SO2和H2O对Y掺杂Mn/TiO2选择性脱除NO的影响

采用溶胶-凝胶法制备了Y掺杂的TiO₂载体,负载硝酸锰构成了Y掺杂的Mn-Y/TiO₂催化剂。考察了焙烧温度、空速对其催化还原NO性能的影响,并对催化剂的抗SO₂、H₂O毒化性能进行了考察。结果表明,催化剂的最佳焙烧温度为500 ℃,催化剂的活性随空速的降低而升高,XRD分析Y掺杂抑制了锐钛矿晶相的转移,有利于催化剂活性组分的分散,从而提高催化剂的活性。Mn-Y/TiO₂的抗毒化性能优于Mn/TiO₂,在反应温度180 ℃、空速14000 h^－1、氧含量为3%、NO浓度600 mL/L及NH₃/NO为1的条件下,同时通入200 mL/L SO₂和4% H₂O,NO转化率从非掺杂的Mn/TiO₂的48.2%上升到57.6%,Y掺杂提高了催化剂的抗毒化能力;FTIR分析表明催化剂中毒是由于生成了铵的硫酸盐或者锰、钇的硫酸盐。     

活性炭上NO和SO2的常温吸附特性研究

通过吸附穿透曲线和吸附容量,考察了两种活性炭吸附剂在不同气氛条件下SO2和NO的常温吸附性能.结果表明,无氧条件下,活性炭对NO吸附能力较弱;有氧时,O2可促进NO在活性炭上的吸附转化;无氧条件下,活性炭吸附SO2的性能远远强于吸附NO;O2的存在均可提高两种活性炭对NO和SO2的吸附能力.预吸附NO形成的某些NOx物种可促进SO2吸附.SO2对NO的吸附有明显抑制作用.同时吸附时,SO2和NO不会单独占据同一活性中心,即SO2与NO可能有共同的吸附位,并形成新的吸附态中间产物.且比较两种活性炭的常温吸附性能,椰壳活性炭强于煤质活性炭.     

微纳米气泡耦合尿素同时脱除NO和SO2及其机理的研究

利用基于尿素溶液的微纳米气泡气液分散体系实施同时脱除NO和SO₂,并考察了不同参数对脱除的影响。结果表明,各种所考察的参数对SO₂脱除效率均无显著影响,但均影响了NO的脱除效率。随着尿素溶液初始pH、尿素浓度以及SO₂浓度的提高,NO的脱除效率均先升高后降低;提高尿素溶液初始温度或NO浓度会降低NO的脱除效率。此外,通过机理分析发现,微纳米气泡释放的羟基自由基对NO和SO₂的脱除起了主导作用,尿素能进一步促进NO的脱除。     

Fe/γ-Al2O3催化剂上CO同时还原NO和SO2研究

研究了不同载体(γ-Al₂O₃、HZSM-5、TiO₂、SiO₂和MgO)负载Fe催化剂上CO还原NO反应及CO同时还原NO和SO₂反应。结果表明,Fe/γ-Al₂O₃催化剂对CO与NO反应具有良好的催化活性,但随着反应时间的延长,催化剂很快失活;在CO和NO反应中加入SO₂,可以明显改善Fe/γ-Al₂O₃催化剂对CO还原NO反应的活性稳定性;O₂和H₂O对催化剂活性的影响较大,CO₂对催化剂的影响较小。XRD结果表明,FeS₂是催化剂的活性中心,在CO与NO反应后,FeS₂转变为催化惰性的Fe₇S₈而导致催化剂活性下降;在CO与NO及SO₂反应体系中引入O₂后,Fe/γ-Al₂O₃催化剂上的活性组分FeS2被氧化为Fe₂O₃,导致催化剂失活。     

WO3/TiO2催化剂活性组分W对SO2的氧化特性

采用超声浸渍法制备了不同W负载量的WO₃/TiO₂催化剂,研究了W负载量、温度及SO₂浓度对催化剂表面SO₂氧化过程的影响。结果表明,催化剂表面SO₂氧化率随W负载量及温度的升高而增大,当W负载量由1%增至7%时,SO₂氧化率由0.034%升高至0.210%;而当温度由280℃升高至400℃时,SO₂氧化率由0.043%升高至0.240%。通过N₂吸附、XRD、Raman、NH₃-TPD、H₂-TPR及XPS等方法对催化剂样品进行表征。结果表明,活性组分W的增加会导致WO_x增加,该结构能够减弱催化剂表面Br?nsted酸性位点强度,增强SO₂在催化剂表面的吸附,同时导致催化剂表面吸附氧(O_α)增多,促进SO₂氧化;针对W负载量5%的催化剂原位红外试验结果表明,通入SO₂     

煤中黄铁矿对活性焦SO2和NO吸附性能的影响及机制

黄铁矿(FeS₂)是煤中主要含铁矿物质,且对煤利用具有重要影响,本研究以物理混合的方式在脱灰宁夏无烟煤上负载不同质量分数(0.5%,1%,2%,3%)的黄铁矿,通过水蒸气活化制备活性焦,分析黄铁矿对活性焦制备及污染物脱除性能的影响。结果表明:黄铁矿在活性焦制备过程中发生分解,在水蒸气的参与下最终转化为赤铁矿(Fe₂O₃),且对活性焦的孔结构、微晶结构和表面化学性质等理化结构的形成起调控作用;黄铁矿的加入进一步促进了活性焦微中孔的发育,过量的黄铁矿使煤焦碳结构的无序性增加、石墨化程度降低、孔结构坍塌,NX-1%FeS₂-AC(NX为宁夏酸洗煤,AC为活性焦)的比表面积最高,达到了771 m²/g;黄铁矿可以促进活性焦酸碱官能团的生成,随着黄铁矿含量的增加,活性焦硫容呈现先升高后下降趋势,NX-1%FeS₂-AC表现出最佳的脱硫能力,为68.49 mg/g;与SO₂吸附相比,NO的吸附效果较差,随着黄铁矿含量的增加,NO转化率降低;同时脱硫脱硝过程中,NO吸附迅速达到饱和,整体硫容升高。     

15 MW生物质循环流化床NOx和温室气体排放特性

生物质是零碳可再生能源,对我国实现碳达峰、碳中和目标具有重要意义。虽然被视为清洁能源,但生物质燃烧过程仍会排放NO_x(NO、N₂O)和温室气体(CH₄、N₂O、CO₂),有必要对生物质直燃的NO_x和温室气体排放特性进行研究。测量某15 MW生物质循环流化床的NO_x和温室气体排放,并探究了改变床压、一二次风比、前后墙二次风比、废木料掺烧比例等因素对NO_x和温室气体排放特性的影响。燃烧调整试验表明：升高床压有利于降低NO排放,但降幅很小,且会造成CO和CH₄体积分数上升,CO₂体积分数降低;随一二次风比增大,NO排放略降低,这意味着可适当降低二次风以降低NO排放量,CO和CH₄体积分数降低,CO₂体积分数升高;当前墙二次风开度/后墙二次风开度较小或较大时,均有利于降低NO,CO和CH₄排放量也较低;高含氮废木...     

N2/CO2气氛下木屑生物质热解特性的实验研究

本研究利用固定床管式炉开展了不同N2/CO₂比例气氛下的木屑生物质热解实验,考察了CO₂浓度、载气流速和停留时间对热解油和焦炭产率的影响。结果表明：热解油和焦炭的产率随反应温度和停留时间的增加而降低,热解油产率随反应气氛中CO₂浓度的升高而增加。在N₂和CO₂气氛下,载气流速升高均使热解油产率下降,而焦炭产率则在15%左右保持不变。添加HZSM-5和ZIF-67两种催化剂,发现ZIF-67在CO₂气氛下的热解油产率可以达到72.3%,相比其在N₂气氛下的热解油产率提升了近1.5倍;而HZSM-5由于其微孔孔道对生物质大分子传质的限制,产生最多焦炭(24.1%)。     

350 MW大型循环流化床锅炉SO2和NOx超低排放运行特性研究

为探究循环流化床锅炉在燃用非设计煤种时脱硫脱硝系统的运行情况,并对其进行经济性分析,以某350 MW超临界循环流化床锅炉(CFB)为研究对象,采用炉内结合尾部半干法两级脱硫超低排放系统,通过实炉试验探究了在满足超低排放条件下,锅炉在燃用三种非设计煤种及三种不同负荷时炉内和尾部半干法脱硫系统的运行情况,并基于自行构建的经济性分析模型,从脱硫脱硝运行费用角度分析了不同条件下满足超低排放时机组的经济性。结果表明：在入炉煤硫含量远高于设计值的情况下,CFB锅炉采用炉内脱硫结合尾部半干法脱硫的超低SO₂排放技术,仍可稳定满足超低排放要求,具有显著优势,通过合理控制炉内脱硫程度(即改变锅炉出口SO₂质量浓度)存在最佳的系统运行经济性;煤种硫含量的变化直接影响着系统的经济运行方式,在硫质量分数分别为0.82%,1.21%,1.62%时,调整锅炉出口SO₂质量浓度分别为1 016 mg/m³,1 158 mg/m³,1 259 mg/m³时,系统的运行经济性最好;锅炉燃用...     

SO42-/TiO2固体超强酸催化合成乙酸乙酯

用固体超强酸SO42-/TiO2为催化剂,以乙醇和乙酸为原料合成乙酸乙酯,探讨了催化剂制备条件酯收率的影响,实验结果表明:当用1 mol.L-1H2SO4浸渍TiO212 h,400℃焙烧2 h所得固体超强酸对催化合成乙酸乙酯显示出较高的催化活性。反应温度80℃,催化剂用量为2.0 g,醇酸摩尔比1.8∶1,反应时间为3.0 h时酯的收率最高可达97%。     

用KMnO4调质钙基吸收剂从燃煤烟气同时脱硫脱硝

在固定床反应器中考察了强氧化剂KMnO₄作为添加剂对钙基吸收剂同时脱硫脱硝的调质效果。实验结果表明,不含KMnO₄时钙基吸收剂不能有效脱除NO,而当KMnO₄存在Ca/(S+0.5N)为1.8时,钙基吸收剂可获得31.4％的脱硫率和13.5％的脱硝率。实验还研究了各种参数变化对脱硫率和脱硝率的影响,反应温度升高能够促进SO2的脱除,但脱硝率对温度的变化不敏感;脱硫率随着烟气相对湿度的增加而增加,但脱硝率与相对湿度的关系不是单调的,存在一个最大值;O₂是脱除NO的必要条件。结合气体分析和产物分析的实验结果发现,NO被脱除的机理是先被氧化为NO₂,然后再与吸收剂和脱硫产物反应生成了硝酸盐和亚硝酸盐。为半干法脱硫技术中加入脱硝功能的可能性提供参考依据。     

Simultaneous SO2/NOx removal by a powder-particle fluidized bed

Simultaneous dry removal of SO₂ and NO_x from flue gas has been investigated using a powder-particle fluidized bed. In a process of flue gas desulfurization by use of solid sorbents such as FeO (dust from a steel plant) and CuO, the smaller the particle size of sorbents, the higher the expected SO₂ conversion. In a powder-particle fluidized bed (PPFB), fine particles less than 40 μm in diameter fed into the bed are fluidized with coarse particles. But only the fine particles are entrained from the bed, and their residence time in the bed is remarkably long.

The reduction of NO_x with NH₃ in the fluidized bed is catalyzed by coarse particles or both coarse and fine particles. In this study, PPFB was applied to simultaneous dry SO₂/NO_x removal process, and several kinds of sorbents or catalysts were evaluated in a PPFB. Using the selected sorbents and catalysts, kinetic measurements were made in the temperature range of 300 to 600°C. SO₂ removal efficiencies were affected by reaction temperature, sorbent/S ratio, and static bed height. NO_x removal efficiencies in excess of 95% were achieved at NH₃/NO_x mole ratio of 1.0. When FeO was used as sorbent, SO₂ conversion increased with increasing temperature and reached 80% at 600°C.     

Low cost coal-based carbons for combined SO2 and NO removal from exhaust gas

The aim of this paper is to show how a cheap carbonaceous material such as low rank coal-based carbon (or char) can be used in the combined SO₂/NO removal from exhaust gas at the linear gas velocity used in commercial systems (0.12 m s⁻¹). Char is produced from carbonization and optionally activated with steam. This char is used in a first step to abate the SO₂ concentration at the following conditions: 100 °C, space velocity of 3600 h⁻¹, 6% O₂, 10% H₂O, 1000 ppmv SO₂, 1000 ppmv NO and N₂ as remainder. In a second step, when the SO₂ concentration in the flue gas is low, NO is reduced to N₂ and steam at the following experimental conditions: 150 °C, space velocity of 900 h⁻¹, 6% O₂, 10% H₂O, 0-500 ppmv SO₂, 1000 ppmv NO, 1000 ppmv NH₃ and N₂ as remainder.It has been shown that the presence of NO has no effect on SO₂ abatement during the first step of combined SO₂/NO removal system and that low SO₂ inlet concentration has a negligible effect on NO reduction in the second step. Moreover, this char can be thermally regenerated after use for various cycles without loss of activity. On the other hand, this regenerated char shows the highest NO removal activity (compared to parent chars, either carbonized or steam activated) which can be attributed to the activating effect of the sulfuric acid formed during the first step of the combined SO₂/NO removal system.     

SO2 and NO removal from flue gas over V2O5/AC at lower temperatures — role of V2O5 on SO2 removal

Supporting V₂O₅ onto an activated coke (AC) has been reported to significantly increase the AC's activity in simultaneous SO₂ and NO removal from flue gas. To understand the role of V₂O₅ on SO₂ removal, V₂O₅/AC is studied through SO₂ removal reaction, surface analysis, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FTIR) techniques. It is found that the main role of V₂O₅ in SO₂ removal over V₂O₅/AC is to catalyze SO₂ oxidation through a VOSO₄-like intermediate species, which reacts with O₂ to form SO₃ and V₂O₅. The SO₃ formed transfers from the V sites to AC sites and then reacts with H₂O to form H₂SO₄. At low V₂O₅ loadings, a V atom is able to catalyze as many as 8 SO₂ molecules to SO₃. At high V₂O₅ loadings, however, the number of SO₂ molecules catalyzed by a V atom is much less, due possibly to excessive amounts of V₂O₅ sites in comparison to the pores available for SO₃ and H₂SO₄ storage.     

UV/H2O2氧化联合CaO吸收脱除NO的传质-反应动力学

在实验室规模的光化学反应器中,基于实验研究﹑动力学理论以及双膜理论,研究了UV/H₂O₂氧化联合CaO吸收(UV/H₂O₂-CaO工艺)脱除燃煤烟气中NO的传质-反应动力学。分析了NO吸收的传质-反应过程,明确了NO吸收过程的主要控制步骤和强化措施,测定了关键的动力学参数,推导了NO吸收过程的理论模型。结果表明:在实验范围内,NO吸收速率随着NO浓度的增加几乎呈线性增加。随着H₂O₂浓度和CaO浓度的增加,NO的吸收速率均呈现先增加后变缓的趋势。UV/H₂O₂-CaO工艺脱除NO是一个拟一级快速反应过程,强化气相主体扰动﹑增加气液接触面积和提高NO分压可有效提高NO的吸收速率。NO吸收速率方程的计算值和实验值具有较好的一致性。     

Influence of CO-evolving groups on the activity of activated carbon fiber for SO2 removal

An investigation was made into the influence of CO-evolving and CO₂-evolving groups on the activities of activated carbon fibers (ACFs) for the oxidative conversion of SO₂ into aq. H₂SO₄ in the presence of O₂ and H₂O. The results indicated that the amount of evolved CO determined the SO₂ removal activity of ACFs, whereas, the amount of evolved CO₂ did not correlate with the ACFs activity for SO₂ removal. A direct proportionality between the amount of evolved CO and the enhanced activity of SO₂ removal was confirmed by using different oxidizing agents for changing the types and amount of oxygen functional groups in ACFs.     

Removal of SO2 using ammonium bicarbonate aqueous solution as absorbent in a bubble column reactor

In this work, the removal of SO₂ from gas mixture with air and SO₂ by ammonium bicarbonate aqueous solution as absorbent was investigated experimentally in a bubble column reactor. The effects of the concentration of ammonium bicarbonate, the SO₂ inlet concentration of gas phase and the gas flow rate on the removal rate of SO₂ were studied. The results showed that the higher the SO₂ inlet concentration and the gas flow rate, the shorter the lasting time of SO₂ completely removed in gas outlet, and then the faster the decrease in the removal rate of SO₂. The lasting time of SO₂ completely removed in gas outlet increased with increasing ammonium bicarbonate concentration. During the process of SO₂ absorption, there was a critical pH of solution. When the solution pH was less than the critical pH, it would sharply fall, resulting in a rapid decrease of the SO₂ removal rate. A theoretical model for predicting the SO₂ removal rate has been developed by taking the chemical enhancement and the sulfite concentration in the liquid phase into account simultaneously.     

Storage of NO2 on BaO/TiO2 and the influence of NO

The influence of NO on the adsorption and desorption of NO₂ on BaO/TiO₂ has been studied under lean conditions. The adsorption of NO₂ involves the disproportionation of NO₂ into an adsorbed nitrate species and NO released to the gas phase with a 3:1 ratio,

BaO+3NO₂→NO+Ba(NO₃)₂.

Three different nitrate species form on the catalyst: surface nitrates on the TiO₂ support, surface nitrates on BaO, and bulk barium nitrate. The stability of the three species in different gas feeds was investigated by temperature-programmed desorption (TPD).

The reverse reaction of the NO₂ disproportionation has also been observed. If NO is added to the feed, nitrates previously formed on the sorbent will decompose into NO₂. Therefore, the above chemical equation should be considered as an equilibrium reaction. Applying this finding to the NO_x storage and reduction catalyst means that NO probably reacts with the previously formed nitrates yielding NO₂ as an intermediate product. This NO₂ is subsequently reduced by the reducing agents (hydrocarbons and CO) present during the regeneration period.     

The mechanism of SO2 effect on NO reduction with propene over In2O3/Al2O3 catalyst

An In₂O₃/Al₂O₃ catalyst shows high activity for the selective catalytic reduction of NO with propene in the presence of oxygen. The presence of SO₂ in feed gas suppressed the catalytic activity dramatically at high temperatures; however it was enhanced in the low temperature range of 473–573 K. In TPD and FT-IR studies, the formation of sulfate species on the surface of the catalyst caused an inhibition of NO_X adsorption sites, and the absorbance ability of NO was suppressed by the presence of SO₂, and the amount of ad-NO₃⁻ species decreased obviously. This leads to a decrease of catalytic activity at higher temperatures. However, addition of SO₂ enhanced the formation of carboxylate and formate species, which can explain the promotional effect of SO₂ at low temperature, because active C₃H₆ (partially oxidized C₃H₆) is crucial at low temperature.