水蒸气对oxy-coal燃烧中NO生成的影响

为了研究H₂O对燃料N向NO转化各个阶段的影响,采用可沿程取样的沉降炉反应器,研究了一种烟煤在1273 K温度下,O₂/N₂、O₂/CO₂以及O₂/CO₂/H₂O气氛下燃烧的燃尽与NO生成的情况.并通过在停留时间为0.2、0.3、0.5、1.1 s与O₂浓度为5%、21%及30%情况下的实验来研究H₂O对NO生成的影响.实验结果表明,相对于O₂/CO₂气氛,H₂O的添加抑制了NO的生成,且该影响主要集中在燃烧初期挥发分N的氧化过程.随着O₂浓度的增加,H₂O添加对oxy-coal燃烧方式下NO生成影响加大.     

不同烟气组分对粉状活性焦吸附汞的影响机理

在模拟燃煤热烟气为热源和介质条件下，以准东褐煤为原料，通过一维沉降炉进行炭化活化（一步法）制备粉状活性焦，考察了活性焦对Hg⁰的吸附能力，探索了SO₂、H₂O、O₂、CO₂、H₂O+O₂、SO₂+O₂及H₂O+SO₂+O₂气氛对活性焦吸附Hg⁰的影响机理。结果表明：一步法获得的活性焦对Hg⁰具有较高的吸附性能。N₂气氛作对比，H₂O、H₂O+O₂、CO₂和SO₂气氛下抑制活性焦对Hg⁰的吸附；O₂、SO₂+O₂和H₂O+SO₂+O₂促进活性焦对Hg⁰的吸附。通过Hg 4f的XPS分析证明了不同气氛组成对活性焦吸附Hg⁰的抑制和促进机理。H₂O覆盖在活性焦活性位上和堵塞孔隙而抑制活性焦对Hg⁰的吸附；SO₂与Hg⁰在活性焦上发生竞争吸附而抑制对Hg⁰的吸附；CO₂ 吸附在活性焦微孔上而抑制对Hg⁰的吸附；O₂气氛下主要形成了HgO, SO₂+O₂气氛下Hg⁰被氧化成HgSO₃，进一步氧化成HgSO₄； H₂O+SO₂+O₂气氛下，Hg⁰被氧化成HgO和HgSO₄。     

燃煤锅炉烟气中SO3生成的化学动力学模型和实验研究

燃煤锅炉烟气中SO₃能对锅炉设备、大气环境造成包括低温腐蚀、粘污和蓝烟等一系列的危害。因而,对烟气中SO₃主要影响因素及其影响规律的研究对于预测和控制烟气中SO₃浓度以满足不断增长的节能减排标准有重要意义。基于文献中的C/H/O/N/S化学动力学模型的优化、整合建立了化学动力学模型,对烟气中SO₃主要影响因素及其影响规律进行计算研究。还基于自主设计搭建了全混流反应器测量装置,对上述计算工况中的SO₃浓度进行测量。研究发现,烟气中SO₃浓度主要受SO₂、O₂和H₂O的浓度,以及温度和反应停留时间等影响。SO₃浓度受烟气中CO、NO的影响也较为显著,但是受CO₂的影响不大。另外,随着反应停留时间的增加,烟气中SO₃浓度先后经历了3个不同阶段：急剧增加,增长趋势逐渐减缓和逐渐减少。     

添加剂CH3COONH4对介质阻挡-电晕放电耦合法脱除NO、SO2的影响

采用自行研究设计的介质阻挡-电晕放电等离子体反应装置在模拟烟气中进行NO、SO₂的脱除研究。考察了O₂、CO₂、水蒸气等气体组分对脱除NO、SO₂的影响,并进一步探讨了添加剂CH₃COONH₄对脱除NO、SO₂的影响及作用机理。实验结果表明：O₂、CO₂和水蒸气浓度的增加对NO脱除有抑制作用,而引入CH₃COONH₄后,这些抑制作用会被减弱,使NO的脱除率得到大幅度提升,但这些抑制作用不会完全消除。在引入CH₃COONH₄后,气体组分和输入电流的变化对脱除SO₂的影响不明显,SO₂脱除率可达到94%左右。在N₂/O₂/CO₂/H₂O/NO/SO₂体系中加入0.27%的CH₃COONH₄后,NO初始浓度不变的条件下,SO₂含量较少时,对NO的脱除影响不明显,随着SO₂浓度的增加,NO的脱除率不断下降,增加CH₃COONH₄的添加量可消除SO₂的影响;另一方面,在SO₂初始浓度恒定的条件下,随着NO含量的增加,SO₂的脱除率保持在94%左右。在N₂/O₂/CO₂/H₂O/NO/SO₂体系中加入0.51%的CH₃COONH₄后,输入电流2.5A时,NO的脱除率达到72%。     

UV/H2O2氧化联合Ca(OH)2吸收同时脱硫脱硝

在小型紫外光-鼓泡床反应器中,对UV/H₂O₂氧化联合Ca(OH)₂吸收同时脱除燃煤烟气中NO与SO₂的主要影响因素[H₂O₂浓度、紫外光辐射强度、Ca(OH)₂浓度、NO浓度、溶液温度、烟气流量以及SO₂浓度]进行了考察。采用烟气分析仪和离子色谱仪分别对尾气中的NO₂和液相阴离子作了检测分析。结果显示:在本文所有实验条件下,SO₂均能实现完全脱除。随着H₂O₂浓度、紫外光辐射强度和Ca(OH)₂浓度的增加,NO的脱除效率均呈现先大幅度增加后轻微变化的趋势。NO脱除效率随烟气流量和NO浓度的增加均有大幅度下降。随着溶液温度和SO₂浓度的增加,NO脱除效率仅有微小的下降。离子色谱分析表明,反应产物主要是SO₄^2-和NO₃^-,同时有少量的NO₂^-产生。尾气中未能检测到有害气体NO₂。     

乙醇胺对介质阻挡耦合电晕放电同时脱除NO、SO2的影响

采用自行设计的介质阻挡耦合电晕放电等离子体反应装置进行了模拟烟气同时脱硫脱硝的研究，分别考察乙醇胺（HOCH₂CH₂NH₂，MEA）在不同模拟烟气体系中对NO、SO₂脱除的影响，深入探讨了MEA在放电过程中与NO的作用机理。结果表明：在N₂/O₂/SO₂/NO体系中，0.56% MEA的加入可以显著消除O₂对NO脱除的抑制作用；在N₂/CO₂/SO₂/NO体系中，MEA会吸收进入体系中的部分CO₂，以减弱CO₂对NO脱除的抑制；在N₂/O₂/CO₂/H₂O/NO/SO₂体系中，0.56% MEA的加入既可以有效减弱H₂O的影响，也可以使NO的脱除率达到71.28%，继续将MEA的体积分数增大至1.20%时，可将该体系下NO脱除率提高到81.25%；同时，MEA可以在短时间内高效吸收体系内的SO₂，且几乎不受其他气体成分的影响，SO₂脱除率保持在95%左右。     

一种典型钒钛系SCR催化剂SO3生成特性研究

选择性催化还原（SCR）技术由于脱硝效率高、选择性好而被广泛应用于烟气氮氧化物排放控制;然而,目前广泛采用的钒钛系SCR脱硝催化剂会使烟气中SO₂氧化成SO₃,烟气中过高的SO₃对电厂安全运行会造成严重影响,也会对环境造成污染。以典型V₂O₅-WO₃/TiO₂催化剂为研究对象,系统研究了SCR脱硝过程中烟气流量、温度、O₂浓度、SO₂浓度等对催化剂表面SO₃生成特性的影响,并进一步对SO₃生成的反应动力学特性进行了分析。研究表明：催化剂表面SO₃生成反应中SO₂的反应级数为0.59,当O₂浓度大于3%时,O₂的反应级数为0,该反应的表观活化能为70.39 kJ/mol;实验条件下,烟气中SO₂浓度增加会使SO₃生成的反应速率提高;O₂浓度对催化剂表面SO₃生成影响并不显著;烟气温度对催化剂表面SO₃生成具有显著影响,高温会促进SO₃的生成。     

烟气组分对汞吸附影响的程序升温脱附

目前燃煤烟气活性炭脱汞技术已经很成熟,但机理方面的相关研究甚少或不全面,为了探讨汞与活性炭在燃煤烟气中的反应路径,本文在固定床上对商业活性炭（FAC）和1% NH₄Br改性活性炭（NBAC）进行了汞吸附实验,分别考察了O₂、SO₂、CO₂、NO及其混合烟气组分对吸附剂汞吸附的影响,然后利用程序升温脱附（temperature programmed desorption,TPD）技术分析了烟气组分对汞吸附的影响机理。固定床测试结果表明溴化铵改性可显著增加活性炭汞吸附性能,O₂、CO₂及NO可促进NBAC对汞的吸附,其中NO最好,而SO₂抑制NBAC对汞的吸附。TPD结果表明,溴素改性促进NBAC表面负载的溴与Hg⁰结合生成HgBr₂,O₂存在促进了Hg⁰的氧化生成HgO,NO存在显著增加了Hg₂（NO₃）₂的生成。SO₂与Hg⁰对活性炭表面的官能团存在竞争吸附的关系,生成C-S,与Hg⁰反应生成HgS。CO₂对NBAC吸附Hg⁰的反应机理影响不大。     

O2浓度对污泥燃烧还原性气体产生及还原NO的双重影响

在模拟水泥预分解炉装置上研究污泥燃烧过程中还原性气体的产生及其对NO的还原，并系统研究了O₂浓度（体积分数为0～5%）对还原性气体产生及NO还原的双重影响。TG-FTIR特征分析表明，污泥燃烧产生的还原性气体主要为HCN、NH₃、CO和CH₄。进一步实验研究发现O₂浓度对HCN和NH₃的产生有明显影响，HCN和NH₃在O₂体积分数为3%时产生速率最大。同时，O₂浓度对污泥燃烧还原NO有较大影响。在污泥燃烧温度为900℃，烟气中CO₂体积分数为25%、NO浓度为600mg/m³、SO₂浓度为200mg/m³、O₂体积分数为3%时，NO还原率可达到最大（55.8%）。通过还原性物质（NH₃、CO、CH₄和污泥焦）对NO的还原实验研究进一步发现，NH₃和CO是污泥燃烧过程中NO还原的关键物质，且NH₃对NO的还原随着O₂浓度的增加而增加，而CO对NO的还原受O₂浓度的限制。综合分析表明，O₂浓度对污泥燃烧NO还原的影响主要是由NH₃的产生速率差异、NH₃和CO对NO的还原起主导作用且受O₂浓度影响较大等多种因素综合导致。采用污泥作为还原剂进行NO还原是一种高效的方法，在水泥生产中可通过控制O₂浓度获得较高的NO还原率。     

SNCR脱硝特性的模拟及优化

对某台使用尿素为还原剂的100 t·h^-1循环流化床锅炉的SNCR性能进行了CFD数值模拟,分析了温度、氨氮摩尔比等影响因素对SNCR脱硝效率、氨泄漏以及N₂O浓度的影响规律。结果表明,SNCR最佳温度窗口的范围为850~1050℃,且随着氨氮比的增大,温度窗口范围变宽;随着温度的升高,氨逃逸量明显下降,当温度超过940℃后,氨逃逸量基本可以忽略不计,而N₂O的生成量则呈现出先增大后减少的趋势。随着氨氮摩尔比的增加,脱硝效率逐渐增大,980℃左右达到峰值;氨泄漏随氨氮摩尔比的增加而增大;N₂O浓度与脱硝效率呈正比关系,最大生成量约为30 μl·L^-1。     

SIMULTANEOUS REACTIONS OF CO, NO, O2 AND NH3 ON Pt/γA12O3 CATALYST IN A TUBULAR REACTOR

A reliable method to continuously monitor NH₃ in a gas stream containing CO—NO—O₂ and H₂O has been developed. The method is based on a quantitative oxidation of NH₃ to NO on a Pt catalyst. The extent of this reaction is affected by temperature, excess oxygen present, and space-velocity. There is a significant effect of inlet O₂ concentration on extent of various reactions in the CO—NO—O₂—H₂O system on a Pt/γAl₂O₃ catalyst. At fixed space-velocity and catalyst temperature, and for fixed reactor inlet concentrations of CO and NO. there is negligible CO—NO reaction either in the absence of oxygen or in the presence of excess oxygen. However, short of the stoichiometric amount of O₂ required for CO oxidation, there is appreciable CO—NO (and possibly also CO—NO—H₂O) reaction whose extent increases with increasing oxygen concentration. This increase is especially dramatic in a narrow window of O₂: concentrations near the stoichiometric point. Interestingly enough, near the stoichiometric point, self-sustained isothermal oscillations in the outlet CO and NO concentrations are also observed (Subramaniam and Varma. submitted for publication)     

喷射鼓泡塔海水脱硫特性

为探究以海水作为脱硫剂在喷射鼓泡塔上的脱硫特性,通过改变废气流量、海水温度、浸液深度、SO₂进口浓度和O₂浓度等操作参数,在自主设计和搭建的喷射鼓泡塔实验平台上进行了船舶模拟废气的脱硫实验。实验结果表明:在喷射鼓泡塔上,海水对SO₂的吸收容量为3.682 mmol·L^-1,约是去离子水的3.92倍;脱硫效率随废气流量、海水温度和SO₂进口浓度的升高而降低,随浸液深度和O₂浓度的升高而升高,与脱硫时间呈线性下降关系。液相总传质系数随废气流量和海水温度的增加而增加,其中废气流量的影响幅度较小,仅为3.16%。增加O₂浓度可显著提高海水对SO₂的吸收容量,O₂浓度从0%增至12%时,海水的吸收容量从3.682 mmol·L^-1增至7.463 mmol·L^-1。     

Combined effect of H2O and SO2 on V2O5/AC catalysts for NO reduction with ammonia at lower temperatures

Combined effect of H₂O and SO₂ on V₂O₅/AC the activity of catalyst for selective catalytic reduction (SCR) of NO with NH₃ at lower temperatures was studied. In the absence of SO₂, H₂O inhibits the catalytic activity, which may be attributed to competitive adsorption of H₂O and reactants (NO and/or NH₃). Although SO₂ promotes the SCR activity of the V₂O₅/AC catalyst in the absence of H₂O, it speeds the deactivation of the catalyst in the presence of H₂O. The dual effect of SO₂ is attributed to the SO₄²⁻ formed on the catalyst surface, which stays as ammonium-sulfate salts on the catalyst surface. In the absence of H₂O, a small amount of ammonium-sulfate salts deposits on the surface of the catalyst, which promote the SCR activity; in the presence of H₂O, however, the deposition rate of ammonium-sulfate salts is much greater, which results in blocking of the catalyst pores and deactivates the catalyst. Decreasing V₂O₅ loading decreases the deactivation rate of the catalyst. The catalyst can be used stably at a space velocity of 9000 h⁻¹ and temperature of 250 °C.     

Alumina- and titania-based monolithic catalysts for low temperature selective catalytic reduction of nitrogen oxides

The selective catalytic reduction of NO+NO₂ (NO_x) at low temperature (180–230°C) with ammonia has been investigated with copper-nickel and vanadium oxides supported on titania and alumina monoliths. The influence of the operating temperature, as well as NH₃/NO_x and NO/NO₂ inlet ratios has been studied. High NO_x conversions were obtained at operating conditions similar to those used in industrial scale units with all the catalysts. Reaction temperature, ammonia and nitrogen dioxide inlet concentration increased the N₂O formation with the copper-nickel catalysts, while no increase was observed with the vanadium catalysts. The vanadium-titania catalyst exhibited the highest DeNO_x activity, with no detectable ammonia slip and a low N₂O formation when NH₃/NO_x inlet ratio was kept below 0.8. TPR results of this catalyst with NO/NH₃/O₂, NO₂/NH₃/O₂ and NO/NO₂/NH₃/O₂ feed mixtures indicated that the presence of NO₂ as the only nitrogen oxide increases the quantity of adsorbed species, which seem to be responsible for N₂O formation. When NO was also present, N₂O formation was not observed.     

Feasibility analysis of SO2 absorption using a hydrophilic ceramic membrane contactor

Hydrophilic ceramic membranes would be potential candidates for membrane gas absorption if they could be applied to appropriate separation processes. This study highlights a novel concept for the practical implementation of SO₂ absorption in hydrophilic ceramic membrane that exhibits outstanding thermal and mechanical stabilities. With this aim, we investigated experimentally the performance of SO₂ absorption into aqueous sodium hydroxide (NaOH) solution in a hydrophilic alumina (Al₂O₃) membrane contactor in terms of SO₂ removal efficiency and SO₂ mass transfer flux, and compared the performance with that in a hydrophobic one. A series of experiments were performed at various conditions over a NaOH concentration range of 0-1.0 mol·L^-1, a liquid flow rate range of 30-180 ml·min^-1, a gas flow rate range of 120-1000 ml·min^-1, an inlet SO₂ concentration range of 400-2000 μl·L^-1, and a temperature range of 10-35℃. It was found that the hydrophilic membrane was more competitive when using a NaOH concentration higher than 0.2 mol·L^-1. Furthermore, it can be inferred that the hydrophilic α-Al₂O₃ membrane exhibited exceptional long-term stability under 480 h continuous operation.     

Carbon oxidation with platinum supported catalysts

The effect of the support oxide, Pt precursor and reactant gas composition on the catalysis of soot oxidation was investigated using carbon black as a model soot and simulated exhaust gases. The Pt precursors used were Pt(NH₃)₄(OH)₂, H₂PtCl₆·6H₂O, Pt(NH₃)₄(NO₃)₂, and Pt(NH₃)₄Cl₂. The support metal oxides used were SiO₂, Al₂O₃, and ZrO₂. Pt/SiO₂ prepared from Pt(NH₃)₄(OH)₂ showed the highest carbon oxidation activity. It had much higher activity in the condition of N₂+O₂+H₂O+NO+SO₂ than without NO and SO₂.     

选择催化还原(SCR)反应机理研究进展

简述了NH₃和NO在催化剂表面吸附、转化活化和反应历程及H₂O和SO₂对以上反应行为的影响。分析表明,NH₃氧化脱氢进而与NO反应是决定NH₃反应性和最终产物的关键。NO以气态（Eley-Rideal机理）或硝基类物质等吸附态（Langmuir-Hinshelwood机理）形式参与选择催化还原（SCR）反应。提高催化剂酸性和氧化还原循环性能,利于NH₃和NO吸附和转化及相互间反应。高温时,H₂O影响轻微,而SO₂增强催化剂酸性,提高脱硝活性。低温时,H₂O和SO₂抑制NO吸附和转化活化,导致硫铵盐累积和活性位转变为硫酸盐使催化剂失活。因此,提高抗H₂O、抗SO₂性能是低温脱硝催化剂研发的重要方向。而发展在线升温等再生工艺以解决硝酸盐或含硫化合物导致的失活问题,对保障低温脱硝系统长期稳定运行具有重要意义。     

Selective catalytic reduction of nitric oxide by ethylene in the presence of oxygen over Cu ion-exchanged pillared clays

Cu²⁺ ion-exchanged pillared clays are substantially more active than Cu²⁺-ZSM-5 for selective catalytic reduction (SCR) of NO by hydrocarbons. More importantly, H₂O (or SO₂) has only mild effects on their activities. First results on Cu²⁺-exchanged TiO₂-pillared montmorillonite were reported by this laboratory (Yang and Li, Ref. [1]), that showed overall activities two to four times higher than Cu²⁺-ZSM-5.

A delaminated pillared clay was subjected to Cu²⁺ ion-exchange and studied for SCR by C₂H₄ in this work. The Cu²⁺ ion-exchanged delaminated Al₂O₃-pillared clay yielded substantially higher SCR rates than both Cu²⁺-exchanged TiO₂-pillared clay and Cu²⁺-ZSM-5 at temperatures above 400°C. The peak NO conversion was 90% at 550°C and at a space velocity of 15,000 h⁻¹ (with O₂ = 2%). The peak temperature decreased as the concentration of O₂ was increased. The macroporosity in the delaminated pillared clay was partially responsible for its higher peak temperatures (than that for laminated pillared clays). At 1000 ppm each for NO and C₂H₄, the NO conversion peaked at 2% O₂ for all temperatures. H₂O and SO₂ caused only mild deactivation, likely due to competitive adsorption (of SO₂ on Cu²⁺ sites and H₂O on acid sites). The high activity of Cu²⁺-exchanged Al₂O₃-pillared clay was due to a unique combination of the redox property of the Cu²⁺ sites and the strong Lewis acidity of the pillared clay. The suggested mechanism involved NO chemisorption (in the presence of O₂) on Cu²⁺OAl³⁺-on the pillars, and C₂H₄ activation on the Lewis acid sites to form an oxygenated species.