Pyrolysis Gas Research Articles

Quantitative analysis of pA66/PA6 blend by pyrolysis gas chromatography-mass spectrometry

Abstract A pyrolysis gas chromatography-mass spectrometry method using correction factor area normalization was applied for quantitative analysis of the PA66/PA6 blend ratio. The PA66/PA6 blend sample with known proportions was prepared. The pyro grams of the sample were obtained at the pyrolysis temperature of 600°C. The characteristic peaks-cyclopentanone and caprolactam of thermally decomposed polyester were selected as the peak to quantitatively determine the blending ratio. A correction factor of the characteristic ion peak area and corresponding mass was obtained and applied to quantitative analysis of the proportion of PA66/PA6 blends in the actual sample. The known content PA66/PA6 blend samples with different PA66/PA6 bending ratios were measured, the rate of recovery was from 96.5% to 106.4%, and the relative standard deviation (RSD) was from 0.8% to 7.6% (n = 3). The result showed that the Pyrolysis Gas Chromatography-Mass Spectrometry method is simple and convenient, accurate, which is suitable for the analysis of the PA66/PA6 blending ratio in the full range.

Improving the Oxidation Resistance of Phenolic Resin Pyrolytic Carbons by In Situ Catalytic Formation of Carbon Nanofibers via Copper Nitrate.

Phenolic resin pyrolytic carbons were obtained by catalytic pyrolysis of phenolic resin at 500 °C, 600 °C, 700 °C, and 800 °C for 3 h in an argon atmosphere using copper nitrate as a catalyst precursor. The effects of copper salts on the pyrolysis process of phenolic resin as well as the structural evolution and oxidation resistance of phenolic resin pyrolytic carbons were studied. The results showed that copper oxide (CuO) generated from the thermal decomposition of copper nitrate was reduced to copper (Cu) by the gas generated from the thermal decomposition of the phenolic resin. Carbon nanofibers with tapered structures were synthesized by Cu catalysis of pyrolysis gas at 500-800 °C. The catalytic pyrolysis of phenolic resin with Cu increased the graphitization degree and reduced the pore volume of the phenolic resin pyrolytic carbons. The combined action improved the oxidation resistance of phenolic resin pyrolytic carbons.

Spectral and chemical characterization of amber from Xixia, Henan Province, China via FTIR, three-dimensional fluorescence spectra and Py (HMDS)-GC-MS

Xixia amber from Henan Province in China has undergone a thorough examination utilizing microscopic observation, infrared spectroscopy, and three-dimensional (3D) fluorescence spectroscopy. This systematic analysis has revealed that there are primarily two varieties of Xixia amber: a light-colored type and a dark-colored type. These can be differentiated based on their coloration, infrared spectra, and distinctive fluorescence attributes. Notably, the infrared spectral profile of Xixia amber features a prominent peak at 1023 cm−1, accompanied by less pronounced peaks at 1088 and 974 cm−1. These spectral characteristics set it apart from amber originating from the Baltic regions, Myanmar, and Fushun. Further distinction is achieved through 3D fluorescence spectra, where Xixia amber exhibits similarities to Burmese and Fushun ambers. Chemical classification via pyrolysis gas chromatography-mass spectrometry (Py-GC-MS) identifies Xixia amber as belonging to Class Ib, characterized by its ordered structure and the absence of succinic acid. This comprehensive study delineates the coloration, infrared spectral properties, photoluminescent behavior, and chemical compositions of Xixia amber, clearly differentiating it from ambers sourced from other geographical locations.

Kinetic, gas emission, reaction pathway and interaction mechanism analysis during oxidative pyrolysis of aluminium electrolysis waste with beech wood

The oxidative pyrolysis kinetic, gas emission, reaction pathway and interaction mechanism during oxidative pyrolysis of spent cathode carbon block (SCCB) and beech wood (BW) were investigated via the thermogravimetry combined with Fourier transform infrared spectrometer (TG-FTIR) analysis. The hemicellulose, cellulose, and lignin in BW and the carbon materials and fluoride in SCCB were determined as the main five components based on thermogravimetric experiment. Compared with pure SCCB, the addition of BW increased the comprehensive oxidative pyrolysis index. Furthermore, the total of 44 kinetic parameters were obtained by the Shuffled Complex Evolution (SCE) method, which were used to further forecast the mass loss of the above five main components. The evolved gases were detected by FTIR, and the results indicated that the main gases for BW/SCCB oxidative pyrolysis were CO2, which corresponded to the oxidation of cellulose, lignin and carbon materials. Small amounts of phenols, alcohols, ethers, ketones, aldehydes, carboxylic acids, CO, aromatics, alkene were attributed to the thermal decomposition of hemicellulose and cellulose. Pyrolysis of cellulose and lignin produced small quantities of hydrocarbons. HF was formed by the thermal decomposition of fluoride. Eventually, the reaction pathway was proposed and the possible interaction mechanism was analyzed during the oxidative pyrolysis of BW/SCCB blends.

Investigation of pyrolysis productions (pyrolysis oil, pyrolysis gas and carbon nanotubes) distribution in co-pyrolysis of torrefied oiltea camellia shells and polypropylene

The co-pyrolysis of torrefied oiltea camellia shells (OCS) and reused polypropylene (PP) was investigated for pyrolysis oil, pyrolysis gas and carbon nanotubes (CNTs) distribution characters in a two-stage pyrolysis system. Compared with raw OCS/PP, the quality of pyrolysis oil from torrefied OCS and PP was upgraded while yield decreased gradually. In particular, torrefaction pretreatment was beneficial to the formation of aromatic hydrocarbons and the higher selectivity of phenols in pyrolysis oil. And serious N2 torrefaction (260 N) and slight CO2 torrefaction (200C) is more conducive to the synthesis of C6–C11 (gasoline component). In addition, torrefaction could contribute to lower volatiles, which resulted in a lower yield of CNTs. For comparison, higher graphitized CNTs was prepared from the co-pyrolysis of torrefied OCS and PP. Appropriate torrefaction temperature and atmosphere have a potential for high value conversion of pyrolysis oil, pyrolysis gas and CNTs from co-pyrolysis of biomass and plastics.

Investigation of Carbon Products Produced by Catalytic Pyrolysis of Natural Gas

Investigation of Carbon Products Produced by Catalytic Pyrolysis of Natural Gas

Effect of three alkaline impurities on the pressure of 1,2, 4-triazole pyrolysis gas

1,2,4-triazole is now widely used in the production of pesticides and medicine, and progress has been made in the application of materials. The structural characteristics of 1,2,4-triazole with high nitrogen content will cause it to the release of a large amount of gas when it occurs pyrolysis, which may have a certain impact on industrial production safety. In the industrial process, there will be some other impurities mixed into it, so the influence of these impurities on the 1,2,4-triazole pyrolysis gas is worth exploring. In this study, the adiabatic acceleration calorimeter was used to simulate the adiabatic conditions to study the pressure value of the gas generated by the pyrolysis of 1,2,4-triazole itself, and the influence of the addition of three basic impurities on the overall pyrolysis pressure value. Experiments show that these three impurities can affect the pressure value of pyrolysis gas in different degrees. The results can provide reference for the loss prevention and control of 1,2,4-triazole in industrial production.

Research and Analysis of Woodblock Printing Ink from the Qing Dynasty Used in the Shuyede Press of Shandong

Archival writing material is an important carrier to record and reflect archival content, and its material and durability are closely related to the life of archives. The “Shuyede” press in Shandong Province, which originated in the reign of Kangxi (1662 AD–1722 AD) in the Qing dynasty, printed many important archives and ancient books of the Qing dynasty (1644 AD–1911 AD). In order to explore the material composition of woodblock printing ink from the Shuyede press, modern analytical and detection techniques such as scanning electron microscopy–energy-dispersive spectrometry (SEM-EDS), Fourier-transform infrared spectroscopy (FTIR), gas chromatography–mass spectrometry (GC/MS), and pyrolysis gas chromatography–mass spectrometry (Py-GC/MS) were applied for the analysis and identification of the ink on woodblock plates from the Shuyede press. The results showed that two kinds of printing ink—pine soot ink and oil soot ink—used were in these woodblocks from the Shuyede press in the Qing dynasty in the collection of Shandong Museum, and the binding material in the ink was animal glue, indicating that both pine and oil soot inks were used as printing ink in the Qing dynasty.

Energy potential of plant and animal biomass using in relation to its thermal processing

Relevance. The need for effective utilization of biomass waste generated in significant quantities. Pyrolysis, accompanied by exothermic reactions, is a promising way of biomass processing. Aim. Assessment of the possibility of covering the thermal costs of plant and animal biomass pyrolysis due to heat release during decomposition. Methods. Proximate and ultimate analysis of biomass are determined according to certified methods. Thermal analysis of the studied raw materials was carried out on a Netzsch STA 449 F5 Jupiter synchronous thermal analyzer with an integrated gas analyzer QMS 403 Aeolos; quantitative yield of pyrolysis products was determined according to GOST 3168-93, gas composition was established using the gas analyzer TEST-1 (БОНЭР, Russia). Results and conclusions. According to the results of thermal analysis, it was found that pyrolysis of plant (pine nut shells) and animal (cattle manure) biomass is accompanied by exothermic reactions associated with the organic part decomposition in the temperature range 240–700°C. The value of heat release of exothermic reactions during pine nut shell destruction is 1.39 MJ/kg, a similar value during manure decomposition is 0.31 MJ/kg. This amount of heat allows you to fully cover the thermal costs of pine nut shell pyrolytic processing, the share of covering the thermal costs of manure pyrolysis is ∼30%. An additional source of heat is pyrolysis gaseous products with energy potential equal to 3.28 and 1.58 MJ of thermal energy per 1 kg of processed pine nut shells and manure, respectively.

Revealing the delithiation process of spent LiMn2O4 and LiNi0.6Co0.2Mn0.2O2 batteries during the biomass-assisted gasthermal and carbothermal reduction

The utilization of biomass-assisted pyrolysis in the recycling of spent lithium-ion batteries has emerged as a promising and reliable process. This article furnishes theoretical underpinnings and analytical insights into this method, showcasing sawdust pyrolysis reduction as an efficient means to recycle spent LiMn2O4 and LiNi0.6Co0.2Mn0.2O2 batteries. Through advanced thermogravimetry-gas chromatography-mass spectrometry analysis complemented by traditional thermodynamic demonstration, the synergistic effects of biomass pyrolysis reduction are elucidated, with minor autodecomposition and major carbothermal and gasthermal reduction pathways identified. The controlled manipulation of transition metals has demonstrated the capability to modulate surface pyrolysis gas catalytic reactions and facilitate the preparation of composite materials with diverse morphologies. Optimization of process conditions has culminated in recovery efficiency exceeding 99.0 % for LiMn2O4 and 99.5 % for LiNi0.6Co0.2Mn0.2O2. Economic and environmental analyses underscore the advantages of biomass reduction and recycling for these two types of spent LIBs: low energy consumption, environmental compatibility, and high economic viability.

Discovery and analysis of microplastics in human bone marrow

The health implications of human exposure to microplastics (MPs) have raised significant concerns. While evidence indicates MPs can accumulate in closed human organs like the heart, placenta, and blood, there is no available data on MP exposure specifically within the human bone marrow. To fill the research gap, this study detected the concentration of microplastics (MPs) in bone marrow samples by pyrolysis gas chromatography-mass spectrometry (Py-GC/MS) and assessed the size range and morphological characteristics of MPs by Laser Direct Infrared Spectroscopy (LD-IR) and scanning electron microscopy (SEM). Our study shows that MPs were present in all 16 bone marrow samples, with an average concentration of 51.29 µg/g ranging from 15.37 µg/g to 92.05 µg/g. Five polymer types-polyethylene (PE), polystyrene (PS), polyvinyl chloride (PVC), polyadiohexylenediamine 66 (PA66), and polypropylene (PP), were identified. PE was the most frequent polymer detected in the bone marrow, with an average concentration of 30.02 µg/g ranging from 14.77 µg/g to 52.57 µg/g, with a detection rate of 93.75 %. PS had the highest detection rate at 100 % of bone marrow samples, while PVC and PA66 were found in 75 % of samples each. LD-IR analysis revealed the identification of 25 polymer types, with an average abundance of 19.72 particles/g. Of these, 89.82 % of the MPs were smaller than 100 µm. In summary, this study has, for the first time, demonstrated the presence of MPs are deeply embedded within human bone marrow, providing a basis for future investigations into their potential toxicological effects and underlying mechanisms affecting the hematopoietic system.

Towards the Development of an In-Process Quality Monitoring System for Polyethylene Recyclates by Pyrolysis Gas Chromatography Ion Mobility Spectrometry

Over the past few decades, the topic of recycling has become increasingly prominent in the field of sustainable materials and circular economy. One significant challenge is the physical separation of different types of plastics to obtain recyclates of one plastic type as pure as possible with comparable quality and properties to those of virgin material. Given the substantial effort involved in such separation, small amounts of contamination from other plastics may be tolerated. However, these contaminations must be monitored to ensure high-level recyclate quality. In recent years, compact, low-cost ion mobility spectrometers (IMS) with high analytical performance have been developed, and have thus become widely used in a variety of sensing applications. Due to their high sensitivity, IMS are particularly suited for detecting lowest concentration levels of various compounds, as required for the detection of impurities in recyclate quality monitoring. When coupled to a miniature gas chromatograph (GC), GC-IMS reach even higher separation power while being still compact. To bring recyclate samples to the gas phase, pyrolysis (Py) is used in this work. A first feasibility study was conducted to assess the potential of such a pyrolysis–gas chromatography-ion mobility spectrometer (Py-GC-IMS) with the objective of detecting contaminations of polyethylene terephthalate (PET) in polyethylene (PE) recyclates. The study clearly demonstrates the ability to identify PET-related fingerprints while suppressing the PE background matrix by design so that Py-GC-IMS seems a promising approach for in-process monitoring PET contaminations in PE recyclates.

Synergistic Interaction during Copyrolysis of Soybean Straw and Tire Waste: Improving Emissions and Product Quality.

This study explores copyrolysis of soybean straw (SS) with hydrogen-rich tire waste (TW) to enhance pyrolytic product quality and reduce pollutant emissions. Addition of TW increased SS biomass conversion from 67.19 to 72.46% and decreased coke/residue formation from 32.81 to 27.54%. The activation energy dropped to 121.84 kJ/mol from 160.73 kJ/mol (as calculated by the Kissinger-Akahira-Sunose method) and 122.78 kJ/mol from 159.76 kJ/mol (as calculated by the Ozawa-Flynn-Wall method). Thermogravimetric analysis coupled with Fourier-transform infrared spectroscopy (TG-FTIR) showed lowered CO2, NO2, and SO2 emissions (5.58, 5.72, 3.38) compared to conventional SS pyrolysis (18.38, 11.55, 12.37). Yields of value-added chemicals (phenols, olefins, aromatics) increased (32.38, 22.17, 30.18%) versus conventional SS pyrolysis (23.56, 13.78, 20.36%). Pyrolysis gas chromatography-mass spectrometry (Py/GC-MS) analysis reveals that the addition of TW leads to a decrease in the production of oxygenates and polycyclic aromatic hydrocarbons, reducing their yields to 8.96 and 7.67%, respectively, down from 19.37 and 14.37%. Simultaneously, it enhances the yields of olefins, aromatics, phenols, and aliphatic hydrocarbons to 23.38, 26.78, 26.17, and 25.78%, respectively, compared to 15.37%, 15.29, 18.36, and 17.25%, respectively, in the absence of TW. In summary, copyrolysis of TW with SS improves product quality and reduces pollutant emissions, marking a significant research contribution.

Pyrolytic Decomposition of Polyethylene in the Presence of Aluminosilicate Materials Containing Nickel Oxide

The work is devoted to the study of the pyrolysis of high-density polyethylene (PE) in the presence of aluminosilicate materials containing nickel oxide. The process of catalytic pyrolysis of plastics makes it possible to convert polymers into chemical compounds, which can later be used as an additional source of fuels, raw materials for the chemical industry or polymer production. The physicochemical parameters of materials containing nickel oxide have been established using the following methods: IR-Fourier spectroscopy; x-ray diffraction analysis; N2 physical adsorption method; thermogravimetric analysis; pyrolytic gas chromatography. The dependences of the chemical composition of PE pyrolysis products on the type of support used and the presence of nickel oxide. The presence of nickel oxide in the studied aluminosilicates increases the Lewis acidity, which increases the content of aromatic compounds in the pyrolysis products. The activation energy of the PE pyrolysis process in the presence of MCM-41 containing nickel oxide was calculated from experimental data.

Selective recovery of pyrolyzates of biodegradable (PLA, PHBH) and common plastics (HDPE, PP, PS) during co-pyrolysis under slow heating

Pyrolytic synergistic interactions, in which the production of pyrolyzates is enhanced or inhibited, commonly occur during the co-pyrolysis of different polymeric materials, such as plastics and biomass. Although these interactions can increase the yield of desired pyrolysis products under controlled degradation conditions, the desired compounds must be separated from complex pyrolyzates and further purified. To balance these dual effects, this study was aimed at examining pyrolytic synergistic interactions during slow heating co-pyrolysis of biodegradable plastics including polylactic acid (PLA) and poly(3-hydroxybutyrate-co-3-hydroxyhexaoate) (PHBH) and petroleum-based plastics including high-density polyethylene (HDPE), polypropylene (PP), and polystyrene (PS). Comprehensive investigations based on thermogravimetric analysis, pyrolysis–gas chromatography/mass spectrometry, and evolved gas analysis-mass spectrometry revealed that PLA and PHBH decompose at lower temperatures (273–378 °C) than HDPE, PP, and PS (386–499 °C), with each polymer undergoing independent decomposition without any pyrolytic interactions. Thus, the independent pyrolysis of biodegradable plastics, such as PLA and PHBH, with common plastics, such as HDPE, PP, and PS, can theoretically be realized through temperature control, enabling the selective recovery of their pyrolyzates in different temperature ranges. Thus, pyrolytic approaches can facilitate the treatment of mixed biodegradable and common plastics.

Preparation of carbon materials by vapor deposition with Fe3+-Modified nickel foam from biomass pyrolysis gas

Biomass carbon materials have attracted attention in various fields due to their excellent properties. In this study, CH4 derived from biomass pyrolysis was utilized as a carbon source gas to synthesize carbon materials by chemical vapor deposition (CVD) in a two-stage reactor with purification system, with Fe3+-loaded nickel foam as the substrate under an argon atmosphere, using a self-designed experimental platform. The reaction process was optimized by examining the effects of the catalyst type, reaction temperature, reaction time, and gas flow rate on the structure and morphology of the carbon materials. The optimal preparation condition was to use FeCl3 ethanol solution as catalyst, with CH4 flow rate of 50 ml/min at 1000 °C for 25 min. The high quality carbon materials with uniform diameters (250–500 nm) were obtained on nickel foam substrate. The carbon materials obtained under optimal conditions were characterized and analyzed to investigate their excellent properties. Surface morphology and structure of as-formed carbon materials were characterized by SEM. The analysis of the XRD spectra and the Raman spectroscopy showed that the graphite diffraction peak (002) at 26.6°, the calculated intensity ratios for ID/IG and I2D/IG were 0.257 and 0.545, respectively, indicated high degree of graphitization and purity of the carbon materials. Furthermore, the growth mechanism of carbon materials on the nickel foam substrate was discussed.

Technical Aspects of Natural Gas Pyrolysis in Liquid Metal Bubble Column Reactors

The pyrolysis of low alkanes (in the following short “pyrolysis”) has already been investigated during the 1960s. However, none of the reactor systems used at the time are capable of continuous operation. Therefore, the Karlsruhe Institute of Technology has intensified the development of the promising liquid metal bubble column technology in recent years, which is capable of continuous operation. Various key aspects have been addressed, such as scale‐up and the pyrolysis of high‐caloric natural gas. Herein, further developments for a pilot scale system have been investigated, which concern increased throughput and long‐term operation capabilities. Careful evaluation of the impact of according measures has been done, which shows that the achieved scale‐up has only negligible effects on the pyrolysis outcome. The effects of the scale‐up on residence times are negligible. The bubble formation behavior depends on the throughput and the characteristics of the orifice. Wall effects are marginal. Fundamental minimization of weeping could not be confirmed. Reactor pre‐chambers in combination with tin collection chambers are recommended for further scale‐up. An increase in the volume flow should be examined. In terms of long‐term operation , head as well as feed pressure control is recommended.

Investigating the Effects of the Physicochemical Properties of Cellulose-Derived Biocarbon on Direct Carbon Solid Oxide Fuel Cell Performance.

This paper presents a study of the characteristic effects of the physicochemical properties of microcrystalline cellulose and a series of biocarbon samples produced from this raw material through thermal conversion at temperatures ranging from 200 °C to 850 °C. Structural studies revealed that the biocarbon samples produced from cellulose had a relatively low degree of graphitization of the carbon and an isometric shape of the carbon particles. Based on thermal investigations using the differential thermal analysis/differential scanning calorimeter method, obtaining fully formed biocarbon samples from cellulose feedstock was possible at about 400 °C. The highest direct carbon solid oxide fuel cell (DC-SOFC) performance was found for biochar samples obtained via thermal treatment at 400-600 °C. The pyrolytic gases from cellulose decomposition had a considerable impact on the achieved current density and power density of the DC-SOFCs supplied by pure cellulose samples or biochars derived from cellulose feedstock at a lower temperature range of 200-400 °C. For the DC-SOFCs supplied by biochars synthesised at higher temperatures of 600-850 °C, the "shuttle delivery mechanism" had a substantial effect. The impact of the carbon oxide concentration in the anode or carbon bed was important for the performance of the DC-SOFCs. Carbon oxide oxidised at the anode to form carbon dioxide, which interacted with the carbon bed to form more carbon oxide. The application of biochar obtained from cellulose alone without an additional catalyst led to moderate electrochemical power output from the DC-SOFCs. The results show that catalysts for the reverse Boudouard reactions occurring in a biocarbon bed are critical to ensuring high performance and stable operation under electrical load, which is crucial for DC-SOFC development.

Pyrolysis char from waste tyres its characteristics, upgrading and application

The pyrolysis of waste tyres can recycle energy and produce reusable products (oil, char and gas). Although there are many reviews in the literature in regard to the pyrolysis characteristics of waste tyres, but this paper critically looked as pyrolysis char as one of the useful product. Its physical characteristics include pore diameter, pore volume, specific surface area, and composition. The common detection techniques of the physical characteristics include elemental analysis, proximate analysis, SEM, EDS, TGA, XRF, BET, and Raman spectroscopy. The chemical characteristics of tyre char mainly include calorific value, the surface functional groups (i.e phenols, alcohols, carboxylic acid and C-O/C-O-C chemical structures) which can be determined by FT-IR, XRD. The higher sulfur retention on the surface of tyre char is obtained at low temperature compared with that obtained at high temperature. Tyre char could also be directly used as a catalyst material to decrease the operational cost, and improve the quality of pyrolysis oil and gas. The modified tyre char with high specific surface area and lower ash content could be used as an activated carbon adsorbent material, catalyst and catalyst support, capacitor electrode to create higher commercial value, as an adsorbent, in batteries and so on. It is suggested that the recycling applications of tyre char should be developed, which can create a high level of potential economic prospects for the waste tyre pyrolysis industry.

Near-zero carbon emission power generation system enabled by staged coal gasification and chemical recuperation

Generating clean, efficient, and low-carbon electricity from coal is imperative for limiting the global temperature rise to 1.5 °C. This study presents a near-zero-carbon-emission power generation system that utilizes staged coal gasification. The innovation of this system is the division of coal gasification into two stages: intermediate-temperature pyrolysis, followed by high-temperature gasification. This process begins with utilizing waste heat from the exhaust of a gas turbine to drive the partial gasification of coal during pyrolysis. The nongaseous products from this stage are then completely gasified in the gasifier, and chemical recuperation is performed, in which heat from the syngas at the gasifier's outlet preheats the reactants at the inlet and aids in reforming pyrolysis gas. For CO2 capture, an oxyfuel combustion strategy is used. Our system produced net electricity and exergy efficiencies of 43.01 and 47.57 %, respectively, surpassing both pre-combustion CO2 capture systems based on staged coal gasification (improvements of 3.04 and 5.37 %, respectively) and coal-water slurry gasification (improvements of 3.55 and 5.8 %, respectively). Moreover, the carbon emissions from our system are approximately 90 g/kWh lower than those from these systems. Thus, this study offers an environmentally sustainable approach to utilizing coal that may facilitate achieving global environmental goals.