火灾中聚合物材料热解对汽油辨识的影响分析

火灾中聚合物材料的燃烧过程产生的热解产物,从而增加化学分析谱图的复杂性,对助燃剂鉴定造成干扰。针对常见的聚合物材料开展了一系列燃烧实验,对其在燃烧过程中的热解机理进行了分析,并通过汽油存在条件下的聚合物材料燃烧实验分析了热解对汽油辨识产生的干扰。     

陈腐垃圾的热解特性及动力学研究

采用热重法研究了陈腐垃圾中不同组分的热解特性。通过实验得到了陈腐垃圾及其主要组分（包括草木、腐殖质和塑料）的TG／DTG曲线。通过对TG／DTG曲线进行分析,得到了它们的热解温度、挥发分完全析出温度等重要参数。采用Doyle法研究了热解过程的动力学特性,计算出了反应的一级反应动力学参数。     

Prediction of high-density polyethylene pyrolysis using kinetic parameters based on thermogravimetric and artificial neural networks

● Reducting the sampling frequency can enhance the modelling process. ● The pyrolysis of HDPE was investigated at three different heating rates. ● The average E_a and k₀ were calculated by Friedman, KAS, FWO, and CR methods. ● ANN was employed to predict the HDPE weight loss with the optimal MSE and R². Pyrolysis is considered an attractive option and a promising way to dispose waste plastics. The thermogravimetric experiments of high-density polyethylene (HDPE) were conducted from 105 °C to 900 °C at different heating rates (10 °C/min, 20 °C/min, and 30 °C/min) to investigate their thermal pyrolysis behavior. We investigated four methods including three model-free methods and one model-fitting method to estimate dynamic parameters. Additionally, an artificial neural network model was developed by providing the heating rates and temperatures to predict the weight loss (wt.%) of HDPE, and optimized via assessing mean squared error and determination coefficient on the test set. The optimal MSE (2.6297 × 10⁻²) and R² value (R² > 0.999) were obtained. Activation energy and pre-exponential factor obtained from four different models achieves the acceptable value between experimental and predicted results. The relative error of the model increased from 2.4 % to 6.8 % when the sampling frequency changed from 50 s to 60 s, but showed no significant difference when the sampling frequency was below 50 s. This result provides a promising approach to simplify the further modelling work and to reduce the required data storage space. This study revealed the possibility of simulating the HDPE pyrolysis process via machine learning with no significant accuracy loss of the kinetic parameters. It is hoped that this work could potentially benefit to the development of pyrolysis process modelling of HDPE and the other plastics.     

大港油田含油污泥热解处理实验研究

采用热解法对含油污泥进行处理.经过筛选,选取活性白土作为催化剂,分别研究反应时间、反应温度、加热速率和氮气吹扫量对热解处理效果的影响.4个影响因素对液相收率的影响顺序为:氮气吹扫量＞反应温度＞反应时间＞加热速率;对反应转化率的影响顺序为:反应温度＞反应时间＞氮气吹扫量＞加热速率.实验理想的反应参数为:反应时间60min,反应温度490℃,加热速率4℃/min,氮气吹扫量90 mL/min.     

模化城市有机垃圾的热解研究

本文简介了对城市有机垃圾(模化垃圾)进行热解的研究结果。得到了产气量、可燃气体成分、热解时间等随热解温度的变化关系。研究结果指出,当城市有机垃圾含水率W~y<50％,热解温度在900℃左右条件下,有机垃圾的潜能不仅能实现自身的处理,而且可输出部分热能。     

污水污泥制油技术研究进展

目前污水污泥传统处理方法存在一定的不足和弊端,污泥制油技术不断得到了研究者的关注。对污泥制油技术的发展进行综述,特别就工艺操作条件、催化剂的使用等方面介绍了污泥低温热解技术,并对污泥制油技术提出几点展望。     

Effect of particle size and dust layer size on ignition characteristics of PMMA dust layer on hot surface

Deposition of combustible dust on a hot surface is a hidden danger of fire. In this work, polymethylmethacrylate (PMMA) dust was selected to analyse the influence of dust layer diameter, dust particle size and dust layer thickness on the ignition characteristics of PMMA dust layer. Critical heating temperatures and ignition time had been measured. The STA-GC/MS-FTIR analysis was used to determine that the main products of PMMA pyrolysis were MMA, CO, CO₂, and C₂H₄, of which CO and C₂H₄ were transported to the ambient to cause gas phase combustion on the surface of the dust layer. For 10 mm thick dust layer, the critical heating temperatures of 5 μm PMMA, 100 nm PMMA, and 30 μm PMMA were 300 °C, 330 °C, and 320 °C. As the thickness of the dust layer increased, the gas transport path became longer, the critical heating temperature and ignition time increased. The characteristic particle size (D [3,2]) was utilized to represent the true particle size, and the ignition time increased with the increase of the characteristic particle size. The increase in the diameter of the dust layer had a slight effect on the temperature history and ignition time of the dust layer.     

Theoretical and experimental studies on the thermal decomposition of 1-butyl-3-methylimidazolium dibutyl phosphate

Ionic liquid, an organic molten salt, has efficient flame-retardant performance. Few researchers have attempted to study its flame-retardant mechanism. Moreover, thermal stability and pyrolysis products have a great impact on the flame retardancy. Therefore, this paper focused on the phosphate ionic liquid of 1-butyl-3-methylimidazolium dibutyl phosphate ([Bmim][DBP]) and analyzed its thermal decomposition products and characteristics. The major bond energies of [Bmim][DBP] were calculated using B3LYP/6–311++G(d,p)//M06–2X/6–311++G(d,p) level. The experimental results show that the pyrolysis products were as followed: alkane or alkene with a carbon chain length of 1–4; imidazole and its derivatives; esters. Furthermore, Gas chromatography-mass spectrometer and Fourier transform infrared spectrometer were utilized to measure the gaseous products and solid phase products of [Bmim][DBP], which were obtained during thermogravimetric analysis. The results of theoretical and experimental analysis were highly consistent. Finally, the possible flame-retardant mechanism of [Bmim][DBP] was proposed.     

Thermogravimetric pyrolysis of waste polyethylene-terephthalate and polystyrene: A critical assessment of kinetics modelling

Pyrolysis is considered as possible technique to thermally convert waste plastics into chemicals and energy. Literature on experimental findings is extensive, although experiments are mostly performed in a dynamic heating mode, using thermogravimetric analysis (TGA) and at low values of the heating rate (mostly below 30 K/min). The present research differs from literature through the application of far higher heating rates, up to 120 K/min. The use of these dynamic results to define the reaction kinetics necessitates the selection of an appropriate reaction mechanism, and 21 models have been proposed in literature considering the rate limiting step being diffusion, nucleation or the reaction itself.The current research studied the cracking of PET and PS by TGA at different heating rates (temperature ramps). Results were used to check the validity of the proposed mechanisms. Several conclusions are drawn: (i) to obtain fair results, the heating ramp should exceed a minimum value, calculated at 30 K/min for PET and 80 K/min for PS; (ii) application of the majority of the models to experimental findings demonstrated that they do not meet fundamental kinetic considerations and are questionable in their use; and (iii) simple models, with reaction order 1 or 2, provide similar results of the reaction activation energy.A further comparison with literature data for dynamic and isothermal experiments confirms the validity of these selected models. Since TGA results are obtained on a limited amount of sample, with results being a strong function of the applied heating rate, the authors believe that isothermal experiments, preferably on a large scale both towards equipment and/or sample size, are to be preferred.     

Influence of poly(bisphenol A carbonate) and poly(ethylene terephthalate) on poly(vinyl chloride) dehydrochlorination

Recycling of poly(vinyl chloride) (PVC) waste is a serious problem because of its high chlorine content. Dehydrochlorination of PVC-containing polymer waste produces solid residue char, for which conversion to pyrolysis oil in a petrochemical plant seems to be an attractive way of recycling PVC waste. Unfortunately, some polymer admixtures react with HCl and cause formation of chloroorganic compounds in a char. This article describes the influence of polycarbonates and poly(ethylene terephthalate) on thermal feedstock recycling of PVC wastes using a two-stage method. It was found that the presence of polycarbonate causes the formation of small amounts of benzyl chloride and other chloroaryl or chloroalkylaryl compounds. Poly(ethylene terephthalate) interacts with HCl forming significant amounts of various chlorocompounds – mainly chloroethyl esters of terephthalic and benzoic acids, but derivatives possessing chlorine directly connected to the aromatic ring are also formed.