Fundamental investigation of NOx formation during oxy-fuel combustion of pulverized coal

NO_x formation was measured during combustion of pulverized coals and pulverized coal char in N₂ and CO₂ environments under isothermal and nearly constant oxygen conditions (i.e. using dilute coal loading). Three different oxygen concentrations (12% O₂, 24% O₂, and 36% O₂) and two representative US coals were investigated, at a gas temperature of 1050 °C. To investigate the importance of NO reburn reactions, experiments were also performed with an elevated concentration (550 ppm) of NO in the gases into which the coal was introduced. For low levels of background NO, the fractional fuel-nitrogen conversion to NO_x increases dramatically with increasing bath gas oxygen content, for both N₂ and CO₂ environments, though the fuel conversion is generally lower in CO₂ environments. Char N conversion is lower than volatile N conversion, especially for elevated O₂ concentrations. These results highlight the importance of the volatile flame and char combustion temperatures on NO_x formation. For the high background NO_x condition, net NO_x production is only observed in the 36% O₂ environment. Under these dilute loading conditions, NO reburn is found to be between 20% and 40%, depending on the type of coal, the use of N₂ or CO₂ diluent, the bulk O₂ concentration, and whether or not one considers reburn of volatile-NO_x. This dataset provides a unique opportunity to understand and differentiate the different sources and sinks of NO_x under oxy-fuel combustion conditions.     

Effect of gasification reactions on biomass char conversion under pulverized fuel combustion conditions

The effect of gasification reactions on biomass char conversion under pulverized fuel combustion conditions was studied by single particle experiments and modelling. Experiments of pine and beech wood char conversion were carried out in a single particle combustor under conditions of 1473-1723 K, 0.0-10.5% O₂, and 25-42% H₂O. A comprehensive progressive char conversion model, including heterogeneous reactions (char oxidation and char gasification with CO₂ and H₂O), homogeneous reactions (CO oxidation, water-gas shift reaction, and H₂ oxidation) in the particle boundary layer, particle shrinkage, and external and internal heat and mass transfer, was developed. The modelling results are in good agreement with both experimental char conversion time and particle size evolution in the presence of oxygen, while larger deviations are found for the gasification experiments. The modelling results show that the char oxidation is limited by mass transfer, while the char gasification is controlled by both mass transfer and gasification kinetics at the investigated conditions. A sensitivity analysis shows that the CO oxidation in the boundary layer and the gasification kinetics influence significantly the char conversion time, while the water-gas shift reaction and H₂ oxidation have only a small effect. Analysis of the sensitive parameters on the char conversion process under a typical pulverized biomass combustion condition (4% O₂, 13% CO₂, 13% H₂O), shows that the char gasification reactions contribute significantly to char conversion, especially for millimeter-sized biomass char particles at high temperatures.     

Nitrogen release during reaction of coal char with O2, CO2, and H2O

The chemistry of char-N release and conversion to nitrogen-containing products has been probed by studying its release and reactions with O₂, CO₂, and H₂O. The experiments were performed in a fixed bed flow reactor at pressures of up to 1.0 MPa. The results show that the major nitrogen-containing products observed depend on the reactant gas; with O₂, NO, and N₂ being the major species observed. Char-N reaction with CO₂ produces N₂ with very high selectivity over a broad range of pressures and CO₂ concentrations, and reaction with H₂O gives rise to HCN, NH₃, and N₂. Observed distributions of nitrogen-containing products are little affected by pressure when O₂ and CO₂ are the reactant gases, but increasing pressures in the reaction with H₂O results in the formation of increasing proportions of NH₃. Formation of NH₃ is also promoted by increasing concentrations of H₂O in the feed gas. The results suggest that NO and HCN are primary products when O₂ and H₂O, respectively, are used as the reactant gases, and that the other observed products arise from interactions of these primary products with the char surface.     

Insights into the interaction kinetics between propene and NOx at moderate temperatures with experimental and modeling methods

This work aims to provide insight into the interaction of propene with NO_x from both experimental and kinetic modeling perspectives. The oxidation of propene at fuel-lean (?=0.23) condition and the oxidation of propene doped with NO_x at fuel-lean (?=0.23) and fuel-rich (?=1.35) conditions have been investigated in a laminar flow reactor at atmospheric pressure in the temperature range of 725-1250 K. Synchrotron vacuum ultraviolet photoionization mass spectrometry (SVUV-PIMS) was used to achieve comprehensive, isomer-resolved identification of major products and critical nitrogenous, carbonyl and hydrocarbon intermediates. To complement the experiments, a detailed kinetic model, starting from widely used core mechanisms, was developed. Rate of production analyses and sensitivity analyses were performed to interpret the experimental observations. The results show that the promoting effects of NO_x on the oxidation reactivity of propene are initiated by the reactions of allyl radical with NO₂ at low temperature, i.e. C₃H₅A+NO₂C₃H₅O+NO. For the oxidation of the fuel-rich propene/NO_x mixture, temperature-dependent mole fraction profiles of propene, O₂ and products show several distinct regions reflecting a competition between chain propagation via C₃H₅A+NO₂C₃H₅O+NO and chain termination via C₃H₅A+NOC₃H₅NO. The formation and consumption chemistry of carbonyl and hydrocarbon intermediates in the presence of NO_x was also analyzed and discussed.     

Effect of CO2 gasification reaction on oxy-combustion of pulverized coal char

For oxy-combustion with flue gas recirculation, as is commonly employed, it is recognized that elevated CO₂ levels affect radiant transport, the heat capacity of the gas, and other gas transport properties. A topic of widespread speculation has concerned the effect of the CO₂ gasification reaction with coal char on the char burning rate. To give clarity to the likely impact of this reaction on the oxy-fuel combustion of pulverized coal char, the Surface Kinetics in Porous Particles (SKIPPY) code was employed for a range of potential CO₂ reaction rates for a high-volatile bituminous coal char particle (130 μm diameter) reacting in several O₂ concentration environments. The effects of boundary layer chemistry are also examined in this analysis. Under oxygen-enriched conditions, boundary layer reactions (converting CO to CO₂, with concomitant heat release) are shown to increase the char particle temperature and burning rate, while decreasing the O₂ concentration at the particle surface. The CO₂ gasification reaction acts to reduce the char particle temperature (because of the reaction endothermicity) and thereby reduces the rate of char oxidation. Interestingly, the presence of the CO₂ gasification reaction increases the char conversion rate for combustion at low O₂ concentrations, but decreases char conversion for combustion at high O₂ concentrations. These calculations give new insight into the complexity of the effects from the CO₂ gasification reaction and should help improve the understanding of experimentally measured oxy-fuel char combustion and burnout trends in the literature.     

Simultaneous catalytic ozonation of NO and dichloromethane on Mn/H-ZSM-5 catalysts: Interaction effect and mechanism

Catalytic ozonation is a promising method for simultaneous removal of NO_x and Cl-VOCs, but needs to clarify their interaction mechanism and the influence of catalyst acidity. In this paper, the simultaneous catalytic ozonation of NO and dichloromethane (DCM) on Mn/H-ZSM-5 molecular sieve catalysts were investigated experimentally. Results show that the overall acidity, acid sites type and intensity have a significant impact on the degradation efficiency, the conversion path of Cl element, and the interaction of NO/DCM adsorption-degradation. Nevertheless, regardless of catalysts, NO could be preferentially oxidized by ozone to generate NO₂ in co-ozonation process, which inhibited and even shielded DCM ozonation at O₃/DCM ratio <1.7. In addition, the highly active oxidizing species such as NO₃/N₂O₅, produced by the deep ozonation of NO₂, exhibited a synergistic effect on the conversion of DCM and intermediates, which in turn weakened NO₂ deep oxidation. Specifically, NO addition caused a general decrease in the HCl selectivity, and a slight increase in the CHCl₃ selectivity of all samples, while the Cl₂ selectivity was determined by the overall catalyst acidity. The samples with higher overall acidity exhibited lower activity for DCM degradation. In particular, for samples with the weak overall acidity but strong acid sites, the sum selectivity of HCl, Cl₂, and CHCl₃ was significantly improved under the interplay effect of NO, indicating that strong acidic sites were beneficial to the complete degradation of DCM. In-situ DRIFTS revealed that aldehydes and carboxylates were the key intermediates of DCM ozonation. In the co-ozonation, NO and its oxidation products (such as nitrates) could promote the formation and conversion of these intermediates, and further converted into CO and CO₂ by the active oxidant from ozone. Finally, the interference of H₂O and SO₂ on the NO/DCM co-ozonation were revealed.     

The kinetics of methane ignition in fuel-rich HCCI engines: DME replacement by ozone

Fuel-rich combustion of methane in a homogeneous-charge compression-ignition (HCCI) engine can be used as a polygeneration process producing work, heat, and useful chemicals like syngas. Due to the inertness of methane, additives such as dimethyl ether (DME) are needed to achieve ignition at moderate inlet temperatures and to control combustion phasing. Because significant concentrations of DME are then needed, a considerable part of the fuel energy comes from DME. An alternative ignition promotor known from fuel-lean HCCI is ozone (O₃). Here, a combined experimental and modelling study on the ignition of fuel-rich partial oxidation of methane/air mixtures at Φ = 1.9 with ozone and DME as additives in an HCCI engine is conducted. Experimental results show that ozone is a suitable additive for fuel-rich HCCI, with only 75 ppm ozone reducing the fuel-fraction of DME needed from 11.0% to 5.3%. Since ozone does not survive until the end of the compression stroke, the reaction paths are analyzed in a single-zone model. The simulation shows that different ignition precursors or buffer molecules are formed, depending on the additives. If only DME is added, hydrogen peroxide (H₂O₂) and formaldehyde (CH₂O) are the most important intermediates, leading to OH formation and ignition around top dead center (TDC). With ozone addition, methyl hydroperoxide (CH₃OOH) becomes very important earlier in the compression stroke under these fuel-rich conditions. It is then later converted to CH₂O and H₂O₂. Thus, ozone is a very effective additive not only for fuel-lean, but also for fuel-rich combustion. However, the mechanism differs between both regimes. Because less of the expensive additives are needed, ozone could help improving the economics of a polygeneration process with fuel-rich operated HCCI engines.     

Conversion of nitrogen oxides in N2:O2:CO2 and N2:O2:CO2:NO2 mixtures subjected to a dc corona discharge

This paper concerns the influence of a direct current (dc) corona discharge on production and reduction of NO, NO₂ and N₂O in N₂:O₂:CO₂ and N₂:O₂:CO₂:NO₂ mixtures. The corona discharge was generated in a needle-to-plate reactor. The positively polarized electrode consisted of 7 needles. The grounded electrode was a stainless steel plate. The gas flow rate through the reactor was varied from 28 to 110 cm³/s. The time-averaged discharge current ranged from 0 to 6 mA. It was found that in the N₂:O₂:CO₂ mixture the corona discharge produced NO, NO₂ and N₂O. In the N₂:O₂:CO₂:NO₂ mixture the reduction of NO₂ was between 6–56%, depending on the concentration of O₂, gas flow rate and corona discharge current. The NO₂ reduction was accompanied by production of NO and N₂O. The results show that efficient reduction of nitrogen oxides by a corona discharge cannot be expected in the mixtures containing N₂ and O₂ if reducing additives are not employed.     

Visible chemiluminescence of ammonia premixed flames and its application for flame diagnostics

We report a spatially resolved spectroscopic study of the visible chemiluminescence emission from different premixed ammonia-air-oxygen flames stabilized on a laminar flat flame burner, with equivalence ratio ranging from 0.7 to 1.35 and an O₂/N₂ ratio of 0.4. In the reaction zone of the observed flames, the visible emission was recognized to be the chemiluminescence of excited NH₂* radicals, while in the post-flame zone, two types of chemiluminescence were observed: NO₂* chemiluminescence dominated in the fuel-lean flames and NH₂* chemiluminescence dominated in the fuel-rich flames. The high-resolution spectra of the NO₂* and NH₂* chemiluminescence in the visible region (400-700 nm) were recorded. The intensity of both spectra increased gradually with wavelength. However, the NO₂*-chemiluminescence spectrum appeared to be continuous and unstructured, while the NH₂*-chemiluminescence spectrum consisted of groups of distinct emission lines. Based on the spectral feature, the ratios of the integrated chemiluminescence intensities over the 598-603 nm wavelength range to the intensities over the 586-592 nm range and 447-453 nm range were used to sense equivalence ratio. In addition, slightly different colors of the fuel-lean and fuel-rich flames were observed, due to the fact that NO₂* chemiluminescence had a relatively stronger signal in the blue region than NH₂* chemiluminescence. The difference was used to infer flame equivalence ratio using the flame images recorded by a RGB digital camera, where the ratio of the signal from the red channel to the signal from the blue channel was calculated.     

The effect of potassium bromide and sodium carbonate on coal char combustion reactivity

The addition of halogens, particularly iodine, to the gas during coal char oxidation has been used in previous studies to quench gas-phase chemistry, thereby allowing one to separate the effects of homogeneous and heterogeneous reactions. Halogen addition suppresses the gas-phase radicals to near-equilibrium levels. A similar effect can be expected from other compounds with high efficiency as fire suppressants, such as alkali metals. The effectiveness of the use of additives in distinguishing homogeneous and heterogeneous reactions during char oxidation relies on the assumption that radicals are suppressed while heterogeneous reactions occurring on the char surface are not affected. The present work tests this assumption for potassium bromide (KBr) and sodium carbonate (Na₂CO₃) reacting with a pulverized eastern bituminous coal char during oxidation. An increase in CO and a slight reduction in particle temperature were observed with the addition of KBr, consistent with known effects of halogens on gas-phase chemistry. An increase in particle size was also observed with the KBr addition. This observation and the results of model calculations suggest that there is significant incorporation of liquid KBr on the char surface under the conditions examined. With Na₂CO₃ addition, the particle temperature did not change, the particle size showed a slight decrease, and CO production increased. Although the mechanisms for Na interaction with radicals at combustion conditions are not well established, char oxidation modeling suggests that a decrease in OH concentration in the particle boundary layer is the cause for the observed increase in CO production. It is concluded that Na₂CO₃ has clear advantages over KBr for inhibiting gas-phase chemistry without affecting char oxidation for the conditions investigated here.     

Attrition of lignite char under fluidized bed gasification conditions: The effect of carbon conversion

The effect of carbon conversion on the attrition of lignite char particles during fluidized bed gasification by CO₂ was studied in a lab-scale apparatus. The influence of bed temperature and inlet CO₂ concentration on carbon conversion and, consequently, on attrition was studied. The mechanical resistance of the char particles was also characterized at different stages of char conversion by specific attrition experiments. A predictive kinetic model for CO₂ gasification of the lignite char was developed from the experimental results, that was able to correctly predict the evolution of carbon conversion versus time. On this basis a semi-empirical model was developed in order to simulate the evolution of carbon elutriation rate with carbon conversion degree, i.e. the gasification-assisted attrition enhancement effect.     

Effect of high CO2 concentration on char formation through mineral reaction during biomass pyrolysis

O₂/CO₂ combustion has attracted considerable attention as a promising technology for CO₂ capture. Using biomass for fuel is considered carbon neutral, and O₂/CO₂ biomass combustion can mitigate the deleterious environmental effect of greenhouse. In this study, the effect of CO₂, the main component gas in O₂/CO₂ combustion, on the pyrolysis characteristics of biomass is investigated. Cellulose, lignin, and metal-depleted lignin pyrolysis experiments were performed using a thermobalance. Information on the surface chemistry of the chars was obtained by Fourier transform infrared (FTIR) spectroscopy to investigate changes in the surface chemistry during pyrolysis under different surrounding gasses. When the temperature increased to 1073 K at heating rate of 1 K s^?1, the char yield of lignin in the presence of CO₂ increased by about 10% compared with that under Ar. However, for cellulose and metal-depleted lignin, no significant difference appeared between pyrolysis under CO₂ and that under Ar. FT-IR showed that a strong peak corresponding to carbonate ions appeared in the char derived from lignin under CO₂. Therefore, salts such as Na₂CO₃ or K₂CO₃ formed during the lignin pyrolysis under CO₂. At around 1650–1770 cm^?1, a significant difference appeared in the FTIR spectra of chars formed under CO₂ and those formed under Ar. C=O groups not associated with an aromatic ring were found only in chars formed under CO₂. It was suggested that these salts affected the char formation reaction, in that the char formed during lignin pyrolysis under CO₂ had unique chemical bands that did not appear in the lignin-derived char prepared under Ar.     

Effect of steam on the single particle ignition of solid fuels in a drop tube furnace under air and simulated oxy-fuel conditions

This article investigates the effect of steam on the ignition of single particles of solid fuels in a drop tube furnace under air and simulated oxy-fuel conditions. Three solid fuels, all in the size range 125–150 µm, were used in this study; specifically, a low rank sub-bituminous Colombian coal, a low-rank/high-ash sub-bituminous Brazilian coal and a charcoal residue from black acacia. For each solid fuel, particles were burned at a constant drop tube furnace wall temperature of 1475?K, in six different mixtures of O₂/N₂/CO₂/H₂O, which allowed simulating dry and wet conventional and oxy-fuel combustion conditions. A high-speed camera was used to record the ignition process and the collected images were treated to characterize the ignition mode (either gas-phase or surface mode) and to calculate the ignition delay times. The Colombian coal particles ignite predominately in the gas-phase for all test conditions, but under simulated oxy-fuel conditions there is a decrease in the occurrence of this ignition mode; the charcoal particles experience surface ignition regardless of the test condition; and the Brazilian coal particles ignite predominately in the gas-phase when combustion occurs in mixtures of O₂/N₂/H₂O, but under simulated oxy-fuel conditions the ignition occurs predominantly on the surface. The ignition delay times for particles that ignited in the gas-phase are smaller than those that ignited on the surface, and generally the simulated oxy-fuel conditions retard the onset of both gas-phase and surface ignition. The addition of steam decreases the gas-phase and surface ignition delay times of the particles of both coals under simulated oxy-fuel conditions, but has a small impact on the gas-phase ignition delay times when the combustion occurs in mixtures of O₂/N₂/H₂O. The steam gasification reaction is likely to be responsible for the steam effect on the ignition delay times through the production of highly flammable species that promote the onset of ignition.     

Selectively strong molecular adsorption on boron nitride monolayer induced by transition metal substrate

We studied adsorption of several molecules (CO, CO₂, H₂O, N₂O, NO, NO₂, and O₂) on hexagonal boron nitride (h-BN) monolayers supported on transition metal (TM) surfaces, using density functional calculations. We observed that all the molecules bind very weakly on the pristine h-BN, with binding energies in the range of 0.02–0.03 eV. Interestingly, however, when h-BN is supported on the TM surface, NO₂ and O₂ become strongly chemisorbed on h-BN, with binding energies of >1 eV, whereas other molecules still physisorbed, with binding energies of ～0.1 eV at most. The electron transfer from TM to p_z states of h-BN played a substantial role in such strong bindings of NO₂ and O₂ on h-BN, as these molecules possess unpaired electrons that can interact with p_z states of h-BN. Such selective molecular binding on h-BN/TM originates from the peculiar distribution of the spin-polarized highest occupied and lowest unoccupied molecular orbitals of NO₂ and O₂. Strong molecular adsorption and high selectivity would make the h-BN/TM system possible for a variety of applications such as catalysts and gas sensors.     

An intrinsic kinetics model to predict complex ash effects (ash film,dilution, and vaporization) on pulverized coal char burnout in air (O2/N2) and oxy-fuel (O2/CO2) atmospheres

During coal combustion, char chemical reaction is the slowest step, particularly in the last burnout stage, where the char consists of small amounts of carbon in a predominant ash framework. Existing kinetics models tend to deviate from experimental measurements of late char burnout due to the incomplete treatment of ash effects. Ash can improve pore evolution through vaporization, hinder oxygen transport by forming an ash film, and reduce active carbon sites and available surface per unit volume by penetrating into the char matrix. In this work, a sophisticated kinetics model, focusing on these three ash evolution mechanisms (ash vaporization, ash film, and ash dilution) during pulverized coal (PC) char combustion, is developed by integrating them into a thorough mechanistic picture. Further, a detailed comparison of the three distinct ash effects on PC char conversion during air (O₂/N₂) and oxy-fuel (O₂/CO₂) combustion is performed. For the modeled coal, the mass of ash vaporization is approximate 3 orders less than the mass of ash remaining, which participates in ash dilution and ash film formation, both in O₂/N₂ and O₂/CO₂ atmospheres. The influence of these phenomena on burnout time follows the order: ash dilution > ash film > ash vaporization. The influence of ash vaporization on burnout time is minor, but through interactions with the ash dilution and ash film forming processes it can have an impact at high extents of burnout, particularly in O₂/CO₂ atmospheres. In O₂/N₂ atmospheres the residual ash predominately exists as an ash film, whereas it mainly exists as diluted ash in the char matrix in O₂/CO₂ atmospheres. The residual ash particle is encased by a thick film when the ash film forming fraction is high (low ash dilution fraction). These results provide in-depth insights into the conversion of PC char and further utilization of the residual ash.     

The influence of NH3 on NO2 conversion in a dc corona discharge in N2:O2:CO2:NO2:NH3 mixture

The aim of this paper is to investigate the influence of NH₃ additive (540–1470 ppm) on the conversion of NO₂ and the creation of NO and N₂O in a mixture of N₂:O₂:CO₂: NO₂:NH₃ subjected to the so-called direct current (dc) corona discharge. The dc corona discharge was generated in a needle-to-plate reactor. Seven positively polarized needles were used as one electrode and a stainless steel plate as the other. The time-averaged discharge current was varied from 0 to 7 mA. It was found that the dc corona discharge decomposed NO₂ and produced NO and N₂O. The reduction of NO₂ was higher without NH₃ additive if the residence time of the operating gas was relatively short. However, in a longer corona discharge processing the NH₃ additive may be useful for reduction of NO₂.Supports from the Research and Development Commitee (KBN) under Programme KBN 0889/P4/93/04 and the Polish Academy of Sciences within IMP 3.1 project are gratefully acknowledged.     

Laminar flame speed and autoignition characteristics of surrogate jet fuel blended with hydrogen

Hydrogen combustion has emerged as one promising option toward the achievement of carbon-neutral in aviation. In this study, the effects of hydrogen addition on laminar flame speeds, autoignition, and the coupling of autoignition and flame propagation for surrogate jet fuel n-dodecane are numerically investigated at representative engine conditions to elucidate the potential challenges for flame stabilization and the autoignition risks in combustor design. Results show that the normalized flame speed increases almost linearly with hydrogen addition for fuel-lean conditions, while for fuel-rich conditions it increases nonlinearly and can be up to 20. This poses great challenges for avoiding flameholding and flashback, particularly for fuel-rich mixtures. Results further show that flame speed enhancement due to the increased flame temperature can be neglected under fuel-lean conditions, but not for fuel-rich mixtures. For the dependence of ignition delay time on temperature, there exists a unique intersection between pure n-dodecane/air and H₂/air mixtures. Near the intersection temperature, there exists subtle kinetic coupling of the two fuels, leading to different H₂ roles, e.g., accelerator or inhibitor, for the autoignition process of n-dodecane/H₂/air mixtures. With this intersection temperature, the diagram for autoignition risks is constructed, which demonstrates that H₂ acts as an inhibitor under subsonic cruise conditions while either an inhibitor or an accelerator under supersonic cruise conditions depending on the combustor inlet temperature and the amount of hydrogen addition. With the potential coupling of autoignition and flame propagation, the 1-D autoignition-assisted flame calculations show that hydrogen addition can alleviate or even eliminate the two-stage ignition characteristics for pure n-dodecane/air flames. For n-dodecane blended with hydrogen, the autoignition-assisted flame propagation speed, as well as the global transition from flame propagation to autoignition, can still be described by an analytic scaling parameterized by the ignition Damkӧhler number.     

Coadsorption of NO and other small gases (H2 and CO) on polycrystalline rhodium surface

The coadsorption of NO and other small gases (H₂ and CO) on a polycrystalline Rh filament has been studied by thermal desorption mass spectroscopy, using ¹⁵NO. The sample was exposed to a mixture of nitric oxide and other gases with various concentrations of ¹⁵NO at room temperature. It is indicated that NO, CO and H₂ coadsorbs on the rhodium surface, and NO desorbs as N₂ and O₂. NO is adsorbed mainly in the dissociation at lower coverage and molecular adsorption becomes dominant at higher coverage. But the amount of desorbed O₂ was very small. The chemisorption of CO is affected by the chemisorbed NO. Thermal desorption of hydrogen is detected when the value of P_15NO/P_CO is very small. The hydrogen adsorbed on the rhodium surface is replaced by NO with a longer exposure time.     

Soot low-temperature combustion on Cu–Zr/ZSM-5 catalysts in O2/He and NO/O2/He atmospheres

Zirconium doped Cu/ZSM-5 catalysts were prepared and characterized in this investigation. Catalytic activity during soot combustion was determined in both O₂/He and NO/O₂/He atmospheres by temperature-programmed oxidation. The use of zirconium reduces the temperature of maximum soot oxidation rate by 229 °C in O₂/He atmosphere and 270 °C in NO/O₂/He atmosphere. The promoting effect of zirconium is discussed in terms of surface dispersion, enrichment of active components, and creation of oxygen vacancies where molecular oxygen or NO_x is adsorbed forming basic surface oxygen species active for soot oxidation. The NO₂ formed at the copper–zirconium interface sites leads to the ignition temperature being significantly decreased to 93 °C, which is inside the exhaust temperature range of diesel engines. To understand the combustion reaction kinetics, the activation energy and reaction order of soot combustion were evaluated. According to the Redhead method, the activation energy for non-catalyzed reaction is 164 kJ/mol under the O₂/He atmosphere. For the Cu/ZSM-5 and Cu–Zr/ZSM-5, the activation energies under the O₂/He atmosphere (134–151 kJ/mol) are slightly higher than those under the NO/O₂/He atmosphere (128–135 kJ/mol). The Freeman–Carroll method is suitable to describe the soot combustion in the NO/O₂/He atmosphere, with the activation energies for the catalysts in the range of 97–112 kJ/mol and the average value of reaction order equal to 1.36.     

煤气化中NO_x及其前驱物释放规律研究

采用U型管反应系统,研究了氧浓度、气流速率和气化温度对神木煤气化过程中NO_x及其前驱物的释放规律.研究发现:气化时生成的HCN和NH_3总量比热解时大幅下降,表明O_2的引入抑制了H自由基的可获得性.随着氧浓度的增加,NO的收率先减后增,而NO_2收率几乎没有变化.氧浓度较低时,生成的高浓度CO阻止了挥发分氮向NO的转化.气流速率对含氮气相产物释放影响各不相同.低温气化产物以NO_2和HCN为主,NO_2主要来自进样期挥发分的缓慢氧化,而高温气化产物中的NH_3的生成主要来源于焦炭氮.