Study of the composition of tars produced from blends of coal and polyethylene wastes using high-performance liquid chromatography

Tars produced at semi-industrial scale in a coke oven of 6 x 10(3) kg capacity were used to investigate the effect of using polyethylene waste as an additive in the carbonization process with coal. The polyethylene wastes used were low-density polyethylene from the agriculture greenhouses and high-density polyethylene from domestic sources. The high-performance liquid chromatography analysis of the soluble fractions in toluene and carbon disulfide, using two polystyrene-divinylbenzene columns and a mixture of dichloromethane-methanol as a mobile phase, provides useful information on the composition of tars and their derived pitches in terms of the substitution and molecular topology of polynuclear aromatic compounds (PACs). Differences in composition of tars produced with polyethylene waste at 1% (w/w) have been found to be negligible, while a higher amount of the waste (3%, w/w) promoted the formation of peri-condensed PACs at the expense of the substituted cata-condensed PACs. This behaviour is due to more extensive secondary reactions of tar precursors via dealkylation and aromatic condensation taking place during the carbonization process as a consequence of a more viscous co-carbonizing system. Changes in tar composition caused by this amount of polyethylene waste addition were comparable to those promoted by an increase in the carbonization temperature at semi-industrial and industrial ovens and by the coal preheating before the carbonization process. The characteristic features in tar composition were also found for the derived pitches from tars obtained with the polyethylene waste addition.     

Devolatilisation characteristics of coal and biomass blends

The characterisation of the initial devolatilisation products could provide important information for understanding synergistic effects and subsequently the formation routes leading to toxic organic compounds and soot during co-combustion. Initial devolatilisation characteristics of the fuels have been characterised following co-pyrolysis experiments. This paper investigates the devolatilisation behaviour during co-pyrolysis of pinewood together with one of three coals of different rank, lignite or high-volatile bituminous of different origin. A range of pyrolysis experiments has been performed over a temperature range from 400 to 900 °C using pyrolysis–GC–MS (py–GC–MS) and thermogravimetric analysis (TGA). Larger scale batch pyrolysis experiments of the hv bituminous coal–pine mixture have been performed enabling collection of the evolved tars. These tars have then been characterised by GC–MS and size exclusion chromatography (SEC). For these batch pyrolysis tests, synergy (non-additive behaviour) was observed and the blend pyrolysis oil contained a decrease in aromatics and an increase in phenols than would be expected for additive behaviour. The molecular weight distributions of the evolved tars also show non-additive behaviour. For the TGA experiments, additive behaviour was seen for all the coal–pine blends studied. Similarly, no obvious synergy was observed by py–GC–MS for the bituminous coal–pine blends, or for model compound–coal and coal–biomass component blends. Non-additive combustion behaviour is not easily explained by studying devolatilisation because of the difficulty in replicating the conditions of temperature profile and residence time experienced by the volatiles. Thus, conflicting behaviour is exhibited depending upon pyrolysis technique.     

The influence of the recycling stress history on LDPE waste pyrolysis

It is elementary to recognize the benefits and the negative impacts of the use of plastic materials on modern societies. Polyethylene (PE) is the major plastic component present in the municipal solid waste. In this paper, two types of low-density PE (LDPE) waste with different mechanical recycling stress histories were used to investigate the influence of recycling cycles on pyrolysis. The kinetic triplet and thermal degradation study were obtained using TGA data.To determine the sample composition and hydrocarbon arrangements, ultimate, proximate and X-ray diffraction analyses were carried out. Taking advantage of these analyses and combining them with differential scanning calorimetry (DSC) data, a series–parallel pyrolysis pathway was formulated. The waste of recycled polyethylene presented low enthalpy of pyrolysis, at about 205 J/g against 299 J/g for a virgin PE. The DSC analyses evidenced a multi-step reaction behavior of the pyrolysis, confirmed by the kinetic study using different isoconversional methods: the waste of recycled polyethylene presented a higher variation of activation energies as a function of the fraction reacted. The main conclusion is that the results suggest that the recycling stress history promotes the increase of long carbon chains while weakening the boundary among the compounds. This explains the fact that recycled waste needs less activation energy than other samples to degrade thermally. Finally, different categories of low-density polyethylene wastes must be considered when dealing with either kinetics or modeling of the product recovery process.     

Modeling pyrolysis kinetics of plastic mixtures

Modeling pyrolysis behavior of waste plastic mixtures is of importance for design and operation of reactors which convert these waste plastics into valuable chemicals. However, because of limited understanding of their degradation behavior even for single component plastic wastes, modeling degradation kinetics of plastic mixtures is a challenging task.In this work, we report modeling of binary and ternary mixture degradation kinetics of polyethylene terephthalate (PET), low density polyethylene (LDPE) and polypropylene (PP). A simple mixing rule approach was used with one cross-kinetic degradation parameter per each binary. Ternary kinetics were completely predictive and showed good agreement with the experimental data.     

Thermal analyses of Ohio bituminous coals

A suite of twenty-one bituminous coal samples from Ohio were analyzed by differential scanning calorimetry (DSC) and non-isothermal thermogravimetry (TG) techniques. Three regions of endothermic activity may be distinguished in the DSC scans in an inert atmosphere. The first peak (25–150°C) corresponds to loss of moisture from the coal, a second, very broad endotherm peaking in the range 400–500°C corresponds to devolatilization of the organic matter and a partially resolved endotherm at temperatures above 550°C probably corresponds to cracking and coking processes subsequent to the pyrolysis step. Evidence obtained from experiments with sealed pans suggest an autocatalytic effect exerted by the pyrolysis products. The use of the DSC technique to quantify the volatile matter content of coal seems less reliable than the proximate analyses obtained from non-isothermal TG in inert and O₂ atmospheres. Good agreement with ASTM values is observed by the latter method for a range of volatile matter and ash content.     

Gas chromatographic-mass spectrometric study of the oil fractions produced by microwave-assisted pyrolysis of different sewage sludges

The pyrolysis of sewage sludge was studied in a microwave oven using graphite as microwave absorber. The pyrolysis temperature ranged from 800 to 1000 degrees C depending on the type of sewage sludge. A conventional electrical furnace was also employed in order to compare the results obtained with both methods. The pyrolysis oils were trapped in a series of condensers and their characteristics such as elemental analysis and calorific value were determined and compared with those of the initial sludge. The oil composition was analyzed by GC-MS. The oils from the microwave oven had n-alkanes and 1-alkenes, aromatic compounds, ranging from benzene derivatives to polycyclic aromatic hydrocarbons (PAHs), nitrogenated compounds, long chain aliphatic carboxylic acids, ketones and esters and also monoterpenes and steroids. The oil from the electric oven was composed basically of PAHs such as naphthalene, acenapthylene, phenanthrene, fluoranthene, benzo[a]anthracene, benzofluoranthenes, benzopyrenes, indenepyrene, benzo[ghi]perylene, and anthanthrene. In contrast, these compounds were not produced in the case of microwave-assisted pyrolysis.     

油棕废弃物热解的TG-FTIR分析

利用热重分析(TGA)和傅里叶红外光谱(FTIR)联用技术对油棕废弃物的热解特性及其气体产物的释放特性进行了研究，采用一级反应计算了油棕废弃物的热解动力学参数。研究表明，油棕废弃物较易于热解，失重集中在220℃～400℃，其热解活化能较小，约为60kJ/mol；气体产物的析出与生物质的热解失重有着相似的特性，气体产物主要在200℃～400℃析出，主要成分为H2O、CO2、CO、CH4和有机碳水化合物的混合物, 其中CO2和有机混合物的析出温度较低，而CO和CH4的析出温度相对较高。随着温度的进一步升高(>400℃)，除少量的CO2和CO外，无其他气体产物析出。气体产物的析出量与生物质样品的化学组成和结构有关，CO2和有机混合物的析出与生物质的热解失重曲线(DTG)有着相似的特性，是引起油棕废弃物热解失重的主要原因。     

Bibliometric analysis and an overview of the application of the non-precious materials for pyrolysis reaction of plastic waste

Huge plastic consumption and depletion of fossil fuels are at the top of the world's environmental and energy challenges. The scientific community has tackled these issues through different approaches. Catalytic pyrolysis of plastic wastes to valuable products has been proved as a sustainable route which fits with the circular economy aspects. The design of catalytic materials is the central factor for performing the catalytic conversion of plastic wastes. This review aims to conduct a Bibliometric analysis of the pyrolysis of plastic wastes and non-precious-based catalysts by mapping research studies over the last fifty years. The analysis was developed via VOSviewer and RStudio tools. It showed the historical progress regarding plastic waste pyrolysis to produce valuable products and chemicals worldwide. The research shows that the top five countries with the highest citations and publications in this field were Spain, China, England, the USA and India. The Journal of Analytical and Applied Pyrolysis had the most comprehensive coverage of plastic waste. The relationship between the catalyst and the mechanism of plastic waste can influence the production yield and selectivity. The research gap and underrepresented research topics were identified, and previous research studies on developing non-precious-based catalysts that were most relevant to the current topic were reviewed and discussed. The challenges and perspectives on catalyst preparation and development for material complexity were critically discussed. Challenges of previous studies and directions for future research were provided. This report might guide the reader to take a general look at plastic waste valorization by pyrolysis and easily understand the main challenges.     

澳大利亚高盐煤中钠在热解过程中的形态变迁

通过对高钠煤进行水洗以及0.1 mol/L的HCl洗涤,并在固定床上考察了不同洗煤热解后的半焦中Na的挥发性及其形态变迁。热解后的半焦用水和0.1 mol/L的HCl逐级萃取,将热解半焦中的钠分为水溶态钠,水不溶但酸溶态钠以及酸不溶态钠。研究结果表明,实验煤中的钠大部分是以水溶态的NaCl盐形式存在,在500℃~550℃由于以羧酸盐形式存在的有机钠以钠原子的形式释放使得在该温度范围内钠的挥发性出现极大值,而酸洗煤由于在600℃以上有一部分酸不溶态的钠转化为水不溶但酸溶态的钠,使得钠的挥发性又有所增加。原煤中的可挥发钠热解后少部分在高温下会转化为水溶态的钠,而水洗煤中的钠随着热解温度的升高与SiO2反应转化为硅酸盐形式存在的酸不溶态的钠。     

Comprehensive two-dimensional gas chromatography of volatile and semi-volatile components using a diaphragm valve-based instrument

A high-temperature configuration for a diaphragm valve-based gas chromatography (GCXGC) instrument is demonstrated. GCxGC is a powerful instrumental tool often used to analyze complex mixtures. Previously, the temperature limitations of valve-based GCxGC instruments were set by the maximum operating temperature of the valve, typically 175 degrees C. Thus, valve-based GCxGC was constrained to the analysis of mainly volatile components; however, many complex mixtures contain semi-volatile components as well. A new configuration is described that extends the working temperature range of diaphragm valve-based GCxGC instruments to significantly higher temperatures, so both volatile and semi-volatile compounds can be readily separated. In the current investigation, separations at temperatures up to 250 degrees C are demonstrated. This new design features both chromatographic columns in the same oven with the valve interfacing the two columns mounted in the side of the oven wall so the valve is both partially inside as well as outside the oven. The diaphragm and the sample ports in the valve are located inside the oven while the temperature-restrictive portion of the valve (containing the O-rings) is outside the oven. Temperature measurements on the surface of the valve indicate that even after a sustained oven temperature of 240 degrees C, the portions of the valve directly involved with the sampling from the first column to the second column track the oven temperature to within 1.2% while the portions of the valve that are temperature-restrictive remain well below the maximum temperature of 175 degrees C. A 26-component mixture of alkanes, ketones, and alcohols whose boiling points range from 65 degrees C (n-hexane) to 270 degrees C (n-pentadecane) is used to test the new design. Peak shapes along the first column axis suggest that sample condensation or carry-over in the valve is not a problem. Chemometric data analysis is performed to demonstrate that the resulting data have a bilinear structure. After over 6 months of use and temperature conditions up to 265 degrees C, no deterioration of the valve or its performance has been observed.     

神木煤显微组分热解和加氢热解的焦油组成

利用色谱-质谱联用技术测定了神木煤镜质组和惰质组在不同热解条件下焦油的组成,考察了显微组分类型和反应气氛对苯类、酚类、萘类、含氧杂环和多环芳烃类化合物产率的影响。结果表明,惰质组和镜质组焦油在组成和长链烃类、芳烃、含氧杂环和多环芳烃的相对质量分数方面存在很大差异。镜质组焦油中长链烃类的种类和相对质量分数较高,惰质组焦油中芳烃、含氧杂环和多环芳烃的种类和相对质量分数较高,反映了镜质组显微组分芳香度较低以及烷基侧链长和多以及惰质组稠环芳烃结构多和芳环缩聚程度高的特点。加氢热解比热解有较高的焦油收率,随氢气压力的增加,焦油的收率大幅度增加。镜质组和惰质组热解和加氢热解焦油组成和相对质量分数的差异反映了热解过程中氢气的加氢稳定化作用和加氢裂解作用。     

Characterization of sulfonated azo dyes and aromatic amines by pyrolysis gas chromatography/mass spectrometry

Sixteen sulfonated and unsulfonated azo dyes as well as eleven sulfonated and unsulfonated aromatic amines were analyzed and qualitatively characterized by means of pyrolysis gas chromatography/mass spectrometry at different temperatures. Aniline and aminonaphthalene were found to be the dominant pyrolysis products of sulfonated aromatic amines and dyes. Azo dye and dye class specific key compounds such as benzidine, vinyl-p-base and 4-aminoazobenzene could be identified by pyrolysis gas chromatography/mass spectrometry of commercial acid, cationic, direct, reactive and solvent dyes. 500 degrees C was the optimal pyrolysis temperature for most of the pyrolyzed compounds. The method was applied to a dried sample of a textile wastewater concentrate from a dyeing process. Reactive azo dyes of the group of Remazol dyes and anthraquinone dyes could be identified as the major compounds of the sample. The finding of caprolactam (a printing additive) suggests that the wastewater contained effluent from a process of heat-activated printing with reactive dyes. p-Chloraniline, a banned aromatic amine, was identified. Chemical reduction of the wastewater sample prior to pyrolysis resulted in the release of volatile aromatic amines and aided the classification of several products of pyrolysis.     

煤与混合废塑料共热解固体产物中氯的赋存形态及在燃烧时的释放特性

通过红外光谱、热重 质谱及燃烧 水解实验，研究了煤与废塑料共热解固体产物中氯的赋存形态及在燃烧过程中氯的释放特性。结果表明，温度低于600℃热解的半焦中存在有机氯化合物；600℃以上热解的半焦（或焦炭）中氯主要以无机盐类存在。燃烧过程中氯的释放率与燃烧温度，煤与废塑料共热解的温度以及共热解时废塑料的加入量有关。燃烧温度越高，氯的释放率越大，900℃燃烧时，氯的释放率都在94%以上；在同一温度燃烧时，热解温度越高，氯的释放率越低。400℃热解的半焦最高释放率达99.86%，而1000℃热解的焦炭的最高释放率为94.35%。     

Coprocessing of Waste Plastic and Hydrocarbons over MFI (HZSM‐5)

The thermal and catalytic degradation of high‐ and low‐density polyethylene (HDPE and LDPE, respectively) and waste plastic film (polyethylene‐based plastic wastes) were analyzed through simultaneous thermogravimetry and differential scanning calorimetry in inert atmosphere. Catalytic degradation was performed using MFI (HZSM‐5) zeolites. Although the catalyst induces a large decrease of the degradation temperature for polyethylene, it has a smaller effect on the waste plastic (WP) degradation temperature. To check the activity of the catalyst after its use in the WP degradation, experiments were conducted with fresh HDPE which confirmed a significant loss of catalytic activity. Mixtures of WP with large paraffin were also analyzed (nC₅₀). The results show that the presence of the hydrocarbon in the mixture grants some protection to the catalyst, allowing it to retain part of its activity during the process even in the presence of the waste contaminants. These findings suggest that larger hydrocarbon: waste plastic ratios promote higher protection to deactivation and that WP coprocessing with oil is feasible. Gas chromatography was used to analyze the products formed in the catalytic degradation of the WP in the presence C₅₀ hydrocarbon at a ratio of 1:12, consisting mostly of light products in the range of C₂ to C₈ hydrocarbons.     

Thermal degradation behaviour of aromatic poly(ester-amide) with pendant phosphorus groups investigated by pyrolysis-GC/MS

The thermal stability of a novel phosphorus-containing aromatic poly(ester-amide) ODOP-PEA was investigated by thermogravimetric analysis (TGA). The weight of ODOP-PEA fell slightly at the temperature range of 300-400 °C in the TGA analysis, and the major weight loss occurred at 500 °C. The structural identification of the volatile products resulted from the ODOP-PEA pyrolysis at different temperatures was performed by pyrolysis-gas chromatography/mass spectrometry (pyrolysis-GC/MS). The P-C bond linked between the pendant DOPO group and the polymer chain disconnected first at approximately 275 °C, indicating that it is the weakest bond in the ODOP-PEA. The P-O bond in the pendant DOPO group was stable up to 300 °C. The cleavage of the ester linkage within the polymer main chain initiated at 400 °C, and the amide bond scission occurred at greater than 400 °C. The structures of the decomposition products were used to propose the degradation processes happening during the pyrolysis of the polymer.     

Research on pyrolysis of PCB waste with TG-FTIR and Py-GC/MS

The purpose of this study is to determine the pyrolysis characteristics and gas product properties of printed circuit board (PCB) waste. For this purpose, a combination of Thermogravimetry-Fourier Transform Infrared Spectrum (TG-FTIR) and pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) techniques is employed. In the TG-FTIR experiment, a heating rate of 10?°C min^?1 and a terminal pyrolysis temperature of 600?°C are applied. The thermal decomposition temperature, weight losses, and the temperature trend of evolving gaseous products of PCB waste are investigated. Py-GC/MS is used for the qualitative and semi-quantitative analysis of the higher-molecular-weight volatile decomposition products. Associated with the analysis results of TG-FTIR and Py-GC/MS for the volatile products, PCB waste degradation could be subdivided into three stages. The main products in the first stage (<293?°C) are H₂O, CH₄, HBr, CO₂ and CH₃COCH₃. High-molecular-weight organic species, including bromophenols, bisphenol A, p-isopropenyl phenol, phenol, etc., mainly evolve in the second stage. In the last stage, at temperature above 400?°C, carbonization and char formation occur. This fundamental study provides a basic insight of PCB waste pyrolysis.     

Recent Trends in the Pyrolysis of Non-Degradable Waste Plastics

Waste plastics are non-degradable constituents that can stay in the environment for centuries. Their large land space consumption is unsafe to humans and animals. Concomitantly, the continuous engineering of plastics, which causes depletion of petroleum, poses another problem since they are petroleum-based materials. Therefore, energy recovering trough pyrolysis is an innovative and sustainable solution since it can be practiced without liberating toxic gases into the atmosphere. The most commonly used plastics, such as HDPE, LDPE (high- and low-density polyethylene), PP (polypropylene), PS (polystyrene), and, to some extent, PC (polycarbonate), PVC (polyvinyl chloride), and PET (polyethylene terephthalate), are used for fuel oil recovery through this process. The oils which are generated from the wastes showed caloric values almost comparable with conventional fuels. The main aim of the present review is to highlight and summarize the trends of thermal and catalytic pyrolysis of waste plastic into valuable fuel products through manipulating the operational parameters that influence the quality or quantity of the recovered results. The properties and product distribution of the pyrolytic fuels and the depolymerization reaction mechanisms of each plastic and their byproduct composition are also discussed.     

Performance of capillary columns for high-temperature gas chromatography

The developments in stationary-phase synthesis and capillary column technology have opened new perspectives in the analysis of high-molecular-weight compounds (600 daltons) and thermolabile organic compounds by high-temperature-high-resolution gas chromatography. This branch of high-resolution gas chromatography deals with analysis performed up to 390 degrees C oven temperature (with some applications going up to 420 degrees C and even a few applications to 450 degrees C maximum). The technique has been applied to many different fields of science (e.g., organic geochemistry, environmental chemistry, archeology, and natural product research). Apolar and medium-polar gum phases can now be operated at temperatures from 400 to 480 degrees C, but these higher temperatures are seldom used because of the thermostability of the material used to make the capillary tubing. This paper shows the performance of nine commercial high-temperature columns when used in routine applications.     

自由落下床中生物质与煤共热解的协同效应对焦油组成的影响

利用溶剂萃取-柱层析方法,将自由落下床中豆秸与大雁褐煤共热解以及单种原料热解的液体产品分为沥青烯、酚类、脂肪烃类、芳香烃类和极性物等组分。结果表明,共热解的沥青烯产率为11.4%,低于根据煤和生物质单独热解的质量加权平均计算值19.0%,且芳香性增大;与计算值相比,低分子量的酚类、甲基苯酚、二甲基苯酚及其衍生物的含量提高了5%;而且长侧链的脂肪烃含量减少。共热解焦油的芳香类组分中十氢萘的质量分数是43.37%,但其在单一原料热解焦油中并没有被检测到。热解油分析结果表明,自由落下床生物质与煤快速共热解过程中存在协同效应,其主要原因是,发生氢解和加氢反应。煤与生物质共热解有利于产生低分子量的化合物,改善油品的质量。     

Detoxification of brominated pyrolysis oils

The development of an innovative technology for the pyrolytic conversion of brominated phenols in a reductive medium aimed at product recovery for commercial use is discussed in this paper. Brominated phenols are toxic products, which contaminate pyrolysis oil of wastes from electronic and electrical equipment (WEEE). The pyrolysis experiments were carried out with 2,6-dibromophenol, tetrabromobisphenol A, WEEE pyrolysis oil and polypropylene or polyethylene in encapsulated ampoules under inert atmosphere in quasi-isothermal conditions (300–400 °C) with a different residence time (10–30 min). Optimal conditions were found to be the use of polypropylene at 350 °C with a residence time of 20 min. The main pyrolysis products were identified as HBr and phenol. A radical debromination mechanism for the pyrolytic destruction of brominated phenols is suggested.