活性炭负载磷钨酸用于烟气脱硝抗水性能实验研究

通过硝酸活化和高温水热活化方法对活性炭进行表面改性,之后在改性活性炭上负载不同含量的磷钨酸考察催化剂在有水蒸汽条件下的催化氧化脱硝催化活性,初始反应条件为：温度80 ℃,空速800 h^-1,O₂体积分数为5%、H₂O体积分数为4.2%、NO含量为443 mg·m^-3。通过FT-IR表征制备的催化剂评价前后表面有机活性基团的变化,将不同磷钨酸负载量下活性炭催化剂的脱硝活性评价结果和红外光谱结合,结果表明,湿气条件下,磷钨酸负载质量分数为10%时制备的催化剂能够较好地保持催化氧化脱硝稳定性,NO脱除效率约40%。考察不同操作参数,如温度、水蒸汽含量、O₂含量和空速对负载质量分数10%磷钨酸的活性炭催化剂催化氧化脱硝抗水性能的影响,最优操作条件：温度120 ℃,O₂体积分数8%,水蒸汽体积分数6%,空速1 000 h^-1,催化氧化反应的NO转化率达62%。     

Research advance in mechanism of low-temperature SCR of NO on carbon materials

简述了不同反应物组合在碳材料表面的行为特征,单组分NO可以形成吸附态的NO₂、二聚体(NO)₂、—NO₂或吡啶类的化合物;O₂存在时NO被吸附态的氧氧化成NO₂;NO、O₂和NH₃同时存在时,反应发生在吸附态的NH₃和吸附态的NO₂之间。着重详述了活性碳纤维（activated carbon fibers,ACF）催化剂上的选择性催化还原（selective catalytic reduction,SCR）NO的机理为：低温时以NH₃为还原剂的SCR（NH₃-SCR）遵循Langmuir-Hinshelwood机理,较高温度时NH₃-SCR 遵循Eley-Rideal机理;分析指出了催化剂孔结构特征和表面化学官能团是ACF能低温选择性催化还原NO的主要影响因素。     

富氧条件下金属催化CO还原NO的研究进展

CO广泛存在于燃煤烟气及汽车尾气中,利用未完全燃烧的CO催化还原NO可同时脱除NO和CO,过程中催化剂起着决定性作用。本文对近年来含氧条件下CO催化还原NO的研究成果进行了系统梳理,重点关注了Pd系、Ir系、Cu系、其他贵金属及金属氧化物催化剂的研究进展,分析了催化剂制备方法、掺杂改性及反应条件对催化性能的影响,同时考察了O₂浓度、H₂O以及SO₂对催化反应的影响,总结并对比了不同体系催化剂的活性位点及其催化机理,指明了O₂在催化还原过程中的抑制机理,得出了几种体系催化剂催化CO还原NO的活性顺序。最后,针对富氧条件下CO催化还原NO所存在的问题和难点,提出深入研究O₂抑制机理、降低贵金属用量、添加活性助剂是今后的研究方向。     

氧化铈基HCl氧化循环制Cl2催化剂研究进展

氯化氢催化氧化技术在副产氯化氢的处理和利用方面有着巨大的应用价值和良好的工业前景。CeO₂基催化剂因其廉价、不易烧结及抗氯化性能优良等诸多优点,被认为是目前最具有应用前景的氯化氢氧化催化剂之一。本文简要地介绍了氯化氢氧化制氯循环工艺,评述了近年来用于氯化氢氧化反应的CeO₂基催化材料,包括CeO₂催化剂、掺杂改性CeO₂催化剂以及CeO₂作助催化剂等。同时在文中还对CeO₂基材料催化HCl氧化的表面反应机理进行阐述。最后结合目前的研究现状,对如何进一步提升CeO₂基催化HCl氧化的反应活性进行了展望。     

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。     

活性炭辅助低温等离子体脱除燃煤烟气中NO

燃煤烟气中氮氧化物以NO为主,其大量排放对自然环境和人类健康危害极大。针对低温等离子体(Nonthermal plasmas, NTPs)技术脱除NO效率低、能耗高的问题,系统研究不同气体流量、O₂含量和NO初始浓度等因素对低温等离子体过程中NO去除效果的影响。结果表明,在N₂/NO混合气体条件下,NO脱除率为90%、气体流量为5 L/min对应的单位能耗NO处理量最高,为4.17 g/kWh。O₂的存在对于NO转化具有一定抑制作用,且在高O₂含量下,升高电源的输出功率反而不利于NO脱除。研究发现,O₂体积分数6%条件下,NO脱除率低于46%,对应单位能耗NO处理量仅为2.29 g/kWh。为实现有氧条件下NO的低能耗高效脱除,在低温等离子体反应段前添加活性炭吸附氧化工艺。首先利用活性炭对高浓度NO进行吸附氧化预处理,降低进入低温等离子体反应器中的NO浓度;随后,采用低温等离子体技术对剩余NO进行深度氧化处理,实现NO的低能耗高效脱除。结果表明,采用该耦合工艺,活性炭吸附氧化N...     

常温下沥青基活性炭纤维对NO的催化氧化性能

以4种比表面积不同的沥青基活性炭纤维为材料,研究了常温下对模拟空气气氛中体积分数为50×10^-6的NO的催化氧化性能,并采用氮吸附法、Raman光谱和红外光谱对活性炭纤维进行了表征。结果表明,活性炭纤维可将NO部分催化转化为NO₂,较低比表面积的活性炭纤维因为其较窄的孔径分布和较大的类石墨微晶而有利于对NO的催化氧化。     

氧化铬催化剂上NO常温催化氧化反应的性能研究

采用沉淀方法制备了氧化铬催化剂,并用于NO催化氧化反应,首次发现该催化剂具有常温氧化活性,考察了沉淀剂和焙烧温度等制备条件对其活性的影响。结果发现,相比于常规的活性炭及活性炭纤维,氧化铬催化剂在常温催化氧化NO方面表现出了更加优异的活性及稳定性,当NO质量分数为15μg/g,空速为43 200 m L/h时,可维持800 min以上100%净化率,采用氨水、碳酸氢铵、氢氧化钾作为沉淀剂时,300℃焙烧得到的氧化铬催化剂具有很好的活性及稳定性。     

纳米碳材料催化液相选择性氧化的研究进展

纳米碳材料是广受关注的高性能材料,其作为无金属催化剂的应用近年来受到了广泛关注。综述了碳材料在不同氧化剂（O₂、H₂O₂、叔丁基过氧化氢、氧化石墨等）的作用下选择性催化氧化烃类、醇类、酮类、胺类等制备有机化学品和氧化降解有机污染物反应过程,着重阐述这些液相氧化反应体系的机理以及碳材料在其中所起的作用。     

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。     

催化裂化再生过程脱硝技术

系统论述了当前主要的脱硝技术、流化催化裂化（FCC）再生工艺及FCC再生过程NO_x产生和转化规律。O₂是影响催化剂脱硝活性的主要因素,从反应器尺度精确控制烧焦再生反应,严格控制过剩氧含量,是提高脱硝效率的一条可行途径。提出了通过再生器内部结构和工艺设计创造出具有氧化区和还原区多层多区的新型再生工艺脱硝思路。从降低NO_x角度考虑,再生温度应不高于700℃,再生烟气中CO浓度不低于4%,O₂浓度至少低于1%。这种新的再生器脱硝是一种经济、高效的脱硝技术,已在中石油大港石化FCC工业装置得到了初步验证,为FCC再生装置和其他化工过程脱硝提供了新思路。     

Catalytic effect of platinum on the kinetics of carbon oxidation by NO2 and O2

The effect of a commercial Pt/Al₂O₃ catalyst on the oxidation by NO₂ and O₂ of a model soot (carbon black) in conditions close to automotive exhaust gas aftertreatment is investigated. Isothermal oxidations of a physical mixture of carbon black and catalyst in a fixed bed reactor were performed in the temperature range 300–450 °C. The experimental results indicate that no significant effect of the Pt catalyst on the direct oxidation of carbon by O₂ and NO₂ is observed. However, in presence of NO₂–O₂ mixture, it is found that besides the well established catalytic reoxidation of NO into NO₂, Pt also exerts a catalytic effect on the cooperative carbon–NO₂–O₂ oxidation reaction. An overall mechanism involving the formation of atomic oxygen over Pt sites followed by its transfer to the carbon surface is established. Thus, the presence of Pt catalyst increases the surface concentration of –C(O) complexes which then react with NO₂ leading to an enhanced carbon consumption. The resulting kinetic equation allows to model more precisely the catalytic regeneration of soot traps for automotive applications.     

碳材料用于低温选择性催化还原脱硝的研究进展

选择性催化还原技术是目前消除NOx的主流技术。碳材料作为自然界广泛存在的一种材料,具有比表面积大、化学稳定性好、结构可调控和表面可改性等优点,广泛应用于低温选择性催化还原反应。综述不同类型碳材料包括活性炭、活性炭纤维、碳纳米管、石墨烯和多孔碳在低温选择性催化还原中的应用,介绍碳材料作为活性组分和催化剂载体的使用情况,讨论表面化学改性对催化NOx性能的影响,阐述碳材料在加快反应速率和提升催化剂抗硫中毒方面的独特性能,并展望碳材料作为新型载体材料在低温选择性催化还原中的应用前景。     

Vanadium loaded carbon-based catalysts for the reduction of nitric oxide

Carbon-based SCR catalysts for the reduction of NO with NH₃ at low temperatures have been prepared using activated carbons obtained from a local Spanish coal, doped with several vanadium compounds. Among them, the ashes of a petroleum coke (PCA) were also employed. Both the catalysts and the carbon supports have been characterized by means of N₂ and CO₂ physisorption, NH₃ and O₂ chemisorption and temperature programmed desorption (TPD). The activity of the catalysts has been tested in a laboratory-scale unit, measuring significant conversions of NO (above 50%) with almost 100% selectivity toward N₂ at 150 °C. The feasibility of using the petroleum coke ashes as the active phase was confirmed comparing the activity of the catalysts doped with these residues, with the one measured for the catalysts prepared using model vanadium compounds. The physical–chemical features of the carbon support resulted of key importance for achieving a considerable catalytic activity. The values of apparent energy of activation calculated for the catalysts presented in this paper were very similar to other carbon-based catalysts and smaller than the ones corresponding to TiO₂-supported systems. The gas residence time on the catalytic bed influences the catalytic activity to a great extent, thus being a determinant parameter for designing the SCR de-NO_x unit. To avoid ammonia slip, inlet concentrations of NH₃ has to be little under the stoichometric NH₃/NO ratio (0.7). The catalysts stability was tested in terms of carbon support gasification followed by termogravimetric analysis and gas chromatography. The activity of the catalysts was maintained at least over 24 h of reaction.     

The selective reduction of NOx with propene on Pt-beta catalyst: A transient study

The mechanism of the NO/C₃H₆/O₂ reaction has been studied on a Pt-beta catalyst using transient analysis techniques. This work has been designed to provide answers to the volcano-type activity behaviour of the catalytic system, for that reason, steady state transient switch (C₃H₆/NO/O₂ → C₃H₆/Ar/O₂, C₃H₆/Ar/O₂ → C₃H₆/NO/O₂, C₃H₆/NO/O₂ → Ar/NO/O₂, Ar/NO/O₂ → C₃H₆/NO/O₂, C₃H₆/NO/O₂ → C₃H₆/NO/Ar and C₃H₆/NO/Ar → C₃H₆/NO/O₂) and thermal programmed desorption (TPD) experiments were conducted below and above the temperature of the maximum activity (T_max). Below T_max, at 200 °C, a high proportion of adsorbed hydrocarbon exists on the catalyst surface. There exists a direct competition between NO and O₂ for Pt free sites which is very much in favour of NO, and therefore, NO reduction selectively takes place over hydrocarbon combustion. NO and C₃H₆ are involved in the generation of partially oxidised hydrocarbon species. O₂ is essential for the oxidation of these intermediates closing the catalytic cycle. NO₂ is not observed in the gas phase. Above T_max, at 230 °C, C₃H_6 ads coverage is negligible and the surface is mainly covered by O_ads produced by the dissociative adsorption of O₂. NO₂ is observed in gas phase and carbon deposits are formed at the catalyst surface. From these results, the state of Pt-beta catalyst at T_max is inferred. The reaction proceeds through the formation of partially oxidised active intermediates (C_xH_yO_zN_w) from C₃H_6 ads and NO_ads. The combustion of the intermediates with O₂(g) frees the Pt active sites so the reaction can continue. Temperature has a positive effect on the surface reaction producing active intermediates. On the contrary, formation of NO_ads and C₃H_6 ads are not favoured by an increase in temperature. Temperature has also a positive effect on the dissociation of O₂ to form O_ads, consequently, the formation of NO₂ is favoured by temperature through the oxygen dissociation. NO₂ is very reactive and produces the propene combustion without NO reduction. These facts will determine the maximum concentration of active intermediates and consequently the maximum of activity.     

Catalytic reduction of NOx by biomass-derived activated carbon supported metals

In this study, to prepare a series of activated carbon-supported metals for the catalytic reduction of NO_x to N₂ in excess O₂, activated carbons derived from lignocellulosic and herbaceous biomasses were selected as the reducing agents, and alkali and transition metals were used as the catalytic active phases. The effects of the type of biomass, carbonization temperature and catalyst composition on NO_x reduction efficiency were analyzed in a fixed-bed flow reactor. The results showed that two temperature regimes are present for the NO_x-carbon reaction:at temperatures below 250℃, the NO_x adsorption process on the carbon surface was predominant, whereas true NO_x reduction by carbon occurred at temperatures above 250℃, producing N₂, CO₂ and CO. The influence of the carbonization temperature on carbon reactivity depended on the effect of the carbonization temperature on the carbon surface area and the reduction of the metal species on carbon. All studied metals catalyzed both NO_x and O₂ reduction by carbon, and potassium could strongly enhance the C-NO_x reaction without substantial carbon consumption by O₂. Moreover, the potassium supported by sawdust-derived activated carbon exhibited higher selectivity and capacity towards NO_x reduction than did its previously reported coal-derived counterparts. These properties were ascribed to the high dispersion of the active potassium species on the carbon surface, as observed through the comparison of X-ray photoelectron spectroscopy and powder X-ray diffraction results for the carbons made from biomass and coal-based precursors.     

Modifications to the surface chemistry of low-rank coal-based carbon catalysts to improve flue gas nitric oxide removal

The effectiveness of carbons as low-temperature selective catalytic reduction (SCR) catalysts will depend upon their physical and chemical properties. Surface functional groups containing oxygen are closely related to the catalytic activity of carbons. These groups are expected to change the interaction between the carbon surface and the reactants through a variation in adsorption and reaction characteristics. This paper presents a more detailed study of the effects of either gas-phase sulfuric acid or oxygen oxidation treatments on the catalytic NO reduction by low-rank coal-based carbon catalysts. Raw and treated carbons were characterized by N₂ and CO₂ surface areas, TPD and ash content. NO removal capacity of carbons was determined by passing a flow containing NO, H₂O, O₂, NH₃ and N₂ through a fixed bed of carbon at 150°C and 4 s of residence time, the effluent concentration being monitored continuously during the reaction. The effects of varying the type and conditions of the treatment on the physicochemical features of carbons were studied. The gas-phase sulfuric acid treatment (corresponding to a first step SO₂ removal) markedly enhanced carbon activities for NO removal. On the contrary, oxygen oxidation enhanced NO removal capacity of chars to a lower extent. Therefore, the carbons studied could be used in a combined SO₂/NO removal process, because the use and regeneration of the carbon in the first step is beneficial for the performance in the second one.     

MnOx/WO3/TiO2低温选择性催化还原NOx机理的原位红外研究

浸渍法制备15% MnO_x/5% WO₃/TiO₂低温脱硝催化剂,利用原位傅里叶变换红外（in situ FT-IR）设计包括多种吸附反应以及不同预处理方式的微观暂态试验与微观稳态试验,研究其NH₃-SCR脱硝反应机理,并推测反应路径。结果表明,催化剂的NH₃-SCR反应主要以Eley-Rideal机理方式进行,仅在一定温度条件下可以看到Langmuir-Hinshclwood反应路径。催化剂表面Lewis酸位的NH₃吸附是还原剂的主要来源,Brønsted酸位吸附的NH₄⁺随温度上升参与反应的比例略有提高。NH₃的吸附活化是整个反应的控制步骤,吸附态NH₃更易与NO₂发生反应,NO与催化剂表面的相互作用明显弱于NO₂。NO会在催化剂表面氧化活性中心形成大量双齿配位型硝酸盐,阻碍NH₃的吸附和活化,O₂存在条件下促进NH₃-SCR反应进行,阻止NO在催化剂表面形成双齿硝酸盐。NO与NH₃在催化剂表面存在吸附竞争,NO的吸附作用强于NH₃,温度达到100℃后吸附的NH₃方可大量活化并与NO_x发生进一步反应。     

Mn2+催化臭氧氧化活性污泥强化溶胞

研究了不同浓度活性炭、活性焦和Mn²⁺催化作用下臭氧氧化污泥碳源释放情况,发现Mn²⁺为较佳催化剂。本文进一步对比考察了不同Mn²⁺投加量对催化臭氧化污泥溶胞释放有机物的影响以及反应前后污泥特性的差异,探究了Mn²⁺催化臭氧化促进溶胞作用的机理。结果表明,在臭氧氧化污泥时添加Mn²⁺能促进污泥碳源的释放,其中当Mn²⁺投加量为1.5mmol/L时,污泥碳源的释放效果较佳,溶解性化学需氧量的变化值（ΔSCOD）质量浓度为76mg/L,约为单独臭氧氧化（O₃组）的4倍;污泥絮体胞外聚合物溶解性蛋白和腐殖质含量较原泥（空白组）和O₃组相比均有显著增加,分别为2倍和2.3倍,证实了Mn²⁺催化氧化促进了活性污泥胞内有机物的溶出。进一步的机理探究得出,O₃+Mn²⁺组·OH产量为O₃组的1.15～1.74倍,说明Mn²⁺催化氧化促进了反应过程中活性自由基尤其是·OH的生成。Mn²⁺催化臭氧氧化活性污泥在强化污泥破胞的同时,对污泥的理化性质影响较小,基本与单独臭氧氧化维持在同一水平,后续将其应用于基于臭氧旁路处理的污泥原位减量连续工艺有较大的可行性和实际意义。