Changes in active functional groups during low-temperature oxidation of coal

Using Fourier Transform Infrared (FTIR) combined with an adiabatic oxidation test, temperature-programmed oxidation and gas analysis, we studied the changes of active functional groups during low-temperature oxidation of lignite, gas coal, fat coal and anthracite. During slow low-temperature heat accumulation, aliphatic hydrocarbons, such as methyl and methylene, are attacked by oxygen atoms absorbed by pores on coal surfaces, generating unstable solid intermediate carbon-oxygen complexes, which then decompose into gaseous products (CO, CO2) and stable solid complexes. At the accelerated oxidation stage, the stable complexes begin to decompose in large amounts and provided new active sites for further oxidation, while the aliphatic structures gained energy and fell from the benzene rings to produce CxHy and H2.

Co-synthesis of vertical graphene nanosheets and high-value gases using inductively coupled plasma enhanced chemical vapor deposition

One-step controllable synthesis of vertical graphene nanosheets （VGs） and high-value gases was achieved using inductively coupled plasma enhanced chemical vapor deposition （ICPECVD）. The basic physical properties of the ICPECVD process were revealed via electrical diagnosis and optical emission spectroscopy. The coil current and voltage increased linearly with the augmenting of injected power, and CH, C2, H2 and H were detected at a wavelength from 300 to 700 nm, implying the generation of abundant graphene-building species. The morphology and structure of solid carbon products, graphene nanosheets, were systemically characterized in terms of the variations of operating conditions, such as pressure, temperature, gas proportion, etc. The results indicated that an appropriate operating condition was indispensable for the growth process of graphene nanosheets. In the present work, the optimized result was achieved at the pressure, heating temperature, applied power and gas proportion of 600 mTorr, 800 ~C, 500 W and 20：20：15, respectively, and the augmenting of both CH4 and H2 concentrations had a positive effect on the etching of amorphous carbon. Additionally, H2 and C2 hydrocarbons were detected as the main exhaust gases. The selectivity of H2 and C2H2, measured in exhaust gases, reached up to 52% and 8%, respectively, which implied a process of free radical reactions and electron collision dissociation. Based on a comprehensive investigation of spectral and electrical parameters and synthesized products, the reaction mechanism of collision, dissociation, diffusion, etc, in ICPECVD could be speculated, providing a probable guide for experimental and industrial applications.

Gas evolution characteristics of three kinds of no-bake resin-bonded sands for foundry in production

No-bake resin-bonded sand is commonly used in casting production.However,its air pollution is relatively serious,especially in the molding and pouring process.For this reason,it is necessary to study the gas evolution characteristics of no-bake resin-bonded sand from room temperature to high temperatures,and not only the amount of gaseous products,but also the composition of the gaseous products.No-bake furan resin-bonded sand(#1),phenolic urethane no-bake resin-bonded sand(#2),and alkaline phenolic no-bake resin-bonded sand(#3)are the three most common no-bake resin-bonded sands in casting.The gas evolution volume and rate of these three no-bake resin-bonded sands were studied.Thermogravimetry-mass spectrometer(TG-MS),headspace-gas chromatography/mass spectrometer(HS-GC/MS),and pyrolysis-gas chromatography/mass spectrometer(PY-GC/MS)were used to measure the composition of the gaseous products emitted from binders at room temperature and high temperatures.The differences between formaldehyde,heterocyclic aromatic compounds(HAC),monocyclic aromatic hydrocarbons(MAH),and polycyclic aromatic hydrocarbons(PAHs)gaseous products from the three types of no-bake resin-bonded sands during the molding and casting process were compared.From the perspective of environmental protection,alkaline phenolic no-bake resin-bonded sand and no-bake furan resin-bonded sand are better than phenolic urethane no-bake resin-bonded sand.

Theoretic heat sink simulation and experimental investigation of the pyrolysis of substituted cyclohexanes

Reaxgen program for the pyrolysis mechanism of cycloalkanes was adopted to simulate the heat sink of substituted cyclohexanes. Thermal cracking of cyclohexanes was performed to examine the cracking performance, wherein the substituent effects were detailedly discussed under supercritical condition. It was found that Reaxgen program played a good part in the screening and optimization of cyclohexanes. A good agreement with the experimental data for the mono-substituted and bi-substituted cyclohexanes was demonstrated, however, some deviation for the tri-substituted cyclohexanes were observed. The experiment results indicated that the gaseous product yield increased sharply for mono- substituted cyclohexanes with short substituents containing no more than two carbons. Nevertheless, continuous increase in the alkyl chain depressed the gaseous product yield smoothly. The cyclic substituent dramatically inhibited the pyrolysis of cyclohexanes. All the substituents but cyclohexyl had no obvious effect on the yield of hydrogen and olefins （≤C4）. For bi-substituted cyclohexanes, the more close the distance between the two substituents, the higher the gaseous product yield was obtained. However, opposite result on the selectivity to hydrogen and olefins （≤C4） was generally obtained except 1,3-dimethylcyclohexane. The position of tri-substituents acted little significance on the gaseous product yield, as well as the selectivity to hydrogen and olefins （≤C4）.

TG-FTIR Study on the Pyrolysis Properties of Lignin from Different Kinds of Woody Biomass

Pyrolysis properties of lignin separated from four different kinds of wood （fir, larch, poplar, and eucalyptus） compared with commercial lignin were investigated using a thermogravimetric analyzer coupled to a Fourier-transform infrared spectrometer（TG-FTIR）. Kinetic parameters of lignin thermal cracking reaction, such as activation energy and pre-exponential factor, were calculated using a three-dimensional diffusion model. The carbon residue rate and activation energy of softwood lignin were higher than those of hardwood lignin, showing that the decomposition of the former is relatively more dif？cult than that of the latter during pyrolysis. The distinct characteristic peaks of small-molecule gases and oxygenated chemicals such as ethers, phenols, acids, aldehydes, and alcohols were observed near the maximum weight loss rate by analyzing the 3D IR spectrum of the gas phase products. The formation routes of the main gaseous products were discussed, and the following order of releasing amounts was noted： CO2〉CH4〉H2O〉CO. It is believed that these results will provide valuable information for the thermo-chemical conversion process of lignin from the point of view of feedstock.

Kinetics of Catalyzed Thermal Degradation of Polylactide and Its Application as Sacrificial Templates

Polylactide(PLA)is an outstanding sacrificial template material for the manufacture of microchannels in a thermosetting matrix.However,the initial thermal degradation temperature of pure PLA is relatively high(about 280℃),which limits its use as a sacrificial template.In this report,we found that TBD,an organic base catalyst,can significantly reduce the thermal degradation temperature of PLA.TBD has higher catalytic activity for the thermal degradation of PLA compared with Tin(II)oxalate(Sn(Oxa)),one catalyst reported in the literature.Moreover,the gaseous products catalyzed by TBD for PLA thermal degradation are mainly lactide,and the formation temperature of the monomer is lower and the yield is higher,which may have potential value for PLA recycling.A combined catalyst,S8T2,was composed of 80%low activity catalyst Sn(Oxa)and 20%high activity catalyst TBD,which can catalyze the rapid degradation of PLA without greatly damaging the mechanical properties of PLA.PLA-S8T2 sacrificial fibers can form high-precision one-dimensional microchannels in the epoxy resin matrix,and 3D-printed PLA-S8T2 sacrificial templates can be used to form three-dimensional microchannels in a thermosetting matrix by vaporization of sacrificial components process(VaSC).These features highlight the great potential of PLA-S8T2 as sacrificial template material for the preparation of the complicated microchannels in the thermosetting matrix.

Chemical looping gasification characteristics and kinetic analysis of Chlorella and its organic components

Chemical looping gasification(CLG)characteristics and kinetic analysis of Chlorella(CHL),simulated Chlorella(V-CHL)and medium-chain triglycerides(MCT)were investigated using a thermogravimetric analyzer coupled with an online mass spectrometer.The apparent activation energy was obtained via Kissinger-Akahira-Sunose(KAS)method.In the result of the weightless behavior,the addition of oxygen carrier inhibited the decomposition of V-CHL at lower temperatures but promoted its decomposition at high temperatures.The values of chemical looping process characteristic parameters showed that a 10 wt%oxygen carrier would maximize the release of volatile products in the CLG of MCT,with 5.12×10^(-6)%⋅min^(-1)⋅℃^(-3).Oxygen carriers also affected gaseous products.The LHV of gaseous products of CHL reached the largest when the oxygen carrier was 10 wt%,which was 8.13 MJ/m^(3).And the gaseous product of MCT had the largest LHV with 30 wt%oxygen carrier,which was 8.83 MJ/m^(3).According to the kinetic analysis,the minimum value of apparent activation energy of MCT chemical looping gasification was 89.54 kJ⋅mol^(-1) with the oxygen carrier of 30 wt%,which was 50%less than that of MCT pyrolysis.And the minimum value for V-CHL was obtained when the mass fraction of Fe2O3 was 50 wt%.This paper could provide a reference for the choice of algae,the design of reactors,and the targeted regulation of the gaseous product for the algae CLG process.