V2O5-WO3/TiO2-SiO2制备及其选择性催化还原脱硝活性

以硫酸氧钛和硅溶胶为原料,通过共沉淀法制备得到高比表面积的TiO2-SiO2复合氧化物(Ti/Si=1:1atom),并以此复合氧化物为载体用浸渍法制备了V2O5-WO3/TiO2-SiO2脱硝催化剂,考察了催化剂脱硝性能。结果表明,TiO2-SiO2复合氧化物载体出现较多的隧道孔,提高了载体的比表面积,同时Ti元素更易分布在复合氧化物的表面。相比较于纯TiO2,以复合氧化物为载体的V2O5-WO3催化剂表现出更好的活性温度窗口,催化剂表面酸性更强,催化剂对NH3的吸附性能更好,在低的NH3/NO摩尔比情况下(0.8～1.0mol?mol?1),仍然具有较好的脱硝活性,反应温度280～350℃时,脱硝率可达到98%。     

以偏钛酸为原料的催化剂的脱硝性能研究

以偏钛酸为原料通过浸渍法和固相物质的热分解法来制备以NH3为还原剂选择性催化还原NOx的催化剂V2O5-WO3/TiO2。着重考察催化剂组成、NH3/NO摩尔比和模拟烟气中O2浓度对催化剂脱硝性能的影响。催化剂的脱硝性能测试结果表明催化剂V2O5(1.2%)-WO3(8.8%)/TiO2具有较高的催化活性和较宽的活性温度窗口,NO的转化率最高可达98.77%。综合考虑NH3逃逸、设备腐蚀和环境问题,NH3/NO摩尔比控制在1.2以内比较合适;富氧条件对脱硝催化反应的进行更有利。     

V2O5负载量对V2O5／TiO2催化剂SCR法脱硝的影响

以TiO2载体,采用浸渍法制备了不同V2O5负载量的用于选择性催化还原NOx的V2O5／TiO2催化剂。利用BET,SEM和Ⅺ①,对不同V2O5负载量的催化剂组成、结构、形貌和性能进行了表征,考察不同V2O5负载量对催化剂制备的影响。结果表明制备的催化剂具有较多的中孔和微孔,催化剂中V2O5含量的增加,会降低催化剂的表面积;V2O5含量为2％的V2O5／TiO2催化剂样品比表面积最大,但是其活性非常低;V2O5含量为4％催化剂比表面积较大,NOx脱转化率高;V2O5的负载量小时,V2O5主要以等轴聚合的钒基型式（V3O7和V6O13）存在,这些钒基是催化剂的活性中心;当负载量超过6％,V2O5主要以结晶相存在,占据大量活性位,降低催化效果。     

制备条件对柴油车用V2O5-WO3/TiO2催化剂催化性能的影响

采用偏NH4VO3和TiO2为前驱体制备选择性催化还原(SCR)催化剂涂层所需浆料,分别以分步涂覆法和一步涂覆法将浆料浸涂在蜂窝陶瓷载体上,得到了整体涂覆式选择性催化还原催化剂.对草酸添加量、焙烧时间及V2O5含量对催化活性的影响进行了研究,结果表明,V2O5(4%)-WO3/TiO2(450℃,3 h)和V2O5(5...     

V_2O_5/TiO_2催化剂上NH_3选择性催化还原NO反应动力学研究

采用浸渍法制备了V2O5/TiO2催化剂,研究了V2O5/TiO2催化剂上NH3选择性催化还原NO的反应动力学,运用Eley-Rideal机理模型确定了相关的动力学参数,推导出本征动力学方程,得到反应的活化能为41.9 kJ/mol。     

选择性催化还原(SCR)脱硝催化剂的性能研究

文章开展了工艺条件对选择性催化还原(SCR)脱硝催化剂的性能研究,采用自行研制开发的V2O5-WO3/TiO2-Al2O3催化剂,考察了温度、空速、NH3与NO摩尔比、NO初始浓度、氧浓度等对这种催化剂脱硝性能的影响,为选择性催化还原(SCR)脱硝催化剂的应用提供科学的实验数据。     

V_2O_5-WO_3/TiO_2催化剂的制备

采用工业钛白粉作为烟气脱硝催化剂的载体原料,通过添加助剂M对其改性,研制出了一种V2O5-WO3/Ti O2烟气脱硝催化剂,并确定助剂M的最佳量为质量分数10%;同时考察了焙烧温度对该催化剂比表面积及脱硝性能的影响,确定了最佳焙烧温度为500℃;最佳活性组分钒含量为质量分数1.5%,稳定助剂钨含量为质量分数8%的催化剂性能最好。     

溶胶-凝胶原位合成宽活性温度V_2O_5/TiO_2脱硝催化剂

利用溶胶-凝胶技术原位合成一系列不同V2O5担载量的V2O5/TiO2催化剂,通过BET、XRD、NH3-TPD及紫外-可见光等手段对催化剂进行表征。结果表明:制备的催化剂均具有介孔结构,V2O5在TiO2表面高度分散,且存在3种典型的酸性位。通过选择性催化还原反应对V2O5/TiO2催化剂进行活性评价,结果显示随着V2O5含量的增加,NO转化率大于75%的温度窗口向低温方向偏移,含10%(质量分数)V2O5的催化剂的NO转化率为80%的温度窗口最宽为200~450℃,240℃时20 h连续实验表现出稳定的抗硫抗水性能。结合紫外-可见光谱分析,揭示了钒掺杂所形成的单聚和低聚钒酸盐为催化剂的活性组分。     

沉淀pH值对TiO_2-SiO_2负载催化剂催化还原NO性能的影响

采用共沉淀法,在不同pH值下制备了3种TiO2-SiO2(TS)复合氧化物,采用BET、XRD、NH3-TPD和FTIR等方法对样品进行了表征;并以3种TS为载体,负载CuO、Cr2O3和CeO2活性组分,考察了不同Cu-Cr-Ce/TS催化剂在140～220℃NH3选择性催化还原NO的性能。结果表明,以pH值10～11的TS载体制备的Cu-Cr-Ce/TS催化剂具有最优的低温活性,这是由于该载体具有较大的比表面积和更多弱酸中心,能吸附大量易于与NO反应的氨。     

V2O5-MoO3/TiO2 催化剂的NOx选择性催化还原及SO2氧化活性

采用浸渍法以TiO₂为载体制备V₂O₅-MoO₃/TiO₂ 选择性催化还原催化剂,研究V₂O₅和MoO₃负载量对于催化剂选择性催化还原反应及SO₂氧化活性的影响,并考察氧含量、氨氮物质的量比和反应空速对3%V₂O₅-6%MoO₃/TiO₂催化剂选择性催化还原脱硝活性的影响。结果表明,随着催化剂中V₂O₅负载质量分数增加,V₂O₅-MoO₃/TiO₂ 催化剂的选择性催化还原活性和SO₂氧化活性均呈上升趋势。MoO₃的负载对催化剂的SO₂氧化活性有明显抑制作用。MoO₃负载质量分数超过9%,制备的催化剂既保持较高的低温选择性催化还原活性,又使选择性催化还原反应中的SO₂转化率小于1%。     

Boosting low-temperature selective catalytic reduction of NO with NH3 of V2O5/TiO2 catalyst via B-doping

A series of B-doped V₂O₅/TiO₂ catalysts has been prepared the by sol-gel and impregnation methods to investigate the influence of B-doping on the selective catalytic reduction (SCR) of NO_x with NH₃. X-ray diffraction, Brunauer-Emmett-Teller specific surface area, scanning electron microscope, X-ray photoelectron spectroscopy, temperature-programmed reduction of H₂ and temperature-programmed desorption of NH₃ technology were used to study the effect of the B-doping on the structure and NH₃-SCR activity of V₂O₅/TiO₂ catalysts. The experimental results demonstrated that the introduction of B not only improved the low-temperature SCR activity of the catalysts, but also broadened the activity temperature window. The best SCR activity in the entire test temperature range is obtained for VTiB_2.0 with 2.0% doping amount of B and the NO_x conversion rate is up to 94.3% at 210 ℃. The crystal phase, specific surface area, valence state reducibility and surface acidity of the active components for the as-prepared catalysts are significantly affected by the B-doping, resulting in an improved NH₃-SCR performance. These results suggest that the V₂O₅/TiO₂ catalysts with an appropriate B content afford good candidates for SCR in the low temperature window.     

燃煤电厂废旧SCR脱硝催化剂中TiO2载体的回收与再利用

以燃煤电厂废弃SCR脱硝催化剂为研究对象,考察了浸出时间、温度、液固比和NaOH浓度对碱浸过程Al、Si、V、W、Ti等元素浸出率以及浸出渣比表面积、孔容的影响。结果表明,碱浸的最优工艺条件为反应时间180 min、温度160℃、液固比15 ml·g^-1、NaOH浓度2.5 mol·L^-1。在最优工艺条件下得到的浸出渣主要成分为锐钛矿型TiO₂,经稀硫酸洗涤后作为载体,通过负载与新鲜催化剂相同含量的WO₃和V₂O₅,制备了V₂O₅-WO₃/TiO₂催化剂。对催化剂进行脱硝活性评价,结果表明,再生载体制备的催化剂脱硝活性恢复至新鲜催化剂水平,300℃时NO转化率达到97.8%,且具有良好的抗硫抗水性。     

溶胶-凝胶原位合成宽活性温度V2O5/TiO2脱硝催化剂

利用溶胶-凝胶技术原位合成一系列不同V₂O₅担载量的V₂O₅/TiO₂催化剂,通过BET、XRD、NH₃-TPD及紫外-可见光等手段对催化剂进行表征。结果表明：制备的催化剂均具有介孔结构,V₂O₅在TiO₂表面高度分散,且存在3种典型的酸性位。通过选择性催化还原反应对V₂O₅/TiO₂催化剂进行活性评价,结果显示随着V₂O₅含量的增加,NO转化率大于75%的温度窗口向低温方向偏移,含10% （质量分数）V₂O₅的催化剂的NO转化率为80%的温度窗口最宽为200～450℃,240℃时20 h连续实验表现出稳定的抗硫抗水性能。结合紫外-可见光谱分析,揭示了钒掺杂所形成的单聚和低聚钒酸盐为催化剂的活性组分。     

Catalytic performance of a novel ceramic-supported vanadium oxide catalyst for NO reduction with NH3

A novel TiO₂/Al₂O₃/cordierite honeycomb-supported V₂O₅–MoO₃–WO₃ monolithic catalyst was studied for the selective reduction of NO with NH₃. The effects of reaction temperature, space velocity, NH₃/NO ratio and oxygen content on SCR activity were evaluated. Two other V₂O₅–MoO₃–WO₃ monolithic catalysts supported on Al₂O₃/cordierite honeycomb or TiO₂/cordierite honeycomb support, two types of pellet catalysts supported on TiO₂/Al₂O₃ or Al₂O₃, as well as three types of pellet catalysts V₂O₅–MoO₃–WO₃–Al₂O₃ and V₂O₅–MoO₃–WO₃–TiO₂ were tested for comparison. The experiment results show that this catalyst has a higher catalytic activity for SCR with comparison to others. The results of characterization show, the preparation method of this catalyst can give rise to a higher BET surface area and pore volume, which is strongly related with the highly active performance of this catalyst. At the same time, the function of the combined carrier of TiO₂/Al₂O₃ cannot be excluded.     

Effects of microwaves on selective oxidation of toluene to benzoic acid over a V2O5/TiO2 system

Two series of catalysts, V₂O₅/TiO₂ and modified V₂O₅/TiO₂, were prepared with a conventional impregnation method. They were tested in the selective oxidation of toluene to benzoic acid under microwave irradiation. The reaction conditions were optimized over V₂O₅/TiO₂. It was found that in the microwave catalytic process the optimum reactor bed temperature of the titled reaction decreases to 500 K (600 K in the conventional process). The modification of V₂O₅/TiO₂ with MoO₃, WO₃, Nb₂O₅ or Ta₂O₅, which has no negative influence on the reaction in the conventional catalytic process, can greatly promote the catalytic activities in the microwave process, leading to a high yield of benzoic acid (41%). The effects of microwave electromagnetic field on the catalysts are discussed.     

Catalytic activation of ceramic filter elements for combined particle separation, NOx removal and VOC total oxidation

The development of a catalytically active filter element for combined particle separation and NO_x removal or VOC total oxidation, respectively, is presented. For NO_x removal by selective catalytic reduction (SCR) a catalytic coating based on a TiO₂–V₂O₅–WO₃ catalyst system was developed on a ceramic filter element. Different TiO₂ sols of tailor-made mean particle size between 40 and 190 nm were prepared by the sol–gel process and used for the impregnation of filter element cylinders by the incipient wetness technique. The obtained TiO₂-impregnated sintered filter element cylinders exhibit BET surface areas in the range between 0.5 and 1.3 m²/g. Selected TiO₂-impregnated filter element cylinders of high BET surface area were catalytically activated by impregnation with a V₂O₅ and WO₃ precursor solution. The obtained catalytic filter element cylinders show high SCR activity leading to 96% NO conversion at 300 °C, a filtration velocity of 2 cm/s and an NO inlet concentration of 500 vol.-ppm. The corresponding differential pressures fulfill the requirements for typical hot gas filtration applications. For VOC total oxidation, a TiO₂-impregnated filter element support was catalytically activated with a Pt/V₂O₅ system. Complete oxidation of propene with 100% selectivity to CO₂ was achieved at 300 °C, a filtration velocity of 2 cm/s and a propene inlet concentration of 300 vol.-ppm.     

含钛高炉渣制备SCR烟气脱硝催化剂

以含钛高炉渣为原料,稀硫酸为溶剂提取钛液,钛液经水解、高温焙烧后制得高比表面积的TiO₂,并以其为载体采用分步浸渍法制备了V₂O₅-WO₃/ TiO₂催化剂。优化了含钛高炉渣的酸解条件,对所得TiO₂进行了XRD、XRF、BET表征,用自制催化剂评价系统考察了所制备催化剂的脱硝性能及抗硫抗水性能。结果表明：H₂SO₄浓度40%、酸渣比1.5、酸解温度80℃、酸解时间3 h条件下,TiO₂浸出率可达90%,水解产物主要为锐钛型TiO₂,纯度达到74%,含有21.2%无定形SiO₂及少量其他杂质。SiO₂的存在提高了产物的比表面积、孔径,有利于活性组分的负载。以含钛高炉渣基TiO₂为原料制备的V₂O₅-WO₃/TiO₂脱硝催化剂相比于以商业TiO₂和TiOSO₄制备的催化剂,在250～450℃具有更高的催化活性,且在300℃具有较好的抗硫抗水性能。     

邻二氯苯在钒-钨-钛催化剂上的完全催化氧化

采用等体积浸渍法制备不同系列钒-钨-钛催化剂,以与二噁英TCDD化学结构式相似的邻二氯苯作为替代物,研究催化剂对邻二氯苯的去除效率,考察钒负载质量分数和钨负载质量分数对邻二氯苯催化氧化性能的影响,通过XRD和催化剂比表面积分析对催化剂的微观结构进行表征。结果表明,随着钒负载质量分数的增加,催化剂比表面积降低,催化剂性能降低;随着钨负载质量分数的增加,催化剂比表面积增加,催化剂性能提高。钨的加入有利于促进活性钒的分散,提高催化剂的比表面积,催化剂比表面积是影响催化剂性能的关键因素。     

Fe2O3对V2O5-WO3/TiO2催化剂表面性质及其性能的影响

催化剂是选择性催化还原(SCR)脱硝技术的核心,研究Fe对钒钛系SCR催化剂脱硝活性及SO₂/SO₃转化率的影响具有重要意义。采用等体积浸渍法制备了不同Fe/V质量比的Fe₂O₃-V₂O₅-WO₃/TiO₂催化剂,并进行表征,研究Fe对钒钛系SCR催化剂脱硝活性及SO₂/SO₃转化率的影响,并讨论Fe对于钒钛系SCR催化剂表面性质的影响。结果表明,随着催化剂表面Fe₂O₃含量增加,催化剂的脱硝效率及二氧化硫氧化率均是先上升后下降,当Fe/V质量比为3.0时,催化剂的脱硝效率和二氧化硫氧化率均达到最大值91.78%、1.01%。XPS及H₂-TPR结果表明,随着Fe₂O₃含量增加,催化剂表面钒活性组分的相对含量及V⁴⁺/V⁵⁺比减小,催化剂表面吸附氧(O_α)浓度增加,催化剂的氧化能力增强。NO-TPD结果表明,随着Fe₂O₃含量增加,催化剂表面吸附NO的能力增强。     

Ammonia activation over catalysts for the selective catalytic reduction of NOx and the selective catalytic oxidation of NH3. An FT-IR study

The adsorption and transformation of ammonia over V₂O₅, V₂O₅/TiO₂, V₂O₅-WO₃/TiO₂ and CuO/TiO₂ systems has been investigated by FT-IR spectroscopy. In all cases ammonia is first coordinated over Lewis acid sites and later undergoes hydrogen abstraction giving rise either to NH₂ amide species or to its dimeric form N₂H₄, hydrazine. Other species, tentatively identified as imide NH, nitroxyl HNO, nitrogen anions N₂⁻ and azide anions N₃⁻ are further observed over CuO/TiO₂. The comparison of the infrared spectra of the species arising from both NH₃ and N₂H₄ adsorbed over CuO/TiO₂ strongly suggest that N₂H₄ is an intermediate in NH₃ oxidation over this active selective catalytic reduction (SCR) and selective catalytic oxidation (SCO) catalysts. This implies that ammonia is activated in the form of NH₂ species for both SCR and SCO, and it can later dimerize. Ammonia protonation to ammonium ion is detected over V₂O₅-based systems, but not over CuO/TiO₂, in spite of the high SCR and SCO activity of this catalyst. Consequently Brönsted acidity is not necessary for the SCR activity.