Journal of Analytical and Applied Pyrolysis最新文献_第5页

A critical review of the influence of supercritical water on the pyrolysis of plastic waste: Modelling approaches and process effects 超临界水对塑料废弃物热解影响的重要综述：建模方法和工艺效应

IF 5.8 2区化学 Q1 CHEMISTRY, ANALYTICAL

Journal of Analytical and Applied Pyrolysis

Pub Date : 2024-10-01 DOI: 10.1016/j.jaap.2024.106805

Gust Popelier , Gilles Dossche , Sphurti Prakash Kulkarni , Florence Vermeire , Maarten Sabbe , Kevin M. Van Geem

Supercritical water has emerged as a promising solvent for the pyrolysis of plastic waste, offering advantageous effects on both the process and its products. Experimental observations have shown that the presence of supercritical water reduces coke formation and enhances liquid yield during plastic waste pyrolysis. However, these effects are not significant for small non-heteroatomic hydrocarbons such as hexane or tert-butylbenzene. Consequently, the influence of supercritical water only becomes prominent for larger hydrocarbons. Despite this, modelling efforts have predominantly focused on these small, often heteroatomic, compounds. This review aims to clarify how supercritical water impacts the pyrolysis of polyolefins, highlighting significant effects and proposing approaches for modelling supercritical water pyrolysis. Essential to understand is the phase behaviour exhibited by water-hydrocarbon systems. To this end, we have further explored promising equations of state for the modelling of such systems, particularly in the supercritical domain. Additionally, the effects of supercritical water on the pyrolysis process are examined both as a medium and as a reactant. As a medium, supercritical water influences the process mainly through phase separation and dilution, but it can also stabilize molecules and affect diffusion limitations. As a reactant in non-heteroatom containing systems, water serves primarily as a radical carrier.

超临界水已成为塑料废弃物热解过程中一种很有前途的溶剂，对热解过程及其产品都有好处。实验观察表明，在塑料废物热解过程中，超临界水的存在可减少焦炭的形成并提高液体产量。然而，这些影响对于正己烷或叔丁基苯等小的非原子烃类并不明显。因此，超临界水只对较大的碳氢化合物有显著影响。尽管如此，建模工作仍主要集中在这些小的、通常是异原子化合物上。本综述旨在阐明超临界水如何影响聚烯烃的热解，强调其重大影响，并提出超临界水热解建模方法。了解水-碳氢化合物体系所表现出的相行为至关重要。为此，我们进一步探索了此类系统建模的可行状态方程，尤其是在超临界领域。此外，我们还研究了超临界水作为介质和反应物对热解过程的影响。作为介质，超临界水主要通过相分离和稀释来影响过程，但它也可以稳定分子并影响扩散限制。作为非异质原子体系中的反应物，水主要是作为自由基载体。

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引用次数: 0

Co-pyrolysis of biomass/polyurethane foam waste: Thermodynamic study using Aspen Plus 生物质/聚氨酯泡沫废料的共热解：使用 Aspen Plus 进行热力学研究

IF 5.8 2区化学 Q1 CHEMISTRY, ANALYTICAL

Journal of Analytical and Applied Pyrolysis

Pub Date : 2024-10-01 DOI: 10.1016/j.jaap.2024.106833

Yaneeporn Patcharavorachot , Supanat Pradiskhean , Tanawat Aentung , Dang Saebea , Amornchai Arpornwichanop

Due to the varieties and identical feature of solid waste, this research aims to consider the use of various feedstocks in pyrolysis process for liquid fuel production. The feedstock considered covers woody and non-woody biomass and plastic waste which are represented by sawdust (SD), palm leaf (PL) and polyurethane foam (PU) waste. In this research, both pure solid waste and the co-pyrolysis of biomass and plastic wastes were determined based on thermodynamics study. The model of pyrolysis process developed through Aspen Plus simulator was implemented to study the product yield, higher heating value (HHV) and energy consumption with a wider range of pyrolysis temperature and blending weight ratio. The simulation results clearly showed that the use of pure PU waste can provide the highest oil yield (∼44 wt%) which is corresponded to highest HHV (∼28 MJ/kg). The pyrolysis, operating at 400 °C, can provide the most significant quantity of oil. For the co-pyrolysis, the results revealed that more PU waste blended in both biomasses can improve both oil yield and HHV while the energy consumption is lower. From the simulation results, the optimal blending weight ratio of biomass and PU waste at 25:75 can provide suitable oil yield (∼43 wt%), HHV (∼26 MJ/kg) and energy consumption (243 kW).

由于固体废弃物种类繁多且特征相同，本研究旨在考虑在热解过程中使用各种原料生产液体燃料。考虑的原料包括木质和非木质生物质以及塑料废料，其中以锯屑（SD）、棕榈叶（PL）和聚氨酯泡沫（PU）废料为代表。本研究根据热力学研究确定了纯固体废物以及生物质和塑料废物的共热解。利用 Aspen Plus 模拟器开发的热解过程模型，研究了在更宽的热解温度和混合重量比范围内的产品产量、高热值（HHV）和能耗。模拟结果清楚地表明，使用纯聚氨酯废料可提供最高的产油量（∼44 wt%），与之相对应的是最高的 HHV（∼28 MJ/kg）。在 400 °C 下进行的热解可以提供最大量的油。对于共热解，结果显示，在两种生物质中掺入更多的聚氨酯废料可提高产油量和 HHV，同时能耗较低。从模拟结果来看，生物质与聚氨酯废料的最佳混合重量比为 25:75，可提供合适的产油量（43 wt%）、高热值（26 MJ/kg）和能耗（243 kW）。

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引用次数: 0

Pyrolysis characteristics and kinetic analysis of coating pitch derived from ethylene tar using model-free and model-fitting methods 使用无模型和模型拟合方法分析乙烯焦油衍生涂层沥青的热解特性和动力学分析

IF 5.8 2区化学 Q1 CHEMISTRY, ANALYTICAL

Journal of Analytical and Applied Pyrolysis

Pub Date : 2024-10-01 DOI: 10.1016/j.jaap.2024.106803

Wei Gao, Yongzheng Zhang, Yanli Wang, Liang Zhan

This work conducted the pyrolysis of coating pitch derived from the ethylene tar through thermogravimetry analysis. The thermogravimetry-mass spectrometry and solid-state ¹³C nuclear magnetic resonance spectroscopy were performed to correlate the structural characteristics with the pyrolysis behavior. Meanwhile, the pyrolysis kinetics were estimated with model-free and model-fitting methods. The TG-DTG results showed that the pyrolysis process was generally divided into drying, fast pyrolysis, and polycondensation stages, accompanied by the decomposition of active functional groups like the aliphatic carbons bonded to oxygen (

f_{al}^{O}

), the pyrolysis of relatively stable groups like the non-protonated aromatic carbon (

f_{a}^{H}

), and the condensation of high bonding-energy aromatic structure like aromatic bridgehead carbon (

f_{a}^{B}

). The activation energy obtained from model-free analysis ranged from 78.12 to 150.92 kJ/mol with the increasing conversion, indicating the pyrolysis process as a multi-step reaction mechanism. Furthermore, the reaction model A1/3 (

g (α) = {[- \ln (1 - α)]}^{3}

) was identified as the most suitable model for the pyrolysis of coating pitch in the conversion range of 0.25–0.8. The modeling values matched well with the experimental data, indicating the accuracy and feasibility of the results.

这项研究通过热重分析法对乙烯焦油衍生的涂层沥青进行了热解。通过热重-质谱法和固态 13C 核磁共振谱分析了结构特征与热解行为的相关性。同时，采用无模型法和模型拟合法估算了热解动力学。TG-DTG 结果表明，热解过程一般分为干燥阶段、快速热解阶段和缩聚阶段，伴随着与氧键合的脂肪族碳（falO）等活性官能团的分解、非质子化芳香碳（faH）等相对稳定的官能团的热解以及芳香桥头碳（faB）等高键能芳香结构的缩聚。随着转化率的增加，无模型分析得到的活化能在 78.12 至 150.92 kJ/mol 之间，表明热解过程是一个多步骤反应机制。此外，反应模型 A1/3（gα=[-ln(1-α)]3）被认为是 0.25-0.8 转化率范围内最适合涂料沥青热解的模型。模型值与实验数据十分吻合，表明了结果的准确性和可行性。

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引用次数: 0

Volatile fatty acid release and metal ion concentration in hydrothermal carbonization liquid 热液碳化液中的挥发性脂肪酸释放和金属离子浓度

IF 5.8 2区化学 Q1 CHEMISTRY, ANALYTICAL

Journal of Analytical and Applied Pyrolysis

Pub Date : 2024-10-01 DOI: 10.1016/j.jaap.2024.106815

Zhe Zhang , Ting Yan , Tao Zhang , Zherui Zhang , Wenzan Wang , Hua Peng , Dong Li , Zhiping Zhu

Hydrothermal carbonisation (HTC) is an efficient technology for converting waste into carbon materials along with a significant by-product known as hydrothermal liquid (HL). This study examined the organic loads, nutrient-rich components, volatile fatty acid (VFA) release, and metal concentrations of HLs obtained under various reaction conditions and material formulations. Structural equation models (SEM) elucidated the relationship between the acidification system and metal concentrations in HL. The chemical oxygen demand (COD) in the HL varied from 4220 mg/L to 51,480 mg/L under different HTC conditions, increasing with reaction temperature, and the pH ranged from 3.5 to 5.6. Acetic acid was the predominant species in the VFAs of HL, the amount of which tended to decrease and then increase with increasing temperature. The metal ion concentrations in HL were K > Mg > Ca > Fe > Zn > Cu. The SEM indicated that COD and pH were the main factors influencing metal ion concentrations in HL. VFAs negatively affected the pH (P < 0.01), indirectly promoting metal ion dissolution, and positive interactions were observed among the metal ions. The concentration of VFAs in HL influences the pH and thus plays an important role in promoting the release of metals.

水热碳化（HTC）是一种将废物转化为碳材料的高效技术，同时还会产生一种重要的副产品，即水热液（HL）。本研究考察了在不同反应条件和材料配方下获得的 HL 的有机负荷、富含营养成分、挥发性脂肪酸 (VFA) 释放量和金属浓度。结构方程模型（SEM）阐明了酸化系统与 HL 中金属浓度之间的关系。在不同的 HTC 条件下，HL 中的化学需氧量（COD）从 4220 mg/L 到 51480 mg/L 不等，随着反应温度的升高而升高，pH 值从 3.5 到 5.6 不等。乙酸是 HL 中挥发性脂肪酸的主要种类，其含量随着温度的升高呈先降后升的趋势。HL 中的金属离子浓度为 K、Mg、Ca、Fe、Zn、Cu。扫描电子显微镜表明，化学需氧量和 pH 值是影响 HL 中金属离子浓度的主要因素。VFAs 对 pH 有负面影响（P <0.01），间接促进了金属离子的溶解，并且金属离子之间存在正相互作用。HL 中的 VFAs 浓度会影响 pH 值，从而在促进金属释放方面发挥重要作用。

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引用次数: 0

Cellulose pyrolysis via liquid metal catalysis 通过液态金属催化热解纤维素

IF 5.8 2区化学 Q1 CHEMISTRY, ANALYTICAL

Journal of Analytical and Applied Pyrolysis

Pub Date : 2024-10-01 DOI: 10.1016/j.jaap.2024.106800

Aaditya Hari Bharanidharan, Kyle McGaughy, Aime Laurent Twizerimana, Kaylen Ocampo, Götz Veser, Mohammad S. Masnadi

Liquid metals are largely unexplored as catalytic media for biomass conversion. Unlike conventional solid-state catalysts which are prone to deactivation, liquid metals, i.e., low-melting metals operated above their melting point, can show resilience against coking, high thermal conductivity, and enhanced liquid-solid contact between catalyst and biomass feedstocks. This promise motivated the present investigation of liquid metals as catalysts for cellulose pyrolysis. Bismuth, tin, and indium were selected as liquid metal candidates, and their impact on cellulose devolatilization kinetics is studied via thermogravimetric analysis. The results indicate that all three metals show catalytic activity, with bismuth catalyzing volatiles formation, while indium and tin enhance char formation. Quantitative analysis of liquid product reveals that bismuth is selective to dehydration and functional rearrangement reactions, leading to anhydro sugars and functionalized furans formation. In contrast, indium and tin are selective towards dehydration, fragmentation reactions, and Diels Alder chemistry, leading to formation of C2-C4 fragments and aromatic compounds, as further confirmed via infrared spectroscopic analysis of the obtained chars. Finally, the Sn and Bi liquid metals’ stability against deactivation via coking is examined against conventional solid-state zeolite catalyst through multiple cellulose pyrolysis runs in the thermogravimetric analyzer (TGA) with the same batch of catalyst. While ZSM-5 zeolite catalyst's activity and selectivity declined and approached non-catalytic sand results (both the TGA curve and the liquid product distribution) within the first few runs, both Sn and Bi fairly maintained their robustness against coking for the conducted durability runs. Overall, the results show significant promise for this new class of catalysts for biomass pyrolysis.

作为生物质转化的催化介质，液态金属在很大程度上尚未被开发。与容易失活的传统固态催化剂不同，液态金属，即在熔点以上工作的低熔点金属，可以显示出抗结焦性、高导热性以及催化剂与生物质原料之间更强的液固接触性。这一前景促使我们对液态金属作为纤维素热解催化剂进行了研究。铋、锡和铟被选为候选液态金属，并通过热重分析研究了它们对纤维素脱溶动力学的影响。结果表明，这三种金属都具有催化活性，其中铋能催化挥发物的形成，而铟和锡则能促进炭的形成。液态产物的定量分析显示，铋对脱水和功能重排反应具有选择性，从而导致脱水糖和功能化呋喃的形成。与此相反，铟和锡对脱水、破碎反应和 Diels Alder 化学反应具有选择性，导致 C2-C4 片段和芳香族化合物的形成，这一点通过对获得的木炭进行红外光谱分析得到了进一步证实。最后，通过在热重分析仪（TGA）中使用同一批催化剂进行多次纤维素热解，考察了锡和铋液态金属与传统固态沸石催化剂相比在焦化失活方面的稳定性。虽然 ZSM-5 沸石催化剂的活性和选择性有所下降，并在最初几次运行中接近于非催化砂结果（TGA 曲线和液体产物分布），但在进行的耐久性运行中，锡和铋催化剂都保持了较强的抗结焦能力。总之，研究结果表明，这类新型催化剂在生物质热解方面大有可为。

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引用次数: 0

Simulation analysis of gas-solid two-phase flow and reaction in a novel catalytic cracking reactor 新型催化裂化反应器中气固两相流动和反应的模拟分析

IF 5.8 2区化学 Q1 CHEMISTRY, ANALYTICAL

Journal of Analytical and Applied Pyrolysis

Pub Date : 2024-10-01 DOI: 10.1016/j.jaap.2024.106792

Jingxiao Wang , Jianliang Xu , Haifeng Liu , Jianhong Gong

A gas-solid two-phase flow reaction model was developed to evaluate the performance of a novel catalytic cracking reactor in the residue-to-chemicals (RTC) process. Coupled TFM, EMMS drag, and 12-lump kinetic models were employed to simulate the flow reaction process. The reaction temperature and product yields at the reactor exit aligned well with real industrial RTC reactor test results, indicating the reliability and effectiveness of the coupling model. Catalyst particles formed an internal circulation structure in the reactor, increasing the instantaneous catalyst-to-oil ratio. The reactor exhibited low axial and radial temperature gradients with higher reaction temperatures, accelerating the catalytic cracking rate and enhancing the selectivity for high-value products. The effects of the catalyst-to-oil ratio, catalyst inlet temperature, and feedstock mass flow rate on the flow reaction process were optimized. Results showed that both the catalyst-to-oil ratio and catalyst inlet temperature influenced the overall catalyst velocity distribution. Within the limit range, increasing the catalyst-to-oil ratio increased feedstock conversion, gasoline, LPG, dry gas, and coke yields, but decreased diesel yield. Conversely, increasing the feedstock mass flow rate showed opposite trends. Different trends in product yields were observed with varying inlet catalyst temperatures, with optimal product distribution at 973.15 K.

为评估新型催化裂化反应器在残渣制化学品（RTC）过程中的性能，开发了气固两相流反应模型。采用耦合 TFM、EMMS 拖动和 12 块动力学模型模拟流动反应过程。反应器出口处的反应温度和产品产量与实际工业 RTC 反应器的测试结果非常吻合，表明了耦合模型的可靠性和有效性。催化剂颗粒在反应器中形成了内循环结构，提高了瞬时催化剂与油的比率。反应器在较高的反应温度下表现出较低的轴向和径向温度梯度，加快了催化裂化速率，提高了高价值产品的选择性。对催化剂与油的比例、催化剂入口温度和原料质量流量对流动反应过程的影响进行了优化。结果表明，催化剂与油的比例和催化剂入口温度都会影响催化剂的总体速度分布。在极限范围内，提高催化剂与油的比例可提高原料转化率、汽油、液化石油气、干气和焦炭产量，但降低柴油产量。相反，提高原料质量流量则呈现出相反的趋势。在不同的入口催化剂温度下，观察到了不同的产品产量趋势，在 973.15 K 时产品分布最佳。

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引用次数: 0

Harnessing artificial neural networks and linear regression models for modeling thermal modification processes: Characterization by FTIR and prediction of the mechanical properties of eucalyptus wood 利用人工神经网络和线性回归模型为热改性过程建模：傅立叶变换红外光谱的表征和桉树木材机械性能的预测

IF 5.8 2区化学 Q1 CHEMISTRY, ANALYTICAL

Journal of Analytical and Applied Pyrolysis

Pub Date : 2024-10-01 DOI: 10.1016/j.jaap.2024.106809

Youssef Elrhayam , Fatima Ezzahra Bennani , Mohamed Berradi , Ahmed El Yacoubi , Abderrahim El Bachiri

In the present study, an artificial neural network model and multiple linear regression method were constructed to establish a relationship between the parameters of the thermal modification process and the mechanical properties of Eucalyptus camaldulensis wood samples. Three influencing parameters on the mechanical properties during heat treatment were considered input variables, namely water absorption, volumetric mass, and mass loss; the other parameters were kept constant (treatment temperature: 200, 220, 240, and 260 °C, and the duration: 5, 60, and 90 minutes). There were five neurons in the hidden layer that were used, as well as an output layer for the mechanical property. According to the results obtained, the mean square error (MSE) for the training, validation, and testing datasets were determined to be 0.21, 0.25, and 0.22 in the prediction modulus of rupture (MOR) and 0.019, 0.017, and 0.023 in the prediction modulus of elasticity (MOE). Higher coefficients of determination (R²) ranging from 0.93 to 0.98 were obtained for all datasets with the proposed ANN models, while the multiple linear regression models found the MSE to be 1.03 and 1.40 for MOR and MOE, respectively, as well as R² to be 0.97 and 0.80, respectively. These results show that ANN models can be successfully used to predict the change in mechanical properties of wood during heat treatment.

本研究采用人工神经网络模型和多元线性回归方法建立了热改性工艺参数与桉树木材样品力学性能之间的关系。热处理过程中影响力学性能的三个参数被视为输入变量，即吸水率、体积质量和质量损失；其他参数保持不变（处理温度：200、220、240 和 260 ℃，持续时间：5、60 和 90 分钟）：5、60 和 90 分钟）。在隐层中使用了五个神经元，以及一个用于机械性能的输出层。根据获得的结果，训练、验证和测试数据集的均方误差（MSE）分别为：预测断裂模量（MOR）0.21、0.25 和 0.22；预测弹性模量（MOE）0.019、0.017 和 0.023。使用所提出的 ANN 模型，所有数据集都获得了 0.93 至 0.98 的较高决定系数 (R2)，而多元线性回归模型发现 MOR 和 MOE 的 MSE 分别为 1.03 和 1.40，R2 分别为 0.97 和 0.80。这些结果表明，ANN 模型可成功用于预测木材在热处理过程中的力学性能变化。

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引用次数: 0

Assessing the effect of size and shape factors on the devolatilization of biomass particles by coupling a rapid-solving thermal-thick model 通过耦合快速解决热厚模型评估尺寸和形状因素对生物质颗粒脱溶的影响

IF 5.8 2区化学 Q1 CHEMISTRY, ANALYTICAL

Journal of Analytical and Applied Pyrolysis

Pub Date : 2024-10-01 DOI: 10.1016/j.jaap.2024.106835

Jiaye Zhang , Zhao Wang , Gaofeng Dai , Stephan Heberlein , Wei Ping Chan , Xuebin Wang , Houzhang Tan , Grzegorz Lisak

In CFD modeling, while the isothermal assumption has conventionally been coupled for updating particle temperature, its applicability diminishes when dealing with thermally thick particles. A thermal-thick discrete phase model (DPM) is developed to simulate pyrolysis of biomass particle group at high heating rates and temperatures, with particles tracked in a Lagrangian scheme. The effects of particle size and shape on the volatile release and heating history are investigated. For spherical particles with a diameter of 9.6 mm, the temperature difference between the surface and center (∆T) does not disappear even up to 50 s. In the particle size range spanning from 200 μm to 9.6 mm, the duration required for a complete volatile release extends from 1.5 to 40 s. For cylindrical particles, in contrast to the particles with an aspect ratio (AR, ratio of particle length to diameter) of 1, the devolatilization time of particles with an AR of 15 can be shortened by more than 50 %. In addition, both the particle shape and size can significantly influence the volatile distribution within the reactor. This work contributes to understanding both the particle size and shape impact on heat and mass transfer during biomass pyrolysis at high heating rates.

在 CFD 建模中，虽然等温假设一直被用于更新颗粒温度，但在处理热厚颗粒时，其适用性就会降低。本研究开发了一种热厚离散相模型（DPM），用于模拟生物质颗粒组在高加热速率和温度下的热解，并采用拉格朗日方案对颗粒进行跟踪。研究了颗粒大小和形状对挥发物释放和加热历史的影响。对于直径为 9.6 毫米的球形颗粒，表面和中心的温度差 (∆T) 即使在 50 秒内也不会消失。在 200 μm 到 9.6 mm 的粒径范围内，完全释放挥发物所需的时间从 1.5 秒到 40 秒不等。对于圆柱形颗粒，与长径比（AR，颗粒长度与直径之比）为 1 的颗粒相比，长径比为 15 的颗粒的挥发时间可缩短 50% 以上。此外，颗粒的形状和大小也会对反应器内的挥发物分布产生重大影响。这项研究有助于了解颗粒大小和形状对高加热速率下生物质热解过程中传热和传质的影响。

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引用次数: 0

Pyrolysis mechanism of 1,1,1,2-tetrafluoroethane and 1,1,1,2-tetrafluoroethane/carbon dioxide as working fluids for transcritical power cycles: Insights from reactive force field molecular dynamics and density functional theory studies 1,1,1,2-四氟乙烷和 1,1,1,2-四氟乙烷/二氧化碳作为跨临界动力循环工作流体的热解机理：反应力场分子动力学和密度泛函理论研究的启示

IF 5.8 2区化学 Q1 CHEMISTRY, ANALYTICAL

Journal of Analytical and Applied Pyrolysis

Pub Date : 2024-10-01 DOI: 10.1016/j.jaap.2024.106838

Junliang Liu, Chuang Wu, Wei Yu, Liyong Xin

Carbon dioxide-based mixtures in transcritical power cycle systems can enhance thermodynamic performance but may pose risks of thermal decomposition, potentially compromising system performance and safety. This study investigates the pyrolysis mechanism of 1,1,1,2-tetrafluoroethane (R134a)/carbon dioxide (CO₂), a typical CO₂-based mixture, using reactive force field molecular dynamics (ReaxFF-MD) simulations and density functional theory (DFT). ReaxFF-MD simulations are conducted at pressures ranging from 4 to 12 MPa and temperatures between 1800 K and 3200 K for various fluid compositions, including pure R134a and R134a/CO₂ mixtures at mole ratios of 0.7/0.3, 0.5/0.5, and 0.3/0.7. The effects of temperature, pressure, and composition on the thermal decomposition of both pure R134a and R134a/CO₂ mixtures are examined, with particular focus on behavior at 8 MPa. In the thermal decomposition of R134a/CO₂ mixtures, CO₂ inhibits the formation of F radicals and reduces their concentration through chemical reactions, thereby suppressing R134a decomposition. Pure R134a decomposes into primary products such as hydrogen fluoride (HF), fluorine (F), tetrafluoroethylene (C₂HF₄), trifluoromethyl radicals (CF₃), and diatomic carbon (C₂). The addition of CO₂ results in the formation of additional products, including carbonyl fluoride (COF), oxygen (O), hydroxyl (HO), and formyl radicals (CHO). The decomposition pathways involve two reaction types: self-decomposition reactions dominate initially, while extraction reactions become more prominent later. Using the DFT approach, reaction energy barriers are analyzed to corroborate the ReaxFF-MD simulation findings. Moreover, the apparent activation energies for these reactions are quantified using first-order kinetics based on the Arrhenius equation, indicating that the thermal decomposition of R134a/CO₂ mixtures is more challenging than that of pure R134a.

在跨临界功率循环系统中，以二氧化碳为基础的混合物可以提高热力学性能，但也可能带来热分解风险，潜在地影响系统性能和安全性。本研究利用反应力场分子动力学（ReaxFF-MD）模拟和密度泛函理论（DFT）研究了 1,1,1,2-四氟乙烷（R134a）/二氧化碳（CO₂）（一种典型的 CO₂ 基混合物）的热分解机理。ReaxFF-MD 模拟是在压力为 4 至 12 兆帕，温度为 1800 K 至 3200 K 的条件下对各种流体成分（包括纯 R134a 和 R134a/CO₂ 混合物，摩尔比分别为 0.7/0.3、0.5/0.5 和 0.3/0.7）进行的。研究了温度、压力和成分对纯 R134a 和 R134a/CO₂ 混合物热分解的影响，尤其侧重于 8 兆帕时的行为。在 R134a/CO₂ 混合物的热分解过程中，CO₂ 通过化学反应抑制 F 自由基的形成并降低其浓度，从而抑制 R134a 的分解。纯 R134a 会分解成氟化氢 (HF)、氟 (F)、四氟乙烯 (C2HF4)、三氟甲基自由基 (CF3) 和二原子碳 (C2) 等初级产品。加入 CO2 会形成其他产物，包括羰基氟化物 (COF)、氧 (O)、羟基 (HO) 和甲酰基 (CHO)。分解途径涉及两种反应类型：自分解反应在初期占主导地位，而萃取反应则在后期变得更加突出。利用 DFT 方法分析了反应能垒，以证实 ReaxFF-MD 模拟的结果。此外，利用基于阿伦尼乌斯方程的一阶动力学对这些反应的表观活化能进行了量化，表明 R134a/CO2 混合物的热分解比纯 R134a 的热分解更具挑战性。

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引用次数: 0

Chemical kinetics of SARA fractions pyrolysis: Saturates and aromatics SARA 馏分热解的化学动力学：饱和物和芳烃

IF 5.8 2区化学 Q1 CHEMISTRY, ANALYTICAL

Journal of Analytical and Applied Pyrolysis

Pub Date : 2024-10-01 DOI: 10.1016/j.jaap.2024.106818

Elia Colleoni , Paolo Guida , Vasilios G. Samaras , Alessio Frassoldati , Tiziano Faravelli , William L. Roberts

This manuscript focuses on presenting a predictive and widely applicable model for describing the pyrolysis of saturates and aromatics, two of the so called SARA (Saturates, Aromatics, Resins, Asphaltenes) fractions. The fractions extracted from two different oil samples, a typical Heavy Fuel Oil 380 and a typical Vacuum Residue Oil, were thoroughly investigated. Different experimental methods elucidated the elemental composition, chemical structure, thermal degradation behavior, and characterized the products released during the pyrolysis of these two oils. Finally, a model to describe the pyrolysis of saturates and aromatics was developed. The model is comprehensive of methodology for the definition of a surrogate and a kinetic mechanism to describe its pyrolysis. The surrogate is defined using a certain number of pseudo-components, whose mass fraction in the mixture is defined to match the chemical properties of the actual fuel. A kinetic mechanism was defined by pairing each pseudo-component with a reaction to describe its thermal decomposition. The model was then validated against literature data and demonstrated to be predictive in describing the pyrolysis of different samples.

本手稿重点介绍了一种可广泛应用的预测模型，用于描述饱和物和芳烃的热解过程，饱和物和芳烃是所谓的 SARA（饱和物、芳烃、树脂、沥青质）馏分中的两种。对从两种不同油样（典型的重燃油 380 和典型的真空渣油）中提取的馏分进行了深入研究。不同的实验方法阐明了这两种油在热解过程中的元素组成、化学结构、热降解行为以及释放产物的特征。最后，建立了一个描述饱和油和芳烃热解的模型。该模型包含定义代用品的方法和描述其热解的动力学机制。代用品是用一定数量的伪成分定义的，其在混合物中的质量分数与实际燃料的化学性质相匹配。通过将每种伪成分与描述其热分解的反应配对来定义动力学机制。然后根据文献数据对该模型进行了验证，并证明该模型在描述不同样品的热解过程中具有预测性。

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引用次数: 0