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1.
E Hampartsoumian  B.M Gibbs 《Fuel》2003,82(4):373-384
The advanced reburning process for NOx emission control was studied in a down-fired 20 kW combustor by evaluating the performance of 15 pulverised coals as reburning fuels. The proximate volatile matter contents of the coals selected ranged from around 4 to 40 wt% (as received) with elemental nitrogen contents from around 0.6 to 2.0 wt%. The effects of reburn fuel fraction, reburning zone residence time, ammonia agent injection delay time (relative to the reburn fuel and burnout air injection points) and the nitrogen stoichiometric ratio are reported in detail and the optimum configurations for advanced reburning, established as a function of operating condition and coal type. The experimental results show that advanced reburning can reduce NOx emissions up to 85%. The maximum benefits of advanced reburning over conventional reburning were observed at the lower reburn fuel fractions (around 10%). The results demonstrate that under advanced reburning conditions equivalent or higher levels of NOx reduction can be achieved while operating the reburn zone closer to stoichiometric conditions compared with conventional reburning operating at high reburn fuel fractions (20-25%). Thus the practical problems associated with fuel-rich staged operation can be reduced. The effect of coal properties on the advanced reburning performance was also investigated. As with conventional reburning, the fuel nitrogen content of the coal used was found to have little influence on the NOx reduction efficiency except at the highest reburn fuel fractions. There was, however, a strong correlation between the effectiveness of advanced reburning and the volatile content of the reburning fuels, which not only depended on the reburn fuel fraction, but also the mode (rich or lean) of advanced reburning operation. These parameters are mapped out experimentally to enable the best operating mode to be selected for advanced reburning as a function of the reburning fuel fraction and volatile content.  相似文献   

2.
Selective catalytic reduction of NO by hydrogen was studied over Cr modified Pt/ZSM-35 catalysts. The preparation process greatly influenced catalytic activity and sample prepared by co-impregnation method exhibits the best activity. In situ DRIFT studies revealed that on Pt–Cr/ZSM-35, (1) new Pt-NOδ+ and NO species adsorbed on Pt were detected upon NO + O2 adsorption; (2) much more ammonia species were formed under reaction condition. Cr addition not only enhanced the adsorption of NOx but also promoted the formation of surface NH4+ species, which should be the origin of promotional effect of Cr on Pt/ZSM-35 for H2-SCR reaction.  相似文献   

3.
B.R. Stanmore  J.-F. Brilhac 《Fuel》2008,87(2):131-146
The reactions reviewed here concern those between elemental carbon and NO2, N2O and NO, sometimes in the presence of oxygen. The section on NO includes only updates to recent reviews. Soots, activated carbons and carbon blacks are more reactive than graphite. The magnitudes of the reaction rates are found to be: NO2 > N2O ≈ NO ≈ O2. The presence of a soluble organic fraction (SOF) in soot is found to influence some reactions, and all three reactions suffer from inhibition by surface products. The mechanisms proposed for the surface adsorbates are summarised. All authors found that two types of active site were present; one forming weak bonds (physisorption), and the other undergoing chemisorption to form groupings such as -C-ONO, -C-ONO2 or -C-NO2. The latter decompose to give oxides of carbon, and are sometimes called redox reactions. The adsorbates appear to be the same for all NOx species. Some elemental nitrogen adsorption takes place, and can involve incorporation into the C skeleton. The attack of NO on carbon proceeds via NO2, so that catalysts that facilitate this oxidation are effective. Gaseous SO2 and H2O assist in the process by forming acids which are good oxidants. The change in activation energy with temperature found experimentally for NO and N2O may be due to the form of nitrogen on the edge carbon atoms.  相似文献   

4.
Selective synthesis of gasoline-range hydrocarbons (C5-C12) was investigated in a fixed-bed micro reactor using two series of CO2-containing syngas with various mole CO2/(CO + CO2) and H2/(CO + CO2) ratios, where Fischer-Tropsch synthesis(FTS) and in situ hydrocracking/hydroisomerization were performed over bifunctional Co/SiO2/HZSM-5 catalyst. CO2 was converted at 0.15-0.55 of CO2/(CO + CO2) ratio under H2-rich condition (H2/(CO + CO2) = 2.0), highest conversion of 20.3% at 0.42. Further increasing CO2 content decreased CO2 conversion and quite amount of CO2 acted as diluting component. For the syngas with low H2 content or H2/(CO + CO2) ratio(< 1.85, H2/CO = 2.0), the competitive adsorption of CO, H2 and CO2 resulted in low CO, CO2 and total carbon conversion, which was 57.9%, 12.7% and 31.4% respectively at 0.74 of H2/(CO + CO2) ratio(H2/CO/CO2/N2 = 40.8/20.4/34.8/4). FTS results indicated that high H2 content and proper H2/(CO + CO2) ratio were favorable for the conversion of CO2-containing syngas. More than 45% selectivity to gasoline-range hydrocarbons including isoparaffins was obtained under the two series of syngas. It was also tested that the catalytic activity of Co/SiO2/HZSM-5 kept stable under CO2-containing syngas(< 7.5%). And the quick catalytic deactivation under high CO2 containing syngas(H2/CO/CO2/N2 = 45.3/23.2/27.1/3.06) was due to carbon deposition and pore blockage by heavy hydrocarbon, tested by thermal gravimetry, N2 physisorption and scanning electron microscopy(SEM).  相似文献   

5.
An experimental parametric study on the NO reduction efficiency by reburning under oxy-fuel conditions has been performed through the gas-phase interactions between different gas mixtures and NO in a CO2 atmosphere, under flow reactor conditions in the 800-1800 K temperature range. The study provides a wide amount of experimental data on reburning under oxy-fuel conditions to be further used in modeling studies. A higher NO reduction is attained in a N2 atmosphere compared to CO2 under fuel-rich and stoichiometric conditions, although the efficiency is similar in both atmospheres under fuel-lean conditions. The formation of HCN in a fuel-rich environment is higher in N2 than in CO2 but comparable for other stoichiometries. The influence of the main parameters of the process under oxy-fuel conditions has been found to present similar trends to those observed in literature for reburning in air. A significant NO reduction can be obtained at moderately high temperatures, fuel-rich conditions, high values of the reburn fuel/NO ratio, sufficiently high residence times and low water vapor contents. C2H6 has been detected to act as a better reburn fuel as CH4, whereas CO itself is unable to reduce NO.  相似文献   

6.
Philippe Dagaut  Franck Lecomte 《Fuel》2003,82(9):1033-1040
The reduction of nitric oxide (NO) by a mixture of methane, ethylene and acetylene with and without addition of SO2 has been studied in a fused silica jet-stirred reactor operating at 1 atm in simulated conditions of the reburning zone. The temperatures were ranging from 800 to 1400 K. In these experiments, the initial mole fractions of NO and SO2 were 0 or 1000 ppm, that of methane, ethylene and acetylene were, respectively, 2400, 1200 and 600 ppm. The equivalence ratio has been varied from 0.5 to 2.5. It was demonstrated that the reduction of NO varies as the temperature and that for a given temperature, a maximum NO reduction occurs slightly above stoichiometric conditions. The addition of SO2 inhibited the process of reduction of NO under the present conditions. The present results generally follow those obtained in previous studies involving simple hydrocarbons or natural gas as reburn fuel. A detailed chemical kinetic modeling of the present experiments was performed using an updated and improved kinetic scheme (1006 reversible reactions and 145 species). An overall reasonable agreement between the present data and the modeling was obtained. Also, the proposed kinetic mechanism can be successfully used to model the reduction of NO by ethane, ethylene, a natural gas blend (methane-ethane 10:1). The kinetic modeling indicates that the reduction of NO proceeds via the following sequence of reactions: HCCO+NO=HCNO+CO; HCCO+NO=HCN+CO2; HCN+O=NCO+H; HCN+O=NH+CO; HCN+H=CN+H2; HCNO+H=HCN+OH; CN+O2=NCO+O; NCO+H=NH+CO; NCO+NO=N2O+CO; NCO+NO=CO2+N2; NH+NO=N2O+H; NH+NO=N2+OH. The inhibition of this process by SO2 is explained by the sequence of reactions H+SO2+M=HOSO+M and HOSO+H=SO2+H2 that acts as a termination process: H+H+M=H2+M.  相似文献   

7.
This study reports on the synthesis of ternary semiconductor (BixSb1−x)2Te3 thin films on Au(1 1 1) using a practical electrochemical method, based on the simultaneous underpotential deposition (UPD) of Bi, Sb and Te from the same solution containing Bi3+, SbO+, and HTeO2+ at a constant potential. The thin films are characterized by X-ray diffraction (XRD), atomic force microscopy (AFM), energy dispersive spectroscopy (EDS) and reflection absorption-FTIR (RA-FTIR) to determine structural, morphological, compositional and optic properties. The ternary thin films of (BixSb1−x)2Te3 with various compositions (0.0 ≤ x ≤ 1.0) are highly crystalline and have a kinetically preferred orientation at (0 1 5) for hexagonal crystal structure. AFM images show uniform morphology with hexagonal-shaped crystals deposited over the entire gold substrate. The structure and composition analyses reveal that the thin films are pure phase with corresponding atomic ratios. The optical studies show that the band gap of (BixSb1−x)2Te3 thin films could be tuned from 0.17 eV to 0.29 eV as a function of composition.  相似文献   

8.
The performance of proton exchange membrane fuel cells (PEMFC) fed with CO-contaminated hydrogen was investigated for anodes with PtWOx/C and phosphotungstic acid (PTA) impregnated Pt/C electrocatalysts. A quite high performance was achieved for the PEMFC fed with H2 + 100 ppm CO with anodes containing 0.4 mg PtWOx cm−2 and also for those with 0.4 mg Pt cm−2 impregnated with ca. 1 mg PTA cm−2. A decay of the single cell performance with time is observed, and this was attributed to an increase of the membrane resistance due to the polymer degradation promoted by the crossover of the tungsten species throughout the membrane.  相似文献   

9.
C.M. NamB.M. Gibbs 《Fuel》2002,81(10):1359-1367
Diesel DeNOx experiments have been conducted using the selective noncatalytic ‘thermal DeNOx’ process in a diesel fuelled combustion-driven flow reactor which simulated a single cylinder (966 cm3) and head equipped with a water-cooling jacket and an exhaust pipe. NH3 was directly injected into the cylinder to reduce NOx emissions. A wide range of air/fuel ratios (A/F=20-40) was selected for NOx reduction where an initial NOx of 530 ppm was usually maintained with a molar ratio (β=NH3/NOx) of 1.5.The results indicate that a 34% NOx reduction can be achieved from the cylinder injection in the temperature range, 1100-1350 K. Most of the NOx reduction occurs within the cylinder and head section (residence time<40 ms), since temperatures in the exhaust are too low for additional NOx reduction. Under large gas quenching rates, increasing β values (e.g. 4.0) substantially increase the NOx reduction up to 60%, which is comparable with those achieved under isothermal conditions. Experimental findings are analysed by chemical kinetics using the Miller and Bowman mechanism including both N/H/O species and CO/hydrocarbon reactions to account for CO/UHC oxidation effects, based on practical nonisothermal conditions. Comparisons of the kinetic calculations with the experimental data are given as regards temperature characteristics, residence time and molar ratio. In addition, the effects of CO/UHC and branching ratio (α=k1/(k1+k2)) for the reaction NH2+NO=products are discussed in terms of NO reduction features, together with practical implications.  相似文献   

10.
Existing energy generation technologies emit CO2 gas and are posing a serious problem of global warming and climate change. The thermodynamic feasibility of a new process scheme combining chemical looping combustion (CLC) and combined reforming (CR) of propane (LPG) is studied in this paper. The study of CLC of propane with CaSO4 as oxygen carrier shows thermodynamic feasibility in temperature range (400-782.95 °C) at 1 bar pressure. The CO2 generated in the CLC can be used for combined reforming of propane in an autothermal way within the temperature range (400-1000 °C) at 1 bar pressure to generate syngas of ratio 3.0 (above 600 °C) which is extremely desirable for petrochemical manufacture. The process scheme generates (a) huge thermal energy in CLC that can be used for various processes, (b) pure N2 and syngas rich streams can be used for petrochemical manufacture and (c) takes care of the expensive CO2 separation from flue gas stream and CO2 sequestration. The thermoneutral temperature (TNP) of 702.12 °C yielding maximum syngas of 5.98 mol per mole propane fed, of syngas ratio 1.73 with negligible methane and carbon formation was identified as the best condition for the CR reactor operation. The process can be used for different fuels and oxygen carriers.  相似文献   

11.
CuO-CoO-Cr2O3 mixed with MFI Zeolite (Si/Al = 35) prepared by co-precipitation was used for synthesis gas conversion to long chain hydrocarbon fuel. CuO-CoO-Cr2O3 catalyst was prepared by co-precipitation method using citric acid as complexant with physicochemical characterization by BET, TPR, TGA, XRD, H2-chemisorptions, SEM and TEM techniques. The conversion experiments were carried out in a fixed bed reactor, with different temperatures (225-325 °C), gas hourly space velocity (457 to 850 h−1) and pressure (28-38 atm). The key products of the reaction were analyzed by gas chromatography mass spectroscopy (GC-MS). Significantly high yields of liquid aromatic hydrocarbon products were obtained over this catalyst. Higher temperature and pressure favored the CO conversion and formation of these liquid (C5-C15) hydrocarbons. Higher selectivity of C5 + hydrocarbons observed at lower H2/CO ratio and GHSV of the feed gas. On the other hand high yields of methane resulted, with a decrease in C5+ to C11+ fractions at lower GHSV. Addition of MFI Zeolite (Si/Al = 35) to catalyst CuO-CoO-Cr2O3 resulted a high conversion of CO-hydrogenation, which may be due to its large surface area and small particle size creating more active sites. The homogeneity of various components was also helpful to enhance the synergistic effect of Co promoters.  相似文献   

12.
Several compositions of NdYb1−xGdxZr2O7 (0 ≤ x ≤ 1.0) ceramics were prepared by pressureless-sintering method at 1973 K for 10 h in air. The relative density, microstructure and electrical conductivity of NdYb1−xGdxZr2O7 ceramics were analyzed by the Archimedes method, X-ray diffraction, scanning electron microscopy and impedance plots measurements. NdYb1−xGdxZr2O7 (0 ≤ x ≤ 0.3) ceramics have a single phase of defect fluorite-type structure, and NdYb1−xGdxZr2O7 (0.7 ≤ x ≤ 1.0) ceramics exhibit a single phase of pyrochlore-type structure; however, the NdYb0.5Gd0.5Zr2O7 composition shows mixed phases of both defect fluorite-type and pyrochlore-type structures. The measured values of the grain conductivity obey the Arrhenius relation. The grain conductivity of each composition in NdYb1−xGdxZr2O7 ceramics gradually increases with increasing temperature from 673 to 1173 K. NdYb1−xGdxZr2O7 ceramics are oxide-ion conductor in the oxygen partial pressure range of 1.0 × 10−4 to 1.0 atm at all test temperature levels. The highest grain conductivity value obtained in this work is 1.79 × 10−2 S cm−1 at 1173 K for NdYb0.3Gd0.7Zr2O7 composition.  相似文献   

13.
This paper presents the second part of work on the effect of hydrogen partial pressure on the hydrogenation of a terpene in a CO2-expanded liquid. The effect of hydrogen partial pressure on the hydrogenation of β-myrcene possessing three CC bonds catalysed by alumina-supported ruthenium and rhodium was studied. Experiments were performed at various hydrogen pressures in the range from 2.0 up to 4.5 MPa at a fixed total pressure of 12.5 MPa. In all the conditions the reaction proceeded in two phases (liquid + gas), that is, the total pressure was below the critical pressure of the CO2 + β-myrcene + H2 system. The liquid phase volume is expanded in relation to the initial volume of β-myrcene in a fashion that is strongly dependent on the hydrogen and carbon dioxide pressures. An increase of H2 pressure concomitantly diminishes carbon dioxide pressure, which leads to the enhancement of the liquid phase in hydrogen and a terpene. It does not direct to straightforward higher reaction rate, but surprisingly the effect of higher concentrations either hydrogen or β-myrcene is opposite. It is attributed to the fact that the hydrogenation of β-myrcene rate-controlling factor turns out to be the hydrogen to β-myrcene ratio which decreases as the hydrogen pressure increases. These unexpected appealing results present that lower pressures of hydrogen guide to higher hydrogen/β-myrcene ratios in the liquid phase, but on the other hand they also amplify the initial reaction rate constant. The obtained results are opposite to the results achieved for effect of hydrogen pressure on the Pd-catalysed hydrogenation of limonene consisting of two CC double bonds.  相似文献   

14.
A double-layer composite electrode based on Ba0.5Sr0.5Co0.8Fe0.2O3−δ + Sm0.2Ce0.8O1.9 (BSCF + SDC) and BSCF + SDC + Ag was investigated to be a promising cathode and also anode for the electrochemical oxygen generator based on samaria doped ceria electrolyte. The Ag particles in the second layer were not only the current collector but also the improver for the oxygen adsorption at the electrode. a.c. impedance results indicated that the electrode polarization resistance, as low as 0.0058 Ω cm2 was reached at 800 °C under air. In oxygen generator cell performance test, the electrode resistance dropped to half of the value at zero current density under an applied current density of 2.34 A cm−2 at 700 °C, and on the same conditions the oxygen generator cell was continual working for more than 900 min with a Faradic efficiency of ∼100%.  相似文献   

15.
C. Casaca 《Fuel》2011,90(3):1090-1100
This article presents a detailed experimental characterization of the reburning process in a large-scale laboratory furnace. Natural gas, pine sawdust and pulverized coal were used as reburn fuels. Initially, the study involved the collection of in-flame combustion data, without reburning, in order to define appropriate locations for the injection of the reburn fuels. Next, flue-gas data were obtained for a wide range of experimental conditions using the three reburn fuels and, subsequently, detailed measurements of local mean O2, CO, CO2, HC and NOx concentrations, and gas temperatures have been obtained in the reburn zone for three representative furnace operating conditions, one for each reburn fuel studied. The flue-gas data revealed that the sawdust reburning leads to NOx reductions comparable or even higher than those attained with natural gas reburning, while coal reburning yields much lower NOx reductions. The detailed data obtained in the reburn zone indicates that the reburning process remains active throughout all the reburn zone in the cases of natural gas and sawdust reburning, while in the case of coal reburning its relatively low volatile matter content is insufficient to establish an effective reburn zone. In the cases of the sawdust and coal reburning the burnout levels remain approximately constant, regardless of the NOx emissions reduction, with the sawdust reburning leading to higher particle burnout performance than the coal reburning.  相似文献   

16.
The solubility of CO2 in water and aqueous solutions of NaCl, KCl, CaCl2, NaCl + KCl (weight ratio = 1:1), NaCl + CaCl2 (weight ratio = 1:1), KCl + CaCl2 (weight ratio = 1:1), and NaCl + KCl + CaCl2 (weight ratio = 1:1:1) was determined at 35.0, 45.0 and 55.0 °C up to 16 MPa, and the concentration of the salt was up to 14.3 wt%. It was demonstrated that solubility increased with increase in pressure, and decreased with increasing temperature. Addition of a salt or salt mixture resulted in reduction in the solubility due to the salting-out effect. At the same salt concentration (wt%), the salting-out effect of KCl was considerably smaller than those of NaCl and CaCl2. The salting-out effect of a salt mixture is between those of its components.  相似文献   

17.
Fuel Cell performance was measured at 792-1095 K for Ni-GDC (Gd-doped ceria) anode-supported GDC film (60 μm thickness) with a (La0.8Sr0.2)(Co0.8Fe0.2)O3 cathode using H2 fuel containing 3 vol% H2O. A maximum power density, 436 mW/cm2, was obtained at 1095 K. The electrical conductivity of GDC electrolyte in N2 atmosphere of 10−15-100 Pa oxygen partial pressures (Po2) at 773-1073 K was independent of Po2, which indicated the diffusion of oxide ions. The conductivity of GDC in H2O/H2 atmosphere increased because of the further formation of electrons due to the dissociation of hydrogen in GDC (H2 → 2H+ + 2e). The hole conductivity was observed at 873 K in Po2 = 100-104 Pa. The key factors in increasing power density are the increase of open circuit voltage and the suppression of H2 fuel dissolution in GDC electrolyte. These are controlled by the cathode material and Gd-dopant composition.  相似文献   

18.
Transparent lutetium oxide (Lu2O3) body was prepared by spark plasma sintering using a two-step pressure profile combined with a low heating rate. The effects of pre-load pressures from 10 to 100 MPa and heating rates from 0.03 to 1.67 K s−1 on the microstructures and optical properties were investigated. With increasing pre-load pressures from 10 to 100 MPa, the grains became smaller with a narrower distribution, whereas the transmittance showed maxima at 30 MPa. The average grain size slightly increased from 0.67 to 0.86 μm as the heating rate increased from 0.03 to 1.67 K s−1, while the transmittance decreased. Transmittances of 60% at 550 nm and 79% at 2000 nm were obtained under a pre-load pressure of 30 MPa at a heating rate of 0.17 K s−1.  相似文献   

19.
The supercritical removal of ethanol from alcoholic beverages (brandy, wine, and cider) was studied using the GC-EoS model to represent the phase equilibria behavior of the CO2 + beverage mixture. Each alcoholic drink was represented as the ethanol + water mixture with the corresponding ethanol concentration (35 wt% for brandy, 9-12 wt% for different wines and 6 wt% for cider). The thermodynamic modeling was based on an accurate representation of the CO2 + ethanol and CO2 + water binary mixtures, and the CO2 + ethanol + water ternary mixture.The GC-EoS model was employed to simulate the countercurrent supercritical CO2 dealcoholization of the referred beverages; the results obtained compared good with experimental data from the literature. Thus, the model was used to estimate process conditions to achieve an ethanol content reduction from ca. 10 wt% to values lower than 1 wt%. The model results were tested by carrying out several extraction assays using wine, in a 3 m height packed column at 308 K, pressures in the range of 9-18 MPa and solvent to wine ratio between 9 and 30 kg/kg.  相似文献   

20.
A. Abad  T. Mattisson  A. Lyngfelt  M. Rydén 《Fuel》2006,85(9):1174-1185
Chemical-looping combustion (CLC) is a method for the combustion of fuel gas with inherent separation of carbon dioxide. This technique involves the use of two interconnected reactors. A solid oxygen carrier reacts with the oxygen in air in the air reactor and is then transferred to the fuel reactor, where the fuel gas is oxidized to carbon dioxide and water by the oxygen carrier. Fuel gas and air are never mixed and pure CO2 can easily be obtained from the flue gas exit. The oxygen carrier is recycled between both reactors in a regenerative process. This paper presents the results from a continuously operating laboratory CLC unit, consisting of two interconnected fluidized beds. The feasibility of the use of a manganese-based oxygen carrier supported on magnesium stabilized zirconia was tested in this work. Natural gas or syngas was used as fuel in the fuel reactor. Fuel flow and air flow was varied, the thermal power was between 100 and 300 W, and the air ratio was between 1.1 and 5.0. Tests were performed at four temperatures: 1073, 1123, 1173 and 1223 K. The prototype was successfully operated at all conditions with no signs of agglomeration or deactivation of the oxygen carrier. The same particles were used during 70 h of combustion and the mass loss was 0.038% per hour, although the main quantity was lost in the first hour of operation. In the combustion tests with natural gas, methane was detected in the exit flue gases, while CO and H2 were maintained at low concentrations. Higher temperature or lower fuel flows increases the combustion efficiency, which ranged from 0.88 to 0.99. On the other hand, the combustion of syngas was complete for all experimental conditions, with no CO or H2 present in the gas from the fuel reactor.  相似文献   

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