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废轮胎单级蒸汽热解所得含碳材料特性的对比分析

Comparative analysis of the characteristics of carbonaceous material obtained via single-staged steam pyrolysis of waste tires.

作者信息

Larionov Kirill B, Slyusarskiy Konstantin V, Ivanov Aleksey A, Mishakov Ilya V, Pak Alexander Y, Jankovsky Stanislav A, Stoyanovskii Vladimir O, Vedyagin Aleksey A, Gubin Vladimir E

机构信息

School of Energy & Power Engineering, Tomsk Polytechnic University, Tomsk, Russia.

Laboratory of Catalysis and Processing of Hydrocarbons, National University of Science and Technology MISIS, Moscow, Russia.

出版信息

J Air Waste Manag Assoc. 2022 Feb;72(2):161-175. doi: 10.1080/10962247.2021.2010619. Epub 2022 Jan 5.

DOI:10.1080/10962247.2021.2010619
PMID:34846272
Abstract

The two-stage technology of porous carbonaceous material obtained via pyrolysis in inert medium with subsequent activation by steam is well known. While steam could be a suitable substance for pyrolysis as well, single-staged technology for waste tire recycling is yet to be developed. A comparative analysis of the characteristics of the carbonaceous materials obtained by the single-staged steam pyrolysis of waste tires was carried out, which could provide a theoretical background for the development of such technology. The steam pyrolysis was performed in a tubular reactor in an overheated steam medium (500°C with 5 kg/h mass flow rate). The technical characteristics of the obtained samples were evaluated in the context of their potential for further application as absorbent and raw material for rubber production according to Chemical Abstracts Service No. 1333-86-4. The composition and physico-chemical properties of the obtained samples were studied using BET and thermogravimetric analysis, atomic emission, transmission and scanning electron microscopies, Raman, X-ray diffraction, and photoelectron spectroscopies. The results revealed that the structure and properties of all obtained carbonaceous material samples were similar. The samples consisted of amorphous carbon (with a disordered graphite lattice) and contained a significant amount of metal oxides. According to experimental data, zinc was present in the form of ZnO with a binding energy of 1022.4 eV, while sulfur was observed in the form of sulfide and oxysulfide with binding energies of 161.8 and 163.2 eV, respectively. According to electron microscopy, the morphology of samples was represented by a set of spherical agglomerates comprising nanosized particles. According to the BET analysis of the samples, the specific surface area varied in the range between 52.0 and 66.0 m/g and the pore volume values were within a range of 0.53-0.87 cm/g, while the average pore size varied from 412 to 527 Å.: Our paper presents original research in the field of characterization of solid material obtained by single-staged steam gasification of waste tires, which were produced and exploited in conditions of Russia. Modern technology allows thermal utilization of waste tires by obtaining powders of carbonaceous material, which could be used as fuel, adsorbent, etc., but this process usually consists of two stages - pyrolysis in inert medium and activation in steam or carbon dioxide. One of the most promising directions of technological development is simplifying this process into single step, ensuring that the obtained material could be used as carbon black or adsorbent for gas steam cleansing. No data on suitability of carbonaceous material obtained by single-step steam pyrolysis of all-season waste tires to be adsorbent and/or carbon black is present in the literature. In order to evaluate the suitability of the obtained material to be adsorbent, the high specific surface area should be determined, while CAS technical standards specify many chemical and physical properties of industrial carbon black.The aim of the current article is to study the properties of carbonaceous material obtained during single-staged steam gasification of four different all-season tires (due to their widespread application worldwide) and evaluate its fitness as industrial-scale carbon black or adsorbent. The additional problem addressed was the evaluation of the variation in characteristics of carbonaceous material obtained due to different origins of tires. Experiments were conducted in a tubular lab reactor in order to simplify the experimental procedure while ensuring the applicability of the obtained results to practical conditions.The obtained results could be used for the development of the technology for closed-cycle tire processing (because black carbon is used for tire production) and adsorbent production. The characteristics of the materials obtained allow us to choose optimal parameters for such treatment and develop special policies and programs, which will integrate and regulate waste tire utilization via steam gasification.

摘要

通过在惰性介质中热解并随后用蒸汽活化获得多孔碳质材料的两阶段技术是众所周知的。虽然蒸汽也可能是热解的合适物质,但用于废旧轮胎回收的单阶段技术尚未开发出来。对通过废旧轮胎单阶段蒸汽热解获得的碳质材料的特性进行了比较分析,这可为该技术的开发提供理论背景。蒸汽热解在管式反应器中于过热蒸汽介质(500°C,质量流量为5 kg/h)中进行。根据化学文摘社编号1333 - 86 - 4,在其作为吸收剂和橡胶生产原料的进一步应用潜力的背景下评估了所得样品的技术特性。使用BET和热重分析、原子发射、透射和扫描电子显微镜、拉曼光谱、X射线衍射和光电子能谱研究了所得样品的组成和物理化学性质。结果表明,所有获得的碳质材料样品的结构和性质相似。样品由无定形碳(具有无序石墨晶格)组成,并含有大量金属氧化物。根据实验数据,锌以结合能为1022.4 eV的ZnO形式存在,而硫分别以结合能为161.8和163.2 eV的硫化物和氧硫化物形式存在。根据电子显微镜观察,样品的形态由一组包含纳米级颗粒的球形团聚体表示。根据样品的BET分析,比表面积在52.0至66.0 m/g之间变化,孔体积值在0.53 - 0.87 cm/g范围内,而平均孔径在412至527 Å之间变化。我们的论文展示了在俄罗斯生产和使用条件下通过废旧轮胎单阶段蒸汽气化获得的固体材料表征领域的原创研究。现代技术允许通过获得碳质材料粉末来对废旧轮胎进行热利用,这些粉末可用作燃料、吸附剂等,但这个过程通常包括两个阶段——在惰性介质中热解和在蒸汽或二氧化碳中活化。技术发展最有前景的方向之一是将这个过程简化为单一步骤,确保所得材料可用于作为炭黑或用于气体蒸汽净化的吸附剂。文献中没有关于通过全季废旧轮胎单步蒸汽热解获得的碳质材料作为吸附剂和/或炭黑适用性的数据。为了评估所得材料作为吸附剂的适用性,应确定高比表面积,而CAS技术标准规定了工业炭黑的许多化学和物理性质。本文的目的是研究在四种不同全季轮胎(由于其在全球广泛应用)的单阶段蒸汽气化过程中获得的碳质材料的性质,并评估其作为工业规模炭黑或吸附剂的适用性。解决的另一个问题是评估由于轮胎不同来源而获得的碳质材料特性的变化。为了简化实验过程并确保所得结果适用于实际条件,在管式实验室反应器中进行了实验。所得结果可用于开发封闭循环轮胎加工技术(因为炭黑用于轮胎生产)和吸附剂生产。所获得材料的特性使我们能够选择这种处理的最佳参数,并制定特殊政策和计划,这些政策和计划将通过蒸汽气化整合和规范废旧轮胎的利用。

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