甲烷/空气射流燃烧中氮氧化物生成模型的研究

With the development of reaction kinetics and transfer science, the modeling of NOx formation plays more and more important roles in the protection of environment and the design of combustion reactors; in this case,turbulence-chemistry model and NOx formation model are the two most important aspects. For thermal NOx mechanism, this article studied the CH4/air system and applied a set of latest NO formation rate constants published at the Leed University which replaced the original model code in FLUENT to increase its precision on prediction of NO concentration. The realizable k-ε model, Reynold Stress model and standard k-ε model were also investigated to predict the turbulent combustion reaction, which indicated that the simulation results of velocities, temperatures and concentrations of combustion productions by the standard k-ε model were in good accordance with the experimental data. With the application of the simulation results to the experimental data to fit some important kinetic parameters in the equation of O atom model and revision of the equation later, this article obtained a new NO formation rate model. It has been proved that the prediction of the developed model coincides well with the measurements.     

不可压缩湍流反应流动的直接模拟和RANS-SOM燃烧模型的检验

The second-order moment combustion model, proposed by the authors is validated using the direct numerical simulation （DNS） of incompressible turbulent reacting channel flows. The instantaneous DNS results show the near-wall strip structures of concentration and temperature fluctuations. The DNS statistical results give the budget of the terms in the correlation equations, showing that the production and dissipation terms are most important. The DNS statistical data are used to validate the closure model in RANS second-order moment （SOM） combustion model. It is found that the simulated diffusion and production terms are in agreement with the DNS data in most flow regions, except in the near-wall region, where the near-wall modification should be made, and the closure model for the dissipation term needs further improvement. The algebraic second-order moment （ASOM） combustion model is well validated by DNS.     

非理想多组分混合物中质量传递过程基于Maxwell-Stefan扩散理论的建模及数值分析(英文)

The Intalox metal tower packing was used to simulate an industrial relevant extractive distillation column for purifying azeotropic multicomponent mixture.In order to explain the inconsistencies in the modeling of transfer process in nonideal multicomponent distillation column,a method was developed with equilibrium stage models(EQ)and non-equilibrium model(NEQ)incorporated with Maxwell-Stefan diffusion equations in the framework of AspenONE  simulator.Dortmund Modified UNIFAC(UNIFAC-DMD)thermodynamic model was employed to estimate activity coefficients.In addition,to understand the reason for the diffusion against driving force and the different results by EQ and NEQ models,explicit investigations were made on diffusion coefficients, component Murphree efficiency and mass transfer coefficients.The results provide valuable information for basic design and applications associated with extractive distillation.     

燃料稀释对传统型和高预热空气稀释型燃烧炉性能的影响的数值研究

This numerical study investigates the effects of using a diluted fuel (50% natural gas and 50% N2) in an industrial furnace under several cases of conventional combustion (air with 21% O2 at 300 and 1273 K) and the highly preheated and diluted air (1273 K with 10% O2 and 90% N2) combustion (HPDAC) conditions using an in-house computer program. It was found that by applying a combined diluted fuel and oxidant instead of their uncombined and/or undiluted states, the best condition is obtained for the estab-lishment of HPDAC’s main unique features. These features are low mean and maximum gas temperature and high radiation/total heat transfer to gas and tubes; as well as more uniformity of theirs distributions which results in decrease in NOx pollutant formation and increase in furnace efficiency or energy saving. Moreover, a variety of chemical flame shape, the process fluid and tubes walls tem-peratures profiles, the required regenerator efficiency and finally the concentration and velocity patterns have been also qualita-tively/quantitatively studied.     

太阳能空气加热器管道中填充三角形小翅片扰流器的湍流传热的实验研究简

The paper presents an experimental study on the heat transfer and flow friction characteristics in a solar air heater channel fitted with delta-winglet type vortex generators （DWs）. The experiments are conducted by varying the airflow rate for Reynolds number in the range of 5000 to 24000 in the test section with a uniform heat-flux applied on the upper channel wall. Firstly, the DW pairs are mounted only at the entrance of the lower wall of the test channel （called DW-E） to create multiple vortex flows at the entry. The effect of two transverse pitches （Re= Pt/H= 1 and 2） at three attack angles （a= 30°, 45° and 60°） of the DW-E with its relative height, b/H= 0.5 （half height of channel） is examined. Secondly, the 30° DWs with three different relative heights （blH = 0.3, 0.4 and 0.5） are placed on the upper wall only （absorber plate, called DW-A） of the test channel. The experimental result reveals that in the first case, the 60° DW-E at Rp = 1 provides the highest heat transfer and friction factor while the 30° DW-E at Rp = 1 performs overall better than the others. In the second case, the 30° DW-A at b/H= 0.5 yields the highest heat transfer and friction factor but the best thermal performance is found at b/H = 0.4.     

丙烷脱氢Cr_2O_3/Al_2O_3催化剂烧焦再生过程的模型化与模拟(英文)

A heterogeneous model is developed for the regeneration of the Cr2O3/Al2O3 catalyst for the propane dehydrogenation process by considering the internal mass transfer and external mass/heat transfer during the coke combustion. Simulation shows that under practical operating conditions, multi-steady states exist for the catalyst pellets and the catalyst temperature is sensitive to gas temperature. However, at increased mass flow rate or lowered oxygen concentration, multi-steady states will not appear. Under the strong influences of film diffusion, the coke in the packed bed reactor will first be exhausted at the inlet, while if the film diffusion resistance is decreased, the position of first coke exhaustion moves toward the outlet of the reactor.     

催化燃烧法去除含氪气体中甲烷的实验研究

为制备满足放射性测量需求的Kr气体源,需对含Kr气体中的高浓度CH4进行初步分离,本文开展了催化燃烧法分离CH4和Kr的实验研究.研究结果表明,CH4的催化燃烧转化率随CH4浓度和催化温度的升高而增加,H2对CH4催化燃烧的抑制作用随着H2浓度的升高而变大,CO对CH4催化燃烧的抑制作用随着CO浓度的升高而变小,模拟气...     

CO2-乙醇体系中界面对流的混合格子Boltzmann方法三维模拟及实验验证（英文）

By using a hybrid lattice-Boltzmann–finite-difference method (hybrid LBM–FDM method), three-dimensional simulations of solutal interfacial convection were conducted for the process of CO2 absorption into ethanol. A self-renewal interface model is adopted as an interfacial perturbation model. The simulation results revealed some three-dimensional features of the induced interfacial convection, such as the development of diverging cellular flow and Rayleigh plume-like convection in liquid phase. The concentration distribution of the simulation result is validated and found to be in wel agreement with the Schlieren visualization results qualitatively. Addi-tionally, the mass transfer enhancements by interfacial convection were investigated via both simulation and experiment for the absorption process, and the mass transfer is shown to be enhanced by the interfacial convec-tion by about two-fold comparing with that by diffusion.     

分子筛对CH_4/空气混合气的变压吸附分离研究

为提高煤层气变压吸附浓缩效果,以一种商品分子筛为对象,研究了该分子筛在小型四塔变压吸附装置上的CH4/空气混合气浓缩分离效果,分析了吸附时间、吸附压力以及原料气浓度对混合气浓缩效果的影响。结果表明,吸附时间过长或吸附压力过高,均不利于获得较好的产品气浓度及回收率。吸附时间180 s,吸附压力300 k Pa时,试验商品分子筛对CH4/N2的浓缩分离效果最佳。其中,10%浓度原料气提浓至30.56%,提高约20%,产品气中CH4回收率达到94.45%,对原料气的处理量达到67.77 m3/(t·h);35%浓度原料气提浓至76.33%,提高约40%,产品气中CH4回收率达到69.68%,对原料气的处理量达到68.99 m3/(t·h);65%原料气提浓至89.18%,提高约25%,产品气中CH4回收率达到87.22%,对原料气的处理量达到83.36 m3/(t·h)。     

面向氢气/甲烷分离分子筛膜微结构调控的研究进展

氢能具有燃烧值高、零碳排放等优势,发展氢能技术是实现“碳达峰、碳中和”战略的重要举措。当前,基于天然气和石油路线的制氢均存在将氢气从甲烷等烃分子中分离的过程。氢气/甲烷分离主要有变压吸附法、深冷精馏法以及膜分离法。分子筛膜具有精准分子筛分、高分离性能和稳定性好等优势,是低能耗分离氢气/甲烷最具发展潜力的膜材料。面向氢气/甲烷分离的应用需求,阐述了沸石分子筛膜和MOFs分子筛膜微结构调控策略、氢气/甲烷分离性能和构效关系的研究现状,分析了分子筛膜材料在氢气/甲烷分离领域的机遇和挑战。绘制了可与2008年聚合物膜Robeson上限图相比的分子筛膜性能数据图,并预测了分子筛膜在制氢分离领域经济可行的分离性能目标区域。     

Study on NO_x Formation in CH_4/Air Jet Combustion

1 INTRODUCTION The nitrogen oxides formed in combustion sys- tems is a significant source of environmental pollution. Nitrogen oxides consist of nitric oxide (NO), nitrogen dioxide (NO2), and nitrous oxide (N2O). NO and NO2 are collectively referred to NOx[1]. In laminar flames, and at the molecular level within turbulent flames, the formation of NOx can be attributed to three distinct chemical kinetic processes. The NOx formed by these three processes is described as thermal NOx, …     

Catalytic combustion of CH4 and CO on La1−xMxMnO3 perovskites

The activities of perovskites depend on compositions and preparation methods. Various perovskites, La_1−xM_xMnO₃ (M=Ag, Sr, Ce, La), have been prepared by two different methods (co-precipitation and spray decomposition). The new preparation method, spray decomposition, produced perovskites of a high surface area of over 10 m²/g. The catalytic activities for CH₄ and CO oxidation have been studied on a series of catalysts, La_1−xM_xMnO₃. The perovskite-type oxide, La_0.7Ag_0.3MnO₃, shows the highest catalytic activity: the complete conversion of CO and CH₄ at 370 and 825 K, respectively.     

Combustion of CH4 over a PdO/ZrO2 catalyst: an example of kinetic study under severe conditions

A kinetic study on CH₄ combustion over a very active PdO/ZrO₂ catalyst with high Pd loading (10% w/w of Pd) is presented as an example of a demanding problem which requires both the development of appropriate experimental tools and a theoretical insight on surface chemistry.

The use of an annular catalytic reactor as a tool to collect kinetic data under unusually severe conditions (high temperature and CH₄ concentration) is described in comparison with the use of a conventional packed bed reactor. In particular, problems related to the biasing effects of mass, heat and momentum transfer are addressed.

Kinetic data addressing the effects of CH₄, O₂, H₂O and CO₂ concentration in a temperature range from 400 to 550 °C are analysed by means of a purely empirical power law model and of a formal kinetic model based on literature indication assuming methane dissociative adsorption as the rate controlling step.     

Catalytic reduction of NOx with H2/CO/CH4 over PdMOR catalysts

Conversion of NO_x with reducing agents H₂, CO and CH₄, with and without O₂, H₂O, and CO₂ were studied with catalysts based on MOR zeolite loaded with palladium and cerium. The catalysts reached high NO_x to N₂ conversion with H₂ and CO (>90% conversion and N₂ selectivity) range under lean conditions. The formation of N₂O is absent in the presence of both H₂ and CO together with oxygen in the feed, which will be the case in lean engine exhaust. PdMOR shows synergic co-operation between H₂ and CO at 450–500 K. The positive effect of cerium is significant in the case of H₂ and CH₄ reducing agent but is less obvious with H₂/CO mixture and under lean conditions. Cerium lowers the reducibility of Pd species in the zeolite micropores. The catalysts showed excellent stability at temperatures up to 673 K in a feed with 2500 ppm CH₄, 500 ppm NO, 5% O₂, 10% H₂O (0–1% H₂), N₂ balance but deactivation is noticed at higher temperatures. Combining results of the present study with those of previous studies it shows that the PdMOR-based catalysts are good catalysts for NO_x reduction with H₂, CO, hydrocarbons, alcohols and aldehydes under lean conditions at temperatures up to 673 K.     

NO reduction by CH4 in the presence of O2 over La2O3 supported on Al2O3

Dispersing La₂O₃ on δ- or γ-Al₂O₃ significantly enhances the rate of NO reduction by CH₄ in 1% O₂, compared to unsupported La₂O₃. Typically, no bend-over in activity occurs between 500° and 700°C, and the rate at 700°C is 60% higher than that with a Co/ZSM-5 catalyst. The final activity was dependent upon the La₂O₃ precursor used, the pretreatment, and the La₂O₃ loading. The most active family of catalysts consisted of La₂O₃ on γ-Al₂O₃ prepared with lanthanum acetate and calcined at 750°C for 10 h. A maximum in rate (mol/s/g) and specific activity (mol/s/m²) occurred between the addition of one and two theoretical monolayers of La₂O₃ on the γ-Al₂O₃ surface. The best catalyst, 40% La₂O₃/γ-Al₂O₃, had a turnover frequency at 700°C of 0.05 s⁻¹, based on NO chemisorption at 25°C, which was 15 times higher than that for Co/ZSM-5. These La₂O₃/Al₂O₃ catalysts exhibited stable activity under high conversion conditions as well as high CH₄ selectivity (CH₄ + NO vs. CH₄ + O₂). The addition of Sr to a 20% La₂O₃/γ-Al₂O₃ sample increased activity, and a maximum rate enhancement of 45% was obtained at a SrO loading of 5%. In contrast, addition of SO⁼₄ to the latter Sr-promoted La₂O₃/Al₂O₃ catalyst decreased activity although sulfate increased the activity of Sr-promoted La₂O₃. Dispersing La₂O₃ on SiO₂ produced catalysts with extremely low specific activities, and rates were even lower than with pure La₂O₃. This is presumably due to water sensitivity and silicate formation. The La₂O₃/Al₂O₃ catalysts are anticipated to show sufficient hydrothermal stability to allow their use in certain high-temperature applications.     

Kinetic measurements of CH4 combustion over a 10% PdO/ZrO2 catalyst using an annular flow microreactor

A kinetic study on CH₄ combustion over a PdO/ZrO₂ (10%, w/w) catalyst has been performed in a temperature range between 400 and 550 °C by means of an annular catalytic microreactor.

The role of mass transfer phenomena including diffusion in the catalyst pore, gas–solid diffusion and axial diffusion in the gas phase, has been preliminary addressed by means of mathematical modeling. Simulation results have pointed out the key role of internal diffusion showing that thicknesses of the active catalyst layer as thin as 10–15 μm are required to minimize the impact of mass transfer limitations. The thermal behavior of the reactor has been also addressed by means of catalytic combustion tests with CH₄ and CO–H₂ mixtures as fuels. The results have demonstrated the possibility to obtain nearly isothermal temperature profiles under severe conditions (up to 3% of CH₄) thanks to effective dissipation of reaction heat by radiation from the catalyst outer skin.

Finally the effect of reactants (CH₄ and O₂) and products (H₂O and CO₂) on CH₄ combustion rate has been addressed. The results have shown that both H₂O and CO₂ markedly inhibit the reaction up to 550 °C. The data have been fitted by the following simple power law expression r=k_rP_CH4P_H2O^−0.32P_CO2^−0.25 with an apparent activation energy of 108 kJ/mol.

Evidences have been found and discussed indicating a key role of the support on the extent of such inhibition effects.     

Effect of alternate CH4-reducing/lean combustion treatments on the reactivity of fresh and S-poisoned Pd/CeO2/Al2O3 catalysts

This work investigates the effect of treatments under different CH₄-containing atmospheres on the reactivity of fresh and S-poisoned 2% w/w Pd/Al₂O₃/CeO₂ catalysts for methane combustion.

Over the fresh catalyst the decomposition/reformation processes of PdO occurring during cycles of CH₄-reducing/lean combustion pulses allowed the complete recovery of activity losses possibly associated with H₂O poisoning which were observed during prolonged exposure under lean combustion conditions. The presence of CeO₂ markedly enhances both the activity losses under lean combustion conditions and the rate of PdO reoxidation/reactivation upon Pd redox cycle.

Under lean combustion conditions, regeneration of catalyst deactivated by exposure to SO₂-containing atmosphere required very high temperatures (above 750 °C) in order to decompose stable sulphate species adsorbed on the support. Treatments consisting of alternate CH₄-reducing/lean combustion pulses allowed a complete recovery of activity at much lower temperatures (550–600 °C) due to the reduction of sulphates by CH₄ activated on the surface of Pd metal. A protecting role of CeO₂ on Pd poisoning due either to exposure to SO₂-containing atmosphere or to spill-back of support sulphates species was also evidenced.     

低浓度甲烷流向变换催化燃烧反应研究

将制备的整体式催化剂应用于小型流向变换催化燃烧反应系统上,在甲烷初始浓度为0.2%,气量为30 L·min-1,换向半周期为10 min的工况条件下考察了不同预热温度对甲烷催化燃烧活性的影响以及反应系统床层轴向温度分布情况。结果表明,随着预热温度升高,甲烷催化燃烧活性呈现升高的趋势,同时,在催化剂中添加助剂元素Pt可以提高催化剂催化活性;催化剂的预热温度对反应器床层温度分布影响较大,特别是反应系统的催化段。     

NO removal by CH4 on Co-NaX-CO and Ag-NaX catalysts in a dual-bed system

NO removal using CH₄ as a reductant in a dual-bed system has been investigated with Co-NaX and Ag-NaX catalysts, which were prepared by Co²⁺-, Ag⁺-ion exchange into zeolite NaX, respectively, and activation for 5 h at 500 °C. The experimental result has been compared with that of a Co-NaX-CO catalyst, additionally pre-treated under CO flow for the Co-NaX catalyst. The cobalt crystal structure of a Co-NaX-CO catalyst is Co₃O₄, which promotes NO oxidation to NO₂ by excess O₂ at a low temperature (523 K). The mechanical mixture of Co-NaX-CO and Ag-NaX catalysts shows a synergy effect on NO reduction to N₂ by CH₄ in the presence of excess O₂ and H₂O, but the NO reduction decreases quickly as time passes. However, the NO reduction to N₂ in a deNO bed at 523 K and a deNO₂ bed at 423 K, which are relatively lower than the reaction temperatures for common SCR systems, still remained at 67% even in a H₂O 10% gas mixture after 160 min.