绝氧热解和催化热解对比研究。结果表明,分子筛催化剂的加入不仅对陈腐垃圾热解产物产率有明显影响,而且对热解气和热解油的品质有明显的提高。对比3种催化剂发现,HZSM-5更有利于热解气的产生,而且所得热解气的热值最高,为67.45 MJ·m^-3,所得热解油中汽油组分最多,为质量分数65.4%,而重馏分油组分仅为6.9%。HY和HBeta则得到相对更高的热解油产量,尤其是轻质柴油,质量分数分别为38.1%和41.4%。3种催化剂截然不同的催化热解产物产率和产品性质与其孔道结构、织构性质和酸性质均密切相关。     

塑料催化热解制备高附加值产品的研究进展

塑料催化热解技术可定向或联产制备低碳烯烃、单环芳烃、碳纳米管（CNTs）和氢气等能源产品,其调控过程简单,且产物选择性好、附加值高,因而受到了广泛的关注。在较短的停留时间（＜1 s）和较高的反应温度（＞800℃）下,塑料热解可得到较高产率的烯烃单体,而芳烃产物的形成更依赖催化剂的酸位点和孔结构。Fe、Co、Ni基催化剂可将塑料热解产生的含碳挥发分转为CNTs和富氢气,其CNTs产率和氢转化效率可分别达到30%（质量）和90%以上。总结了塑料催化热解制备高附加值能源化工产品的研究进展,讨论总结了温度、停留时间、催化剂等因素对产物分布和品质的作用机制,并对各类产物形成机理和制备方法分别进行了回顾与展望。     

塑料催化热解制备高附加值产品的研究进展

塑料催化热解技术可定向或联产制备低碳烯烃、单环芳烃、碳纳米管（CNTs）和氢气等能源产品,其调控过程简单,且产物选择性好、附加值高,因而受到了广泛的关注。在较短的停留时间（＜1 s）和较高的反应温度（＞800℃）下,塑料热解可得到较高产率的烯烃单体,而芳烃产物的形成更依赖催化剂的酸位点和孔结构。Fe、Co、Ni基催化剂可将塑料热解产生的含碳挥发分转为CNTs和富氢气,其CNTs产率和氢转化效率可分别达到30%（质量）和90%以上。总结了塑料催化热解制备高附加值能源化工产品的研究进展,讨论总结了温度、停留时间、催化剂等因素对产物分布和品质的作用机制,并对各类产物形成机理和制备方法分别进行了回顾与展望。     

Hydrogen balance for catalytic pyrolysis of atmospheric residue

The catalytic pyrolysis of atmospheric residue over the commercial catalytic pyrolysis process catalyst (Al₂O₃/Fe₂O₃/Na₂O (46.3, 0.27 and 0.04 wt.%, respectively)) was investigated in a confined fluidized bed reactor. The yield of light olefins was above 37 wt.% at reaction temperature above 600 °C and it reached a maximum of 47 wt.% at 660 °C. The main components in light olefins were ethylene and propylene, and those in liquid samples were aromatics. The main components in light alkanes were propane and i-butane at low reaction temperature (600 °C), and those were methane and ethane at high reaction temperature (700 °C). The hydrogen content of light olefins was about 14.27 wt.%, that of light alkanes was above 18.5 wt.%, that of gasoline was below 12.5 wt.%, and that of diesel was below 7.8 wt.%. The percentage of the hydrogen in light alkanes to total hydrogen was above 29% and that in light olefins was above 40%. The effective utilization ratio of hydrogen decreased from 66.60% at 600 °C to 61.44% at 700 °C.     

关于一次性塑料包装材料与环境问题的思考

扼要评述了塑料包装材料及其废弃物所面临的环境问题及其严重挑战，分析了当前塑料废弃物对环境带来的负面影响，并提出了加强管理，回收利用和降解塑料等治理措施。     

废塑料裂解新进展

废塑料的裂解是回收再利用塑料的方法之一。本文详细介绍了废塑料的选择和分离技术,裂解反应器及工艺条件,裂解催化剂,裂解产物的综合利用等。对进一步优化裂解技术有一定的指导意义。     

城市污水污泥催化快速热解制备芳香烃和烯烃

将城市污水污泥干燥处理,在小型热解分析系统中使用沸石分子筛进行催化快速热解实验,研究热解条件对芳香烃和烯烃产率及选择性的影响。结果表明：污泥快速热解产物中,烃类物质和含氮化合物较多,这些组分主要源自污泥中的蛋白质和油脂成分;添加催化剂后,芳香烃和烯烃的产率明显提高;在热解温度500℃、催化温度600℃条件下芳香烃和烯烃的产率分别为24%和19%。另外,污泥中大部分的N、P、Na和K等元素依然保留在炭粉中。     

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。     

Kinetics of diffusion of a pollutant from a recycled polymer through a functional barrier: Recycling plastics for food packaging

Recycled polymers containing a pollutant can be used for food packaging if the food is protected by a functional barrier made of virgin polymer. The mathematical treatment of the diffusion of pollutant through the packaging is established when the diffusivity is constant and when there is no transfer through the packaging-food interface. A functional barrier not only reduces but also delays migration during a lag phase. An increase in the relative thickness of the functional barrier dramatically increases its efficiency. Practical examples are presented. The difficulties of control of migration through functional barriers are pointed out. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 597–607, 1997     

Thermal deactivation studies of coconut shell pyrolysis

The kinetics of pyrolysis of predried coconut shell sample has been investigated in the temperature range of 523 K to 1023 K in an inert atmosphere by captive sample technique. A kinetic scheme has been proposed where two parallel reactions are given for the production of volatiles and char. The reaction rate constants are found to decrease with high temperatures above 673 K due to chemical and physical changes of the reactant during devolatilisation reaction. Several deactivation models have been proposed to give good agreement with the experimental data.     

木质素催化热解用催化剂的研究进展

木质素是一种结构复杂、产量丰富但利用率较低的生物质资源,可通过催化热解解聚为高附加值产物,具有广阔的应用前景。本文介绍了催化剂机理研究方法和催化剂作用方式,比较了催化木质素热解常用的分子筛类催化剂、金属氧化物类催化剂和金属盐类催化剂的催化性能、产物收率、产品分布、催化机理及优缺点。文中指出：分子筛类催化剂的脱氧能力强、酸度高,但液体产物收率较低;金属氧化物类催化剂具有液体产物收率较高、热稳定性强等优点,但依赖于催化剂酸碱性的调控;金属盐类催化剂虽高效、价格低廉,但热稳定性差、易失活。同时,本文对木质素催化热解领域提出了展望,未来热解催化剂的研究有待深入和系统化,根据木质素种类和目标产物设计复合型催化剂、核壳型催化剂和多催化剂协同催化是未来热解催化剂发展的趋势。     

催化裂解制低碳烯烃技术研究进展

对以石油路线生产低碳烯烃的催化裂解工艺进行了综述。催化裂解结合了传统蒸汽裂解和流化催化裂化的优势,表现出良好的原料适应性和较高的低碳烯烃产率,针对不同的石油裂解原料已经开展了相应工艺技术的研究。本文总结了目前催化裂解制低碳烯烃技术的研究进展,指出ZSM-5分子筛催化剂、热力学平衡限制和动力学反应条件是催化裂解反应过程中的重要影响因素和研究内容。催化剂研究仍是催化裂解工艺开发的重点,而热力学和动力学是研究反应规律的有效方法,这是今后实现石油烃类定向转化的研究方向。     

废塑料裂解及塑料油精制研究进展

废塑料对环境造成的污染日趋严重,其有效处理成为全球关注的重要问题。对废塑料裂解后产生的废塑料油进一步加工处理得到高附加值化工产品是废塑料资源化利用的有效途径之一。综述目前废塑料裂解制油的发展状况和常用工艺,并比较各种工艺优缺点。介绍所得废塑料油后续精制加工的研究进展,并提出今后的研究方向。     

废塑料与废机油共催化裂解制取燃料油的研究

以废塑料和废机油为原料,共催化裂解制备燃料油,克服了废塑料裂解因传热差,裂解炉中温度极不均匀、结焦的难题,提高了燃料油得率。实验中考察了裂解温度、不同油固比、萃取剂对燃料油得率和组成的影响。在混合废塑料为PE∶PP∶PS=3∶1.2∶1、裂解温度为420℃、油固比为1.5、ZSM-5/50H分子筛为催化剂的条件下,燃料油得率可达到89%以上,汽、柴油比例达83%。采用络合萃取剂精制裂解产物可显著提高燃料油的安定性。     

Mathematical modeling of polyethylene terephthalate pyrolysis in a spouted bed

A model has been developed for pyrolysis of polyethylene terephthalate (PET) in a spouted bed reactor based on the conservation equations for heat, mass, and momentum transports. A spouted bed has been constructed and the kinetic parameters have been obtained within the temperature range of 723–833 K, using two particle size ranges, (0.1–1.0) × 10^?3 and (1.0–3.0) × 10^?3 m. The model' predictions for the radial distributions of temperature and concentration confirm the excellent mixing of particles. Thus, spouted beds are appropriate equipments for performing kinetic studies of PET pyrolysis. The inlet gas temperature and the mass of PET highly affect PET conversion. The amount of inert particles has a negligible effect on the conversion and it can be reduced as far as a stable spouting is preserved. The gas flow suffices to eliminate the external heat and mass‐transfer limitations. It can be reduced to the minimum value to decrease the energy consumption. © 2015 American Institute of Chemical Engineers AIChE J, 61: 1900–1911, 2015     

催化剂制备与研究热解温度对自模板法制备纳米催化剂催化活性的影响

金属有机骨架材料(MOFs)作为典型的自模板材料已被广泛应用于催化、电化学和吸附等领域。采用水热法合成两种含氮的Co-Ni-MOF和Co-Cu-MOF材料,并以两种材料为模板剂,在不同温度热解制备Co-Ni@NC和Co-Cu@NC纳米催化剂。将两种纳米催化剂用于乙基苯选择性氧化制备苯乙酮反应, 研究热解温度对催化剂催化活性的影响。结果表明,随着热解温度升高,催化活性逐渐增强,当热解温度达到900 ℃时,催化活性最高,苯乙酮收率为98%~99%,催化剂还表现出较好的重复使用性能。     

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。