连续双螺杆反应器衍生的废轮胎热解油的燃料和化学性质,Energy & Fuels

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连续双螺杆反应器衍生的废轮胎热解油的燃料和化学性质
Energy & Fuels ( IF 5.2 ) Pub Date : 2020-08-26 , DOI: 10.1021/acs.energyfuels.0c02271
Felipe Campuzano _{1,

2,

3} , Abdul Gani Abdul Jameel ₄ , Wen Zhang ₅ , Abdul-Hamid Emwas ₅ , Andrés F. Agudelo ₂ , Juan Daniel Martínez ₁ , S. Mani Sarathy ₃

Affiliation

轮胎热解油（TPO）是碳氢化合物（HC）的复杂混合物，它是从废轮胎（WT）的热解中获得的有用馏分之一。由于其高能量密度（HHV〜43 MJ / kg），在燃烧系统中将TPO用作燃料是回收WT的一种有前途的方法。然而，TPO的基本燃料特性和燃烧特性仍未得到开发，这成为潜在应用的瓶颈。这项工作是对实验室规模的双螺杆反应器生产的TPO的结构特征的全面了解，这是确定应用程序和升级策略的第一步。因此，先进的分析技术，例如傅立叶变换离子回旋共振质谱（FT-ICR MS）和¹ H和¹³利用了C核磁共振（NMR）光谱。此外，我们还介绍了将CaO添加到WT中获得的TPO的特性，它是用于原位升级的低成本催化材料，在本文中称为TPO [CaO]。FT-ICR MS结果表明，纯HC（HC _（TPO） = 74.9％和HC _{（TPO [CaO]）} = 78.6％）和含有一个硫原子（S ₁）的HC （S _1（TPO） = 14.3 _）的显着存在。％和S _{1（TPO [CaO]）}＝ 13.9％。HC化合物主要以三芳烃（26％），四芳烃（13％和15％）和五芳烃（22％和30％）的形式存在，而S ₁化合物主要以二苯并噻吩（31％）和苯并萘噻吩（34％）的形式存在。通过FT-ICR MS解析的化合物分别显示出TPO和TPO [CaO]的平均双键当量（DBE）数分别为11.3和12.2。这些高的DBE值表明明显存在稠合的芳族结构。¹ H NMR分析表明，亚甲基（CH ₂），甲基（CH ₃）和环烷基中的氢原子以及芳族结构中的氢原子占两种燃料的80％以上。同样，链烷烃基团中的碳原子（CH ₂和CH ₃）和芳环中的质子化碳一起构成TPO和TPO [CaO]中碳原子的50％以上。这项工作中报告的信息提供了对TPO结构特征的新见解，该结构是一种有前途的技术（用作双螺杆反应堆）用作燃料的技术，以及用于升级策略的设计。

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Fuel and Chemical Properties of Waste Tire Pyrolysis Oil Derived from a Continuous Twin-Auger Reactor

Tire pyrolysis oil (TPO) is a complex mixture of hydrocarbons (HC), and it is one of the useful fractions obtained from the pyrolysis of waste tires (WT). As a result of its high energy density (HHV ∼ 43 MJ/kg), TPO use as a fuel in combustion systems is a promising approach for recycling WT. However, fundamental fuel characteristics and combustion properties of TPO are still unexplored, which stand as a bottleneck for potential applications. This work pursues a comprehensive understanding of the structural characteristics of a TPO produced in a lab-scale twin-auger reactor as a first step toward defining applications and upgrading strategies. Therefore, advanced analytical techniques such as Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) and ¹H and ¹³C nuclear magnetic resonance (NMR) spectroscopy were utilized. In addition, we also present the characterization of a TPO obtained from adding CaO to WT, as a low-cost catalytic material for its in situ upgrading, herein named TPO[CaO]. FT-ICR MS results revealed the significant presence of pure HC (HC_(TPO) = 74.9% and HC_(TPO[CaO]) = 78.6%) and HC containing one sulfur atom (S₁) (S_1(TPO) = 14.3% and S_1(TPO[CaO]) = 13.9%). HC compounds were found mainly in the form of triaromatics (26%), tetra-aromatics (13 and 15%), and penta-aromatics (22 and 30%), while S₁ compounds were found mainly in the form of dibenzothiophene (31%) and benzonaphthothiophene (34%). The resolved compounds by means of FT-ICR MS exhibited an average double bond equivalent (DBE) number of 11.3 and 12.2 for TPO and TPO[CaO], respectively. These high DBE values were indicators of the significant presence of condensed aromatic structures. ¹H NMR analysis showed that hydrogen atoms in methylene (CH₂), methyl (CH₃), and naphthenic groups and hydrogen atoms in aromatic structures make up more than 80% of both fuels. Similarly, carbon atoms in paraffinic groups (both CH₂ and CH₃) and protonated carbons in aromatic rings together form more than 50% of the carbon atoms in TPO and TPO[CaO]. The information reported in this work provides new insights into the structural characteristics of the TPO obtained in a promising technology as the twin-auger reactor for its use as a fuel, as well as for the design of upgrading strategies.

更新日期：2020-10-16

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