Influence of different stalks on the metallization degree of FeCl3-derived magnetic biochar through pyrolysis behavior and compositional differences.

To investigate the effect of stalk type on the metallization degrees in FeCl3-derived magnetic biochar (MBC), MBC was synthesized via an impregnation-pyrolysis method using six different stalks. The Fe0 content in MBC significantly influenced its magnetic properties and ostensibly governed its catalytic capabilities. Analysis of the interaction between stalks and FeCl3 revealed that the variation in metallization degrees, resulting from FeCl2 decomposition (6.1%) and stalk-mediated reduction (20.7%), was directly responsible for the observed differences in MBC metallization. The presence of oxygen-containing functional groups and fixed carbon appeared to promote metallization in MBC induced by reduction. A series of statistical analyses indicated that the cellulose, lignin, and hemicellulose content of the stalks were key factors contributing to differences in MBC metallization degrees. Further exploration revealed that hemicellulose and cellulose were more effective than lignin in enhancing metallization through FeCl2 decomposition and reduction. Constructing stalk models demonstrated that the variance in the content of these three biomass components across the six stalk types could lead to differences in the metallization degree attributable to reduction and FeCl2 decomposition, thereby affecting the overall metallization degree of MBC. A prediction model for MBC metallization degree was developed based on these findings. Moreover, the elevated Si content in some stalks facilitated the formation of Fe2(SiO4), which subsequently impeded the reduction process. This study provides a theoretical foundation for the informed selection of stalk feedstocks in the production of FeCl3-derived MBC.

Study on phase evolution and promoting the pozzolanic activity of electrolytic manganese residue during calcination.

Electrolytic manganese residue (EMR) is a harmful by-product in the electrolytic manganese industry. Calcination is an efficient method for disposing EMR. In this study, thermogravimetric-mass spectrometry (TG-MS) combined with X-ray diffraction (XRD) was used for analysing the thermal reactions and phase transitions during calcination. The pozzolanic activity of calcined EMR was determined by the potential hydraulicity test and strength activity index (SAI) test. The leaching characteristics of Mn were determined by TCLP test and BCR SE method. The results showed that MnSO4 was converted into stable MnO2 during calcination. Meanwhile, Mn-rich bustamite (Ca0.228Mn0.772SiO3) was converted into Ca(Mn, Ca)Si2O6. The gypsum was transformed into anhydrite and then decomposed into CaO and SO2. Additionally, the organic pollutants and ammonia were completely removed following calcination at 700 °C. The leaching concentration of Mn decreased from 819.9 mg L-1 to 339.6 mg L-1 following calcination at 1100 °C. The chemical forms of Mn were transformed from acid-soluble fraction to residual fraction. The pozzolanic activity tests indicated that EMR1100-Gy maintained a complete shape. The compressive strength of EMR1100-PO reached 33.83 MPa. Finally, the leaching concentrations of heavy metals met the standard limits. This study provides a better understanding for the treatment and utilization of EMR.

On-Line Thermally Induced Evolved Gas Analysis: An Update-Part 1: EGA-MS.

Advances in on-line thermally induced evolved gas analysis (OLTI-EGA) have been systematically reported by our group to update their applications in several different fields and to provide useful starting references. The importance of an accurate interpretation of the thermally-induced reaction mechanism which involves the formation of gaseous species is necessary to obtain the characterization of the evolved products. In this review, applications of Evolved Gas Analysis (EGA) performed by on-line coupling heating devices to mass spectrometry (EGA-MS), are reported. Reported references clearly demonstrate that the characterization of the nature of volatile products released by a substance subjected to a controlled temperature program allows us to prove a supposed reaction or composition, either under isothermal or under heating conditions. Selected 2019, 2020, and 2021 references are collected and briefly described in this review.

Analysis on thermal behavior of fluorides and cyanides for heat-treating spent cathode carbon blocks from aluminum smelters by TG/DSC-MS & ECSA®.

This paper adopts a novel data-processing method of ECSA® based on TG/DSC-MS system to basically study the characteristics of release and conversion of fluorides and cyanides during heat treatment of the spent cathode carbon block (SCCB). All the experiments were conducted at 10 K⋅min-1 heating rate and under Ar or Ar-O2 atmospheres. The results indicate that the release of fluorides was just a steady but slow phase transition process under both Ar and Ar-O2 atmospheres, which can be comparatively accelerated when the carbon material was burnt. The cyanides were effectively decomposed at high temperature and at Ar-O2 atmosphere, with around three quarters of the cyanides being converted to the N2 and nearly a quarter being to the NO. Finally, analysis on the flue gas composition indicates that it had a more complicated composition of CO2, N2, NO, NO2, HCN under Ar-O2 atmosphere but only had a composition of CO2 and NO under Ar atmosphere.

A Comprehensive Pyrolysis Mechanism of Binuclear Chromium-Based Complexes for Superior OER Activity.

Transition metal oxides are widely pursued as potent electrocatalysts for the oxygen evolution reaction (OER). However, single-metal chromium catalysts remain underexplored due to their intrinsic activity limitations. Herein, we successfully synthesize mixed-valence, nitrogen-doped Cr2O3/CrO3/CrN@NC nanoelectrocatalysts via one-step targeted pyrolysis techniques from a binuclear Cr-based complex (Cr2(Salophen)2(CH3OH)2), which is strategically designed as a precursor. Comprehensive pyrolysis mechanisms were thoroughly delineated by using coupled thermogravimetric analysis and mass spectrometry (TG-MS) alongside X-ray diffraction. Below 800 °C, the generation of a reducing atmosphere was noted, while continuous pyrolysis at temperatures exceeding 800 °C promoted highly oxidized CrO3 species with an elevated +6 oxidation state. The optimized catalyst pyrolyzed at 1000 °C (Cr2O3/CrO3/CrN@NCs-1000) demonstrated remarkable OER activity with a low overpotential of 290 mV in 1 M KOH and excellent stability. Further density functional theory (DFT) calculations revealed a much smaller reaction energy barrier of CrO3 than the low oxidation state species for OER reactivity. This work reveals fresh strategies for rationally engineering chromium-based electrocatalysts and overcoming intrinsic roadblocks to enable efficient OER catalysis through a deliberate oxidation state and compositional tuning.

Characteristics of pollutant generation from 3D-printed photocured waste combustion.

With the rapid advancement of photopolymerization-based 3D printing technology, the volume of PCW has experienced a sharp increase. The potential environmental ramifications of PCW disposal demand careful consideration, especially given its current practice of being incineration alongside MSW. In this study, the TG-MS/FTIR system was carried out to probe the thermogravimetric characteristics and volatile byproducts during combustion. Various product compositions resulting from different mixing ratios of PCW incineration with MSW were investigated. It was observed that fluorene (C13H10) and triphenylene (C18H12) produced by PCW combustion 0.52 mg/g and 0.43 mg/g respectively, which are twice as abundant as those generated from normal plastic. When PCW incineration along with MSW, compounds such as naphthalene (C10H8), cyclohexane (C6H12), and heptane (C7H16) were generated in concentrations of 1.25 mg/g, 1.05 mg/g, and 0.95 mg/g respectively, which are at least twice as much as with MSW incineration alone. The incineration of PCW with rubber and textiles resulted in the production of 2.34 mg/g to 3.76 mg/g more PAHs compared to PCW combustion alone. The incineration of PCW with paper resulted in the production of 3.12 mg/g to 5.15 mg/g more heptane, nonane, cyclohexane, pyrene, and anthracene than PCW combustion alone. Incineration of PCW with wood proved to be the cleanest method, with product contents primarily below 0.10 mg/g. When incinerated with food residues or normal plastic, most of the product content remained below 0.05 mg/g. Considering the environmental pollution resulting from PCW combustion, the disposal of PCW warrants careful consideration and management.

Influence mechanisms of different stalks on iron species type of magnetic biochar prepared from Fe2O3.

The current selection of biomass feedstock for magnetic biochar (MBC) catalysts is highly blind. Consequently, this study delves into understanding how the types of biomass influence the iron species present in MBC catalysts. The process involved the creation of MBC through simulated impregnation-pyrolysis, utilizing six types of stalks and Fe2O3. The type of iron species significantly impacted magnetic properties and likely influenced catalytic properties of MBC. MBC's iron species type was shaped by the reduction effects of the diverse stalks on Fe2O3. During the pyrolysis, discrepancies were observed in the release of reducing gases and direct reduction for the different stalks. These differences in reduction behavior directly accounted for the distinct reduction effects. To delve deeper, the reduction behavior and effect of the main components of the stalk (hemicellulose, cellulose, and lignin) on Fe2O3 were analyzed, highlighting lignin as the most effective. Nonetheless, the absolute values of Pearson's r between lignin content in the stalk and reduction behavior/effect ranged only from 0.078 to 0.421. In contrast, the values for K, Ca, and Si content in the stalks and their influence on reduction behavior and MBC's reduction/metallization degree ranged from 0.410 to 0.910. The catalytic impacts of K and Ca were confirmed through their incorporation into cotton and reed stalks. The disparities in K, Ca, and Si content among the six stalks appeared to be the primary driver behind the diverse iron species in MBC. This work provides a scientific basis for the rational selection of biomass feedstock for MBC catalysts.

Synthesis, Curing and Thermal Behavior of Amine Hardeners from Potentially Renewable Sources.

Research into bio-based epoxy resins has intensified in recent decades. Here, it is of great importance to use raw materials whose use does not compete with food production. In addition, the performance of the newly developed materials should be comparable to that of conventional products. Possible starting materials are lignin degradation products, such as vanillin and syringaldehyde, for which new synthesis routes to the desired products must be found and their properties determined. In this article, the first synthesis of two amine hardeners, starting with vanillin and syringaldehyde, using the Smiles rearrangement reaction is reported. The amine hardeners were mixed with bisphenol A diglycidyl ether, and the curing was compared to isophorone diamine, 4-4'-diaminodiphenyl sulfone, and 4-Aminonbenzylamine by means of differential scanning calorimetry. It was found that the two amines prepared are cold-curing. As TG-MS studies showed, the thermal stability of at least one of the polymers prepared with the potentially bio-based amines is comparable to that of the polymer prepared with isophorone diamine, and similar degradation products are formed during pyrolysis.

Thermal analysis technology to utilize waste biomass and waste heat to produce high-quality combustible gas through simulations and experiments.

To ensure the proper utilization of waste biomass (WB) and high-temperature waste heat, this study proposes a new method for obtaining gaseous fuels by pyrolyzing WB and using waste heat in the converter vaporization cooling flue (CVCF). This study is theoretically based on the simulation software Factsage 6.1 and the release patterns of the gaseous products including CO, H2, CH4 and CO2 obtained from waste biomass, were studied at different temperatures and pressures. Thermogravimetric-mass spectrometer (TG-MS) was used to investigate the pyrolysis of WB at heating rates of 5, 10, 15, and 20 °C/min from room temperature to 1400 °C. Kinetics parameters were calculated by using the Flynn-Wall-Ozawa (FWO) and Kissinger-Akahira-Sunose (KAS) models. To investigate the effects of temperature, a settling furnace was also used to simulate CVCF. Thermal decomposition produced the primary gases namely CO, CH4, and H2. Pyrolysis had an average activation energy of 183.29 kJ/mol. As the temperature increased from 800 °C to 1200 °C, the CO content increased from 39.7 % to 48.9 % and the H2 content increased from 35 % to 45.1 %. As the temperature rose from 800 to 1200 °C, the lower heating value (LHV) increased from 11.38 to 12.05 MJ/Nm3. The findings primarily confirmed the feasibility of injecting biomass into the CVCF to generate gaseous fuels from waste heat.

Coupled and Simultaneous Thermal Analysis Techniques in the Study of Pharmaceuticals.

Reliable interpretation of the changes occurring in the samples during their heating is ensured by using more than one measurement technique. This is related to the necessity of eliminating the uncertainty resulting from the interpretation of data obtained by two or more single techniques based on the study of several samples analyzed at different times. Accordingly, the purpose of this paper is to briefly characterize thermal analysis techniques coupled to non-thermal techniques, most often spectroscopic or chromatographic. The design of coupled thermogravimetry (TG) with Fourier transform infrared spectroscopy (FTIR), TG with mass spectrometry (MS) and TG with gas chromatography/mass spectrometry (GC/MS) systems and the principles of measurement are discussed. Using medicinal substances as examples, the key importance of coupled techniques in pharmaceutical technology is pointed out. They make it possible not only to know precisely the behavior of medicinal substances during heating and to identify volatile degradation products, but also to determine the mechanism of thermal decomposition. The data obtained make it possible to predict the behavior of medicinal substances during the manufacture of pharmaceutical preparations and determine their shelf life and storage conditions. Additionally, characterized are design solutions that support the interpretation of differential scanning calorimetry (DSC) curves based on observation of the samples during heating or based on simultaneous registration of FTIR spectra and X-ray diffractograms (XRD). This is important because DSC is an inherently non-specific technique. For this reason, individual phase transitions cannot be distinguished from each other based on DSC curves, and supporting techniques are required to interpret them correctly.

Mechanism of carbon nanotube growth in expanded graphite via catalytic pyrolysis reaction using carbores P as a carbon source.

Carbon nanotubes (CNTs) had potential applications in energy conversion and storage devices, and it could be prepared by expanded graphite loaded with catalyst at high temperature, however, the mechanism of carbon nanotube growth in expanded graphite need further confirmation. In this work, carbon nanotubes' in situ growth in expanded graphite (EG) were prepared via catalytic pyrolysis reaction using carbores P as a carbon source and Co(NO3)3•6H2O as a catalyst. The results of X-ray diffraction (XRD), scanning electron microscope (SEM) and energy dispersive X-ray spectroscope (EDS) indicated the carbon nanotubes could generate in, EG with the presence of carbores P as a carbon source and cobalt nitrate as a catalyst. More interestingly, the growth mechanism of carbon nanotubes could be concluded by the results of differential thermal analysis-thermogravimetry-mass spectrometry (DTA-TG-MS) and X-ray photoelectron spectroscopy (XPS) analysis. The pyrolysis products of carbores P were mainly hydrocarbon gas such as CH4 gas, which reacts with Co(NO3)3·6H2O catalyst to reduces CoOx to Co particles, then the carbon form pyrolysis was deposited the on the surface catalyst Co particles and, after continuous solid dissolution and precipitation, carbon nanotubes were at last generated in EG at last.

Flue gas torrefaction of municipal solid waste: Fuel properties, combustion characterizations, and nitrogen /sulfur emissions.

Flue gas torrefaction (FGT) was proposed as the pretreatment of the municipal solid waste (MSW) combustion process to improve the fuel properties of MSW and achieve better combustion performance. The optimal FGT parameters were obtained at 300 ℃ and 30 min, with the energy-mass co-benefit index (EMCI) reaching the maximum of 23.38. FGT could significantly increase the heating value and energy density of MSW while reducing the H/C and O/C ratio. Then, the pyrolysis and combustion experiments were performed by tube furnace and TG-MS. The results proved the chemical compositions of MSW were altered, and the heat transfer was enhanced. With FGT, NOx and SO2 emissions could be reduced by 25.7 % and 52.4 %, respectively. This study provides an in-depth understanding of the mechanism of FGT and paves the way for the clean treatment and energy utilization of MSW.

Pyrolysis Combustion Characteristics of Epoxy Asphalt Based on TG-MS and Cone Calorimeter Test.

To examine the pyrolysis and combustion characteristics of epoxy asphalt, the heat and smoke release characteristics were analyzed via TG-MS and cone calorimeter tests, and the surface morphology of residual carbon after pyrolysis and combustion was observed via scanning electron microscopy. The results showed that the smoke produce rate of epoxy asphalt was high in the early stage, and then sharply decreased. Moreover, the total smoke produced was close to that of base asphalt, and the surface of residual carbon presented an irregular network structure, which was rough and loose, and had few holes, however most of them existed in the form of embedded nonpenetration. The heat and smoke release characteristics of epoxy asphalt showed that it is not a simple fusion of base asphalt and epoxy resin. Instead, they promote, interact with, and affect each other, and the influence of epoxy resin was greater than that of base asphalt.

An integrated study on the pyrolysis mecanism of peanut shell based on the kinetic analysis and solid/gas characterization.

An in-depth understanding of peanut shell pyrolysis reaction is essential for its efficient utilization. Detailed analysis of thermodynamics, kinetics, and reaction products can provide valuable information about pyrolysis reaction. In this work, pyrolytic reaction mechanism was elucidated with the analysis of thermogravimetric-mass spectrometry and the structural characterization of the derived biochar. The thermodynamic and kinetic parameters of three sub-stages were matched well in different model-free methods. The positive ΔH and ΔG values indicated that the pyrolysis reactions for three stages were endothermic and nonspontaneous. The reaction mechanism predicted by integral master-plots were F3 (f(α) = (1-α)3), F1 (f(α) = (1-α), and F3 (f(α) = (1-α)3) for the three sub-stages, respectively. The negative ΔS in the third stage was related to the reduced releasing of low-molecular weight gases and ordered graphite-like carbon structure. This study provides a prospective approach to understand the pyrolysis mechanism of biomass.

Flue gas torrefaction of distilled spirit lees and the effects on the combustion and nitrogen oxide emission.

Flue gas torrefaction (FGT) integrated with combustion was introduced for the clean treatment of distilled spirit lees (DSL). The effects of temperature, residence time, and volumetric flow rate of FGTs were investigated. The improvement in the physicochemical and combustion characteristics of the torrefied DSL and the reaction mechanisms were clarified by a tube furnace and the TG-MS device. The results showed that FGT could effectively improve the properties of DSL. With increasing temperature, residence time, and volumetric flow rate, the mass and energy yields decreased. FGT showed positive effects on the removal of free and bonding water, as well as the enrichment of lignin. FGT effectively inhibited the release of NOx. The overall emission of NOx was reduced by 57.3%. Additionally, the cost of DSL drying and denitrification could be greatly reduced by FGT. This study provided a practical treatment for DSL and new insight into FGT.

TG- MS study on in-situ sulfur retention during the co-combustion of reclaimed asphalt binder and wood sawdust.

Reclaimed asphalt binder (RAB) releases large amounts ·of hazardous sulfur-containing gases during combustion. This study attempts to introduce wood sawdust (WS) as an in-situ inhibitor of sulfur release during the combustion of refuse-derived fuel (RDF) blended with RAB-WS. The combustion characteristics, gaseous sulfur-containing products, interactions and combustion kinetics of RDF were investigated through thermogravimetry and mass spectrometry (TG-MS), and the mechanisms on migration and distribution of sulfur were revealed. Results indicated that WS additive inhibits the volatilization of light components and promotes the degradation of macromolecular components. WS addition improved the combustibility, burnout performance and combustion stability of RAB. The sulfur release of RAB-based RDF was mainly derived from resins and asphaltenes. WS addition generally decreased all gaseous sulfur-containing compounds (CH3SH, COS, SO2, CS2 and thiophene). Interactions between RAB and WS restrained all sulfur-containing gas emissions, and the normalized sulfur inhibition ratio reached 40.99 %. The Sarink and DAEM models could well describe the kinetic process of the co-combustion of RAB and WS. WS addition led to a decrease in activation energy, namely, it lowered the reaction barrier. Sulfur could be retained in-situ into incineration residue through the formation of sulfate minerals during the co-combustion of RAB and WS.

Effect of slow pyrolysis conditions on biocarbon yield and properties: Characterization of the volatiles.

Slow pyrolysis of spruce and birch was performed at various heating programs and conditions in a horizontal quartz tube reactor heated by an electric furnace. The effects of feedstock and carbonization conditions on the yield of biocarbon, liquid and gaseous products were studied. The thermal properties, volatile matter (VM) content and the evolution profiles of volatiles from the biocarbons were characterized by thermogravimetry/mass spectrometry. The composition of volatiles was analyzed in detail by pyrolysis-gas chromatography/mass spectrometry. Increased char yield was observed when staged pyrolysis program, low purging flow rate or covered sample holder were applied. Spruce produced more charcoal than birch due to the higher lignin content of softwood. The amount and the evolution profiles of the main gaseous products were similar from spruce and birch biocarbons prepared under the same conditions. The relative amount of aromatic and polyaromatic compounds in VM drastically decreased with increasing carbonization temperature.

Multi-response optimization toward efficient and clean (co-)combustions of textile dyeing sludge and second-generation feedstock.

The rapid growth of textile dyeing sludge (TDS) necessitates feeding it back into a circular economy in an efficient and clean way. This study aimed to optimize the clean and efficient operational conditions to co-combust TDS and incense sticks (IS). The (co-)-combustions exhibited four distinctive stages of thermal degradation. According to the master-plots method, the reaction mechanisms of reaction order (F2.4 and F1.5), three-dimensional diffusion (D3), and nucleation growth (A1.5) best explained the four stages, respectively. The interaction between TDS and IS exerted an inhibition effect in the range of 400-500 °C and a facilitation effect in the range of 600-1000 °C. At 300 °C as the main reaction temperature, the main evolved gas and functional groups such as CO2, H2O, CH4, CË­O, C-O, and C-H were detected. The addition of IS improved the comprehensive combustion index, inhibited SO2, but enhanced CO2, HCN, and NOx emissions. CaO in IS enabled Fe to remain in TDS and fixed more S in ash. Multi-response optimizations based on the best-fit artificial neural networks revealed the range of 545-605 °C and the co-combustion of 25% TDS and 75% IS as the cleaner and more efficient operational conditions.

Dielectric, Thermal and Water Absorption Properties of Some EPDM/Flax Fiber Composites.

This paper deals with the dielectric and sorption properties of some flax fiber-reinforced ethylene-propylene-diene monomer (EPDM) composites containing different fiber loadings as well as their behavior after exposure to different doses of electron beam irradiation. Three relaxation processes were evinced, a weak relaxation ß at sub-Tg temperatures and two α-type relaxations above the Tg. The EPDM/flax composites exhibited higher values of dielectric constant, dielectric loss and conductivity as compared to a pristine EPDM sample. Using thermogravimetric analysis (TG) coupled with Fourier transform infrared spectroscopy (FTIR) and mass spectrometry (MS) (TG/FTIR/MS system), the degradation products can be identified. The water uptake increased as the flax fiber level increased in composites. The water uptake tests of irradiated composites showed that the highest water content was obtained for a flax fiber level of 20 phr.

Analysis of Four Solvatomorphs of Betulin by TG-DTA-EI/PI-MS System Equipped with the Skimmer-Type Interface.

Betulin (BE) has exceedingly become a potential natural product, providing multiple pharmacological and biological activities, including anti-cancer, anti-viral, and anti-inflammatory benefits. Previous research indicated that the solvatomorphism of BE can easily occur through crystallization with different organic solvents. This property of BE can directly affect its extraction, isolation, and preparation process. In this study, a system of thermogravimetry (TG)-differential thermal analysis (DTA) coupled with mass spectrometry (MS) with electron ionization (EI) and photoionization (PI) capability, equipped with the skimmer-type interface (i.e., skimmer-type interfaced TG-DTA-EI/PI-MS system), as a real-time and onsite analysis technique, was employed. Then, four solvatomorphs of BE, namely, with pyridine and water (A), sec-butanol (B), n,n-dimethylformamide (DMF) (C), and isopropanol (V), were analyzed for the first time. Finally, five kinds of the main volatile gaseous species, including H2O, pyridine, sec-butanol, DMF, and isopropanol, were identified clearly. Furthermore, the multi-step desolvation processes of the four solvatomorphs of BE were revealed by this system for the first time. This system showed great potential for the rapid and accurate analysis of various solvatomorphs of natural products.