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1.
Particulate matter (PM) from diesel vehicles is harmful to humans and should be removed from the exhaust gases before its emission into the atmosphere. Plasma PM oxidation is an advanced method to be used for oxidative PM removal. Factors influencing plasma PM oxidation include gas temperature, gas composition, PM amount, the geometry of plasma reactors. The PM oxidation in atmospheric air discharges was carried out using a pulsed dielectric barrier discharge reactor at temperatures of 100, 150, and 200 °C. It was found that PM is oxidized to CO and CO2. CO2/CO concentration ratio is a function of PM amount in the discharge space. PM removal efficiency (PM amount oxidized per kWh energy injection) increased with increasing air temperature and PM amount in the discharge space. Water promotes PM oxidation, which suggested that oxygen atoms produced in the discharge space react with water to yield hydroxyl free radicals that are of more reactivity than oxygen atoms. The activation energy of plasma PM oxidation was kinetically calculated to be 15.4 kJ/mol.  相似文献   

2.
Thermal decomposition of an amorphous precursor for S-doped titania (TiO2) nanopowders, prepared by controlled sol–gel hydrolysis–condensation of titanium(IV) tetraethoxide and thiourea in aqueous ethanol, has been studied up to 800 °C in flowing air. Simultaneous thermogravimetric and differential thermal analysis coupled online with quadrupole mass spectrometer (TG/DTA-MS) and FTIR spectrometric gas cell (TG-FTIR) have been applied for analysis of released gases (EGA) and their evolution dynamics in order to explore and simulate thermal annealing processes of fabrication techniques of the aimed S:TiO2 photocatalysts with photocatalytic activities under visible light. The precursor sample prepared with thiourea, released first water endothermically from room temperature to 190 °C, carbonyl sulfide (COS) from 120 to 240 °C in two stages, ammonia (NH3) from 170 to 350 °C in three steps, and organic mater (probably ether and ethylene) between 140 and 230 °C. The evolution of CO2, H2O and SO2, as oxidation products, occurs between 180 and 240 °C, accompanied by exothermic DTA peaks at 190 and 235 °C. Some small mass gain occurs before the following exothermic heat effect at 500 °C, which is probably due to the simultaneous burning out of residual carbonaceous and sulphureous species, and transformation of amorphous titania into anatase. The oxidative process is accompanied by evolution of CO2 and SO2. Anatase, which formed also in the exothermic peak at 500 °C, mainly keeps its structure, since only 10% of rutile formation is detected below or at 800 °C by XRD. Meanwhile, from 500 °C, a final burning off organics is also indicated by continuous CO2 evolution and small exothermic effects.  相似文献   

3.
Energetic materials such as a mixture of guanidine nitrate (GN)/basic copper nitrate (BCN) are used as gas generators in automotive airbag systems. However, at the time of the airbag inflation, the gas generators release toxic combustion gases such as CO, NH3, and NOx. In this study, we investigated the combustion and thermal decomposition behaviors of GN/BCN mixture, focusing primarily on their exhaust gas composition. As a result, when the exhaust gas of the combustion under constant pressure in an inert gas stream was analyzed using a detection tube, the amount of NOx (mainly NO) yielded greater decrease with increasing atmospheric pressure as compared to the amounts of CO and NH3. Thus, provided GN/BCN is ignited in a closed container, a large amount of NOx is presumed to have been released during the initial stage of combustion, which yielded comparatively low pressure. Results of the thermogravimetry–differential scanning calorimetry–Fourier transform infrared spectroscopy (TG/DSC/FTIR) indicated that the GN/BCN mixture caused endothermic decomposition at 170 °C and exothermic decomposition at 208 °C, which was accompanied by 66% mass loss. The decomposition gases, CO2, N2O, and H2O, were detected via FTIR spectrum. Because N2O was not detected in the combustion gas, it was suggested that the detected N2O was generated at a low temperature and decomposed in high-temperature combustion.  相似文献   

4.
Improvement of indoor air quality regarding volatile organic compounds (VOCs) requires the development of innovative oxidation processes. This paper investigates the coupling of a metal oxide sorbent with non-thermal plasma (NTP) in an especially designed reactor. TiO2 was selected as model sorbent and acetone was used as model VOC. The analyses of gas phase species at the reactor downstream have been performed using FTIR spectroscopy. In a first step, acetone adsorption on TiO2 surface under dry air was characterized in terms of total amount adsorbed, as well as reversibly and irreversibly adsorbed fractions. Obtained results were compared and discussed with literature in terms of acetone reactive adsorption on TiO2 surface. Mesityloxide was proposed as the major compound in the irreversibly adsorbed fraction. In a second time, acetone saturated TiO2 surface was exposed to NTP surface discharge. Irrespectively of the injected power, <30 % of the initially adsorbed acetone has been recovered as CO, CO2 and desorbed acetone. Finally, thermal desorptions have been performed. They evidenced that (1) NTP treatment modifies the nature of the adsorbed organic species, (2) mineralization rate is considerably improved. Based on desorbed species temporal profile analysis, carboxylates and more especially formates are suggested as major adsorbed species after NTP treatment (Pinj > 0.2 W). This hypothesis has been evaluated and confirmed. This paper finally evidenced that NTP can be used as an efficient pretreatment technique to promote the mineralization of adsorbed acetone for further thermal treatment.  相似文献   

5.
The ageing characteristics of pyrotechnic compositions are influenced not only by temperature, but also by surrounding effects as humidity and vibrations. In this paper the thermal stability of the pyrotechnic system magnesium–sodium nitrate will be investigated. In an inert helium atmosphere two steps of mass loss, which were not completely separated from each other, were observed in the temperature range from 65 to 265°C: a mass loss of about 15% between 65 and 160°C and about 34% between 160 and 265°C. It is assumed that these two steps are caused by different processes. The separation between the two steps was not or hardly detectable for measurements that were performed in a nitrogen atmosphere. Using MS and FTIR (mass spectrometry/Fourier transform infrared spectroscopy) the evolved gases were analysed. Only above about 170°C evolving gases were detected (which means that during the first step no gases were detectable). The detected gas mainly consists of CO2, CO and N2O, with smaller amounts of NO2, NO and possibly HCN. A third step of mass loss (8–9%) was observed above 314°C. The process which caused this step of mass loss is considered not to contribute significantly to the ageing of the material at much lower temperatures of maximum 80°C, which is of interest in view of the use of the materials.  相似文献   

6.
Thermal behavior of highly crystalline ε-Fe2O3 nanoparticles of different apparent crystallite sizes was characterized using thermogravimetry, differential thermal analysis, and analysis of evolved gas by mass spectrometry. Phase composition of the samples was monitored ex situ by X-ray powder diffraction. The results show that the thermal stability of this metastable iron oxide polymorph decreases with increasing particle size. For the particle diameter of 19(2) nm, the transformation temperature was equal to 794(5) °C, while for 28(2) nm only 755(10) °C. Surface of the nanoparticles contained adsorbed water and carbon dioxide. Elimination of these species proceeds in two steps. Water is removed at temperatures below 200 °C and CO2 in the temperature range between 200 and 450 °C.  相似文献   

7.
The products evolved during the thermal decomposition of kaolinite–urea intercalation complex were studied by using TG–FTIR–MS technique. The main gases and volatile products released during the thermal decomposition of kaolinite–urea intercalation complex are ammonia (NH3), water (H2O), cyanic acid (HNCO), carbon dioxide (CO2), nitric acid (HNO3), and biuret ((H2NCO)2NH). The results showed that the evolved products obtained were mainly divided into two processes: (1) the main evolved products CO2, H2O, NH3, HNCO are mainly released at the temperature between 200 and 450 °C with a maximum at 355 °C; (2) up to 600 °C, the main evolved products are H2O and CO2 with a maximum at 575 °C. It is concluded that the thermal decomposition of the kaolinite–urea intercalation complex includes two stages: (a) thermal decomposition of urea in the intercalation complex takes place in four steps up to 450 °C; (b) the dehydroxylation of kaolinite and thermal decomposition of residual urea occurs between 500 and 600 °C with a maximum at 575 °C. The mass spectrometric analysis results are in good agreement with the infrared spectroscopic analysis of the evolved gases. These results give the evidence on the thermal decomposition products and make all explanation have the sufficient evidence. Therefore, TG–MS–IR is a powerful tool for the investigation of gas evolution from the thermal decomposition of materials and its intercalation complexes.  相似文献   

8.
The indium complex, mer-trichlorotris(thiourea)-indium(III) (In(tu)3Cl3, 1), crystallized from aqueous solution of InCl3 and SC(NH2)2 (tu) with molar ratio of 1:3, is a single-source precursor for In2S3 films by chemical spray pyrolysis. The structural model of the triclinic crystal 1 (space group P-1 with a = 8.4842(2) Å, b = 10.5174(2) Å, c = 13.1767(2) Å, α = 111.1870(10)°, β = 98.0870(10)°, γ = 97.889(2)°) has been improved by single crystal X-ray diffraction analysis through successful separation of the disordered positions of the asymmetric complex molecule situated on the inversion centre into two spatial arrangements. Thermal decomposition of 1 occurs with very similar mass loss courses till 400 °C in both nitrogen and air, anyhow the DTA curve indicates a gas-phase oxidation with an additional exothermic heat effect at 255 °C in air. Partial or more advanced oxidation of the initially evolved CS2 has taken place in both atmospheres, as its oxidation products, SO2, COS, CO2 are accompanied by the release of NH3, HCl in temperature range of 205–275 °C, while H2NCN and HCN evolve in air. In the third mass loss step, in the temperature interval of 405–750 °C in nitrogen and 405–700 °C in air, two processes, evaporation and oxidation of the solid residues are competing with each other, resulting in final decomposition product of 1 in air In2O3, while also some In2O3 in inert atmosphere beyond the main phase of In2S3 where, in addition considerable extent of loss of indium occurs, probably through volatile dimeric indium chloride species, which could not be detected either by EGA-MS or EGA-FTIR systems of ours. Nevertheless, evolution of HNCS is confirmed by EGA-FTIR, and release of CO2, H2NCN, SO2, and a little HCl is detected at temperatures above 450 °C in both atmospheres.  相似文献   

9.
The research shows theoretical calculations on the thermodynamics of digestion/gasification processes where glucose is used as a surrogate for biomass. The change in Enthalpy (?H) and Gibbs Free Energy (?G) is used to obtain the Attainable Region (AR) that shows the overall thermodynamic limits for digestion/gasification from 1 mol of glucose. Gibbs Free Energy and Enthalpy (GH) plots were calculated for the temperature range 25–1500 °C. The results show the effect of temperature on the AR for the processes when water is in both liquid and gas states using 25 °C, 1 bar as the reference state. The AR results show that the production of CO, H2, CH4 and CO2 are feasible at all temperatures studied. The minimum Gibbs Free Energy becomes more negative from ?418.68 kJ mol?1 at 25 °C to ?3024.34 kJ mol?1 at 1500 °C while the process shifts from exothermic (?141.90 kJ mol?1) to endothermic (1161.80 kJ mol?1) for the respective temperatures. Methane and carbon dioxide are favoured products (minimum Gibbs Free Energy) for temperatures up to about 600 °C, and this therefore includes Anaerobic Digestion. The process is exothermic below 500 °C, and thus Anaerobic Digestion requires heat removal. As the temperature continues to increase, hydrogen production becomes more favourable than methane production. The production of gas is endothermic above 500 °C, and it needs a supply of heat that could be done, either by combustion or by electricity (plasma gasification). The calculations show that glucose conversion at temperatures around 700 °C favours the production of carbon dioxide and hydrogen at minimum G. Generally, the results show that the gas from high-temperature gasification (>~800 °C) typically carries the energy mainly in syngas components CO and H2, whereas at low-temperature gasification (<500 °C) the energy is carried in CH4. The overall analysis for the temperature range (25–1500 °C) also suggests a close relationship between biogas production/digestion and gasification as biogas production can be referred to as a form of low-temperature gasification.  相似文献   

10.
The reduction of silver phosphate with graphite under vacuum conditions was studied at final reaction temperatures varying from 430 to 915°C to determine: (i) the CO2 extraction yield, and (ii) the oxygen isotopic composition of CO2. The CO2 yield and oxygen isotopic composition were determined on a calibrated dual inlet and triple collector isotope ratio mass spectrometer. We observed the following three stages of the reduction process. (1) At temperatures below 590°C only CO2 is formed, while silver orthophosphate decays to pyrophosphate. (2) At higher temperatures, 590–830°C, predominantly CO is formed from silver pyrophosphate which decays to metaphosphate; this CO was always converted into CO2 by the glow discharge method. (3) At temperatures above 830°C the noticeable sublimation of silver orthophosphate occurs. This observation was accompanied by the oxygen isotope analysis of the obtained CO2. The measured δ18O value varied from ?11.93‰ (at the lowest temperature) to ?20.32‰ (at the highest temperature). The optimum reduction temperature range was found to be 780–830°C. In this temperature range the oxygen isotopic composition of CO2 is nearly constant and the reaction efficiency is relatively high. The determined difference between the δ18O value of oxygen in silver phosphate and that in CO2 extracted from this phosphate is +0.70‰. Copyright © 2010 John Wiley & Sons, Ltd.  相似文献   

11.
Low-input high-diversity (LIHD) mixtures of native grassland perennials were subjected to a supercritical treatment process with the aim of obtaining hydrogen-rich gases. The process was studied based on the following treatment variables: reaction temperature (374 °C to 575 °C, corresponding to a pressure range of 22.1 to 40 MPa), residence time (10 to 30 min), biomass content in the feed, and catalysts (0% to 4% NaOH and solid alkali CaO–ZrO2). The gaseous phase produced from gasification of LIHD primarily consisted of hydrogen (H2), with a mixture of carbon monoxide (CO), methane (CH4), and carbon dioxide (CO2). The statistical significance of treatment variables was evaluated using analysis of variance (ANOVA). It showed that at the level of P?<?0.05, temperature, catalysts, and biomass content in the feed significantly affected gas yields, while residence time was not significant.  相似文献   

12.
For fullerite C60 with intercalated oxygen, a sharp (by three orders of magnitude) increase in the intensity of the EPR signal with a g-factor of 2.0024 was observed at ~200°C. Studies of gases formed in heating of the sample in a vacuum showed that molecular oxygen was largely released at temperatures below 100°C, whereas the gas phase formed as the temperature increased to 200°C contained carbon oxides CO and CO2 in addition to oxygen. The conclusion was drawn that the intensity of the EPR signal was determined by the products of oxygen interaction with fullerene rather than the concentration of oxygen in the sample.  相似文献   

13.

Oxyfuel combustion represents one way for cleaner energy production using coal as combustible. The comparison between the oxycombustion and the conventional air combustion process starts with the investigation of the pyrolysis step. The aim of this contribution is to evaluate the impact of N2 (for conventional air combustion) and CO2 (for oxy-fuel combustion) atmospheres during pyrolysis of three different coals. The experiments are conducted in a drop tube furnace over a wide temperature range 800–1400 °C and for residence time ranging between 0.2 and 1.2 s. Coal devolatilized in N2 and CO2 atmospheres at low temperatures (?1200 °C) and longer residence times (>?0.5 s), the char-CO2 reaction is clearly observed, whose intensity depends on the nature of the coal. Furthermore, the volatile yields are simulated using Kobayashi’s scheme and kinetic parameters are predicted for each coal. The char gasification under CO2 is also accounted for by the model.

  相似文献   

14.
In order to determine the intrinsic reactivity behavior from thermogravimetry studies, the experimental conditions should be such that the reactions are not mass transfer limited. Biomass char usually has a higher reactivity than coal chars. Therefore, mass transfer limitations may be more problematic when studying biomass char reactivity. Chemical reaction kinetics and mass transfer processes present in thermogravimetry are used for modeling the overall reaction rate for spruce bark CO2 gasification. Thermogravimetric experiments are carried out between 700 and 900 °C, and the CO2 concentration is varied between 10 and 90 vol%. The intrinsic activation energy is found to be 120 kJ mol?1. The transition temperature between regimes I and II is here defined when the fraction apparent to true activation energy equals 0.75. Higher external mass transfer (e.g., by decreasing the diffusion path through the crucible’s freeboard), decreasing the sample amounts, and higher CO2 partial pressures for the Langmuir–Hinshelwood reaction type increase the transition temperature. The results show that the transition temperature between regimes I and II conditions is approx. 1,030 °C for 90 vol% CO2.  相似文献   

15.
Carbon capture and storage is an important strategy for stabilizing the increasing concentration of atmospheric CO2 and the global temperature. A possible approach toward reversing this trend and decreasing the atmospheric CO2 concentration is to remove the CO2 directly from air (direct air capture). Herein we report a simple aqueous guanidine sorbent that captures CO2 from ambient air and binds it as a crystalline carbonate salt by guanidinium hydrogen bonding. The resulting solid has very low aqueous solubility (K sp=1.0(4)×10−8), which facilitates its separation from solution by filtration. The bound CO2 can be released by relatively mild heating of the crystals at 80–120 °C, which regenerates the guanidine sorbent quantitatively. Thus, this crystallization‐based approach to CO2 separation from air requires minimal energy and chemical input, and offers the prospect for low‐cost direct air capture technologies.  相似文献   

16.
Two methods are described for doping of fullerite C60 with molecular oxygen at a pressure of ∼104 Pa and at temperature 20–30 °C. It was found by mass spectrometry using oxygen 18O as dopant that a portion of molecular oxygen absorbed by the pre-decontaminated fullerite (first method) is removed as CO and CO2 at the heating temperature ≤200 °C. Doping during fullerite precipitation from the liquid phase (second method) makes it possible to prepare samples with the oxygen content ≥1.2 at.%. The fullerite doped with oxygen to this level is diamagnetic. The paramagnetic properties of an O2 molecule disappear when O2 is incorporated into the fullerene lattice. This is interpreted on the basis of quantum chemical calculations as a sequence of equilibrium formation of the adduct C60O2. Calculations showed that the subsequent chemical transformation of C60O2 resulting in the O-O bond cleavage is energetically favorable, enabling prerequisites for the formation of products of incomplete (CO) and deep (CO2) oxidation of fullerene under mild conditions. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 662–671, April, 2006  相似文献   

17.
Tin dioxide (SnO2) has intrinsic characteristics that do not favor its photocatalytic activity. However, we evidenced that surface modification can positively influence its performance for CO2 photoreduction in the gas phase. The hydroxylation of the SnO2 surface played a role in the CO2 affinity decreasing its reduction potential. The results showed that a certain selectivity for methane (CH4), carbon monoxide (CO), and ethylene (C2H4) is related to different SnO2 hydrothermal annealing. The best performance was seen for SnO2 annealed at 150 °C, with a production of 20.4 μmol g−1 for CH4 and 16.45 μmol g−1 for CO, while for SnO2 at 200 °C the system produced more C2H4, probably due to a decrease of surface −OH groups.  相似文献   

18.
In this study, Cu and Co doped Ni/Al2O3 nanocatalyst was synthesized via impregnation and sol–gel methods. The physiochemical properties of nanocatalyst were characterized by XRD, field emission scanning electron microscopy (FESEM), particle size distribution, BET, fourier transform infrared spectroscopy (FTIR), TG–DTA and energy dispersive X-ray (EDX) analysis. The samples were employed for CO2-reforming of methane in atmospheric pressure, temperature range from 550 to 850 °C, under various mixture of CH4/CO2 and different gas hourly space velocity. XRD patterns besides indicating the decline of the peaks intensity in sol–gel method, proved the potential of this procedure in diminishing the crystal size and preventing the NiAl2O4 spinel formation. Moreover, high surface area might derive of smaller particle size and uniform morphology of sol–gel prepared ones, confirmed by FESEM and BET analysis. TG–DTG analysis as well supported the higher surface area for sol–gel made ones, represented the proper calcination temperature (approximately 600 °C). Also, presence of the active phases and elemental composition of nanocatalysts determine via EDX analysis. Promoting the basicity and the adsorption rate of CO2, is attributed to the higher amount of OH groups for sol–gel prepared samples, proved by FTIR. Ni–Co/Al2O3 due to the synergetic effect of sol–gel method and cobalt addition depicted excellent characterization such as higher surface area, smaller particle size, supplying more stable support and enhanced morphology. Therefore, this nanocatalyst represented the best products yield (H2 = 98.21 and CO = 95.64), H2/CO close to unit (0.92–1.05) and stable conversion during 1,440 min stability test. So, Ni–Co/Al2O3 among all of the prepared nanocatalysts demonstrated the best catalytic performance and presented it as a highly efficient catalyst for dry reforming of methane. Despite of the stable yield of Ni–Cu/Al2O3, it depicted the lower catalytic activity and H2/CO ratio than the unprompted nanocatalysts.  相似文献   

19.
Oxidative thermal degradation studies were performed on polytetrafluoroethylene in air and oxygen by using a stagnation burner arrangement. The autoignition behavior as a function of temperature and oxidizing medium and the nature and relative proportion of the volatiles produced prior to ignition, on ignition, and during combustion were determined. In oxygen only COF2, CO2, and CF4 were formed; in air C2F4 was observed, together with a spectrum of rearrangement derived fluorocarbons in addition to the expected oxidation products. The autoignition temperature in air was found to be considerably higher than in oxygen (575°C compared to 512°C).  相似文献   

20.
Hexakis[p-(hydroxymethyl)phenoxy]cyclotriphosphazene (HHPCP) is prepared and characterized by FTIR, 1H-NMR, and 31P-NMR spectroscopy. Then an investigation of the flame retardancy, thermal decomposition behavior of epoxy resin (EP) containing HHPCP is carried out using limiting oxygen (LOI) test, horizontal flame test, smoke density rate (SDR) test, thermogravimetric analysis (TG), and thermal gravimetric analyzer-mass spectrometry (TG-MS). The decomposition process of HHPCP is studied by TG-MS and FTIR. The result shows that the LOI value of EP increase from 20.5 to 26.5 %, when 7.5 mass% HHPCP is added into EP. The addition of 1 mass% nano-montmorillonite (nMMT) into EP–7.5 mass% HHPCP sample as synergist can increase the LOI value of EP–7.5 mass% HHPCP–1 mass% nMMT sample from 26.5 to 27.5 %. The SDR test indicates that smoke suppression of HHPCP on EP is not significant. TG analysis reflects that the EP–7.5 mass% HHPCP sample and EP–7.5 mass% HHPCP–1 mass% nMMT show higher thermal stability properties with an increasing T onset and T max comparing with neat-EP. TG-MS result indicates that the main pyrolysis product of EP is H2O, CO, CO2, C6H6, C6H5OH, HOC6H4CH3, and flammable hydrocarbon fragments CxHy. Compared with neat-EP sample, nonflammable water vapor of EP–7.5 mass% HHPCP sample increased, whereas CO2 and the flammable hydrocarbon fragments CxHy and flammable gas CO decreased. TG-MS and FTIR result suggests that HHPCP decomposed first by inter-molecular dehydration, then P–N hexatomic ring of HHPCP decomposed during 470 and 560 °C, and a little no-flame gas containing nitrogen element volatilized into the gaseous phase.  相似文献   

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