分子筛类催化剂上甲烷选择性催化还原NOx研究进展

选择性催化还原NOx是处理工业废气和稀燃汽车尾气NOx的有效方法。由于还原剂甲烷廉价易得,甲烷选择性催化还原NOx（简称CH4-SCR）已成为近年来的研究热点,而分子筛类催化剂因催化活性高而得到广泛研究。本文综述了CH4-SCR脱除NOx体系中不同金属负载的分子筛催化剂及反应机理方面的研究进展,包括Co系、Pd系、In系等分子筛催化剂在催化性能、反应机理及掺杂改性等方面的研究现状,并提出了分子筛类催化剂用于CH4-SCR的研究方向。     

富氧条件下稀土修饰的Co/MOR催化剂上甲烷选择性催化还原一氧化氮性能

以丝光沸石分子筛(MOR)为载体,采用浸溃法制备以钴为主活性组分和稀土金属为催化剂助剂的M(1)Co(10)/MOR(M=La、Ce、Pr和Nd)系列催化剂,考察其在富氧条件下选择性催化还原NO的性能.采用XRD、热重-质谱连用系统和NH3-TPD等方法对催化剂进行表征.XRD结果表明,Co物种主要以Co3O4形式存在...     

H-USY负载MnOx催化剂上CH4选择催化还原NOx性能的研究

采用高比表面积、抗硫、抗湿的新型USY分子筛为载体制备MnOx催化剂,考察了以CH4为还原剂,在不同Mn含量MnOx催化剂上,选择性催化还原NOx的性能和有关影响因素.研究表明:5%(wt.)的Mn/H-USY具有最高的NO选择性还原活性,在500℃时NOx达最大转化率20.8%;分段填装Mn/H-USY和Ni/H-USY催化剂可显著拓宽活性温度范围,促进NO转化率(最高转化率可达24.4%),降低N2O生成量.本实验中使用傅立叶红外分析仪进行在线检测反应物与产物浓度.     

NOx低温选择性催化还原催化剂研究进展

催化剂是选择性催化还原脱硝技术的核心,其催化性能直接关系到脱硝效果的好坏。本文介绍了该领域新开发的贵金属、金属氧化物、分子筛、碳基催化剂等低温脱硝体系及其最新研究进展。对碳纳米材料催化剂和新型杂多酸催化剂等新成果作了介绍,并且对今后的研究方向作了展望。     

选择性催化还原NOx的反应机理研究

选择性催化还原法（SCR）脱除NOx具有较高的效率,是目前工业中应用最广泛的工艺。催化还原NOx的反应过程相当复杂。概括了H₂、CO、烃类、NH₃和尿素等作为还原剂选择性催化还原氮氧化物的各种反应机理,详细论述了催化还原过程中形成的中间体,如亚硝基甲烷、烯醇式物质[CH₂=O)、NO₂［NH₄+］₂、NO_y、C_xH_yO_zN、C_xH_yO_z、NO⁺、NCO或C_tH_xO_yN_z等,并讨论了催化剂和载体表面上的氧空缺和活性中心对SCR的影响,展望了这一领域的研究方向。     

选择性催化还原NOx催化剂的研究进展

综述了选择性催化还原法脱除NOx的各类催化剂,包括贵金属、分子筛、金属氧化物等。传统催化剂由于不能同时兼备优良的催化活性、热稳定性、抗中毒能力,因此难以真正实现商业化。由不同类型催化剂优化组合而成的复合型催化剂和NOx的存储一还原型催化剂克服了传统催化剂的上述缺点,在脱除NOx领域具有广阔的应用前景。     

铜系催化剂选择性催化还原脱除NOx研究

以硅胶改性堇青石蜂窝陶瓷为载体,分别制备了以Cu-O、Cu-Ce-O和Cu-Ce-Mn-O为活性组分的催化剂。以CO(NH₂)₂为还原剂,在固定床反应器中进行选择性催化还原NO的研究。采用XRD、SEM和BET等测试方法对催化剂进行表征。结果表明,在温度(300～500) ℃,催化剂Cu-Ce-Mn-O/SiO₂/堇青石的活性优于催化剂Cu-O/SiO₂/堇青石和Cu-Ce-O/SiO₂/堇青石,反应温度为450 ℃、空速为8 000 h^-1时,Cu-Ce-Mn-O/SiO₂/堇青石催化剂催化还原NO的转化率可达到88%。     

氮氧化物选择性催化还原催化剂研究进展

氮氧化物是形成酸雨和光化学烟雾的主要物种和引发物,消除氮氧化物污染是环境保护中的重点和难点。选择性催化还原作为一种有效脱除氮氧化物的方法,在近年来得到了广泛深入的研究。本文对有关催化体系的文献进行了总结。     

选择性催化还原脱硝催化剂研究进展

催化剂是选择性催化还原(selective catalytic reduction,SCR)脱硝技术的核心,催化剂的低温活性、选择性和稳定性直接影响到NOx的脱除效果.SCR脱硝催化剂性能主要取决于催化剂活性组分和催化剂载体.简述了以氨、尿素和碳氢化合物等不同物质作为SCR还原剂的化学反应原理;介绍了以贵金属(Pt,Pd,Rh,Au等)和金属氧化物(V2O5,WO3,FeaO3,CuO,CrOx,MnO2.MoO3和NiO等)为催化剂活性组分.以分子筛、柱撑黏土、碳基材料和TiO2等为催化剂载体的SCR脱硝催化剂的研究进展.以V2O3为主要活性组分,以TiO2为载体的钒钛类催化剂因其理想的综合性能,目前已商业化应用.纳米有序结构TiO2薄膜可望成为理想的SCR脱硝催化荆新型载体.     

Influence of sulphate doping on Pd/zirconia based catalysts for the selective catalytic reduction of nitrogen oxides with methane

The effect of sulphating zirconia on the selective catalytic reduction of NO by CH₄ in oxygen excess of Pd catalysts has been investigated. Since both the acidity and the Pd dispersion both contribute to the activity and selectivity of these catalysts a series of samples were prepared with different sulphate contents but maintaining the amount of Pd constant. Significant chemical and textural changes were caused by sulphating the zirconium hydroxide starting material, which lead to a clear improvement in the catalytic behaviour. A medium sulphate doping (≈4 wt.% expressed as SO₄²⁻) was found to be the most adequate to promote activity and selectivity in these Pd-sulphate zirconia based catalysts.     

Selective catalytic reduction of nitrogen oxides by ammonia on iron oxide catalysts

In this study, new Fe₂O₃ based materials are developed for the selective catalytic reduction (SCR) of NO_x by NH₃ in diesel exhaust. As a result of the catalyst screening, performed in a synthetic model exhaust, ZrO₂ is considered to be the most effective carrier for Fe₂O₃. The modification of the Fe₂O₃/ZrO₂ system with tungsten leads to drastic increase of SCR performance as well as pronounced thermal stability. These results show that tungsten acts as bifunctional component. The highest catalytic activity is observed for ZrO₂ that is coated with 1.4 mol% Fe₂O₃ and 7.0 mol% WO₃ (1.4Fe/7.0W/Zr). By the use of this catalyst quantitative conversion of NO_x is obtained between 285 and 430 °C with selective formation of N₂. Here, the turnover frequency of NO_x per Fe atom is found to be 35 × 10⁻⁵ s⁻¹ that indicates a high catalytic performance. The SCR activity of the 1.4Fe/7.0W/Zr material is decreased in the presence of H₂O and CO₂, whereas it is increased by NO₂.Temperature programmed reduction by H₂ (HTPR) analyses show that the Fe sites of the 1.4Fe/7.0W/Zr catalyst are mainly in the form of crystalline Fe₂O₃, whereby relatively small oxide entities are also present. The strongly aggregated Fe₂O₃ species are associated with the presence of the promoter tungsten. Based upon stationary catalytic examinations as well as diffuse reflectance infrared fourier transform spectroscopy (DRIFTS) studies we postulate an Eley Rideal type mechanism for SCR on 1.4Fe/7.0W/Zr catalyst. The mechanistic model includes a redox cycle of the active Fe sites. As first reaction step, we assume dissociative adsorption of NH₃ that leads to partial reduction of the iron as well as to production of very reactive amide surface species. These amide intermediates are supposed to react with gaseous NO to form N₂ and H₂O. In the final step, the reduced Fe sites be regenerated by oxidation with O₂. As a side reaction of SCR, imide species, originated from decomposition of amide, are oxidized by NO₂ or O₂ into NO.     

富氧条件Co/H-ZSM-5催化剂上CH4选择催化还原NO的研究

采用离子交换法制备了一系列具有不同硅铝比和不同Co负载量的Co/H-ZSM-5催化剂样品。富氧条件下考察了硅铝比、Co负载量、空速、O₂浓度及酸位对催化剂选择催化还原活性的影响。并对其进行了XRD、BET、H₂-TPR和DRS-UV-vis等表征。催化结果表明，催化剂的催化活性随Co负载量的增加而增加，随硅铝比的增加而减少；NO转化率随着空速的增加而降低。O₂体积分数为2%时，NO达最大转化率。表征结果表明，Co²⁺为活性中心，酸中心的存在对催化活性有一定的促进作用。     

Selective catalytic reduction of nitrogen monoxide with methane over impregnated In/HZSM-5 in the presence of excess oxygen

In/HZSM-5 catalyst prepared by the impregnation method was active for NO reduction with methane. Complete reduction of NO was obtained at 450°C over an In/HZSM-5 catalyst. The presence of oxygen in the feed greatly enhanced the NO reduction activity of In/HZSM-5. Co/HZSM-5 and Ga/HZSM-5 were less effective than In/HZSM-5. Cu/HZSM-5, In/Na-ZSM-5 and In₂O₃/Al₂O₃ were ineffective for NO reduction with CH₄. The NO reduction activity was proportional to the level of indium impregnated onto HZSM-5 but excess amounts of indium were detrimental to the catalytic activity. Phase analysis by XRD measurements demonstrated that there was a threshold value in the indium content, i.e., the maximum dispersion capacity of indium oxides. It is concluded that highly dispersed indium species are the active centers for the selective catalytic reduction of NO with CH₄.     

氧化铝负载镍催化剂催化丙酮胺化选择性合成异丙胺

通过XRD、XRF和BET分析表征浙江省低碳脂肪胺工程技术研究中心提供的氧化铝负载镍催化剂a和催化剂b的结构,将催化剂用于催化丙酮胺化反应合成异丙胺,考察原料配比、反应温度、反应压力和丙酮空速对合成异丙胺反应的影响。结果表明,催化剂的比表面积和装填方式影响催化剂活性。丙酮胺化合成异丙胺的最佳合成条件为:反应压力(0.3~0.4)MPa,反应温度(383.15~393.15)K,n(丙酮)∶n(氨气)∶n(氢气)=1∶3∶(3~4),空速(0.30~0.35)h-1,在最佳条件下,异丙胺选择性100%,异丙胺产率最高达97.22%,催化剂连续使用4个月仍保持较好的催化活性。氧化铝负载镍催化剂上丙酮胺化反应机理主要是加成-消除-还原反应机理,而还原-取代反应机理是次要形式。     

Selective reduction of nitrogen oxides by hydrocarbons on hydrotalcite Co and Ni catalysts

Hydrotalcitelike Co-Al and Ni-Al catalysts of different compositions (with the atomic ratio M ²⁺/Al³⁺ = 0.5–3.0) were studied in the reaction of selective reduction of NO by propane, propylene, and n-decane in the presence of O₂. The higher activity of the catalysts with M ²⁺/Al³⁺ = 0.5 is connected with high dispersity of Ni or Co cations stabilized by a significant amount of Al³⁺ ions. Propylene was shown to be the most efficient reducing agent for nitrogen oxide. The highest degree of conversion to the extent of 90–99% was attained at 400 and 420–440°C for Ni-Al and Co-Al samples, respectively. When propane and decane were used as reducing agents, the conversion of both catalysts was characterized by the volcano-shaped dependence on temperature due to the fact that the catalyst took part in the concurrent reaction of hydrocarbon (reducing agent) oxidation. Hydrotalcitelike materials are promising representatives of inexpensive bi- and multicomponent systems. The design strategy for new active catalysts for processes of purification of gas exhausts from NO _x , that are stable in the presence of water and sulfur oxides, may be based on usage of hydrotalcites with modified ions introduced into them.     

Selective catalytic reduction of NOx with propene over double wash-coat monolith catalysts

Selective catalytic reduction (SCR) among the approaches for alleviating NOx emission was much attracted. Zeolites have the advantage for adsorption of propene, and noble metal catalyst has the advantage for oxidation of NO to NO₂. Pt (or Au)/Al₂O₃ (or SiO₂) were used as the lower layer of double wash-coated monolith catalysts. Zeolites (H-mordenite or ZSM-5) were coated as the upper layer. The catalytic performance of the double wash-coated catalyst was, remarkably, improved. Also, temperature window was shifted to lower temperature and broadened. It was known that the combined noble metal monolith catalyst with zeolite was very effective in removing NOx by SCR with hydrocarbons.     

Selective catalytic reduction of NO and NO2 at low temperatures

The fast SCR reaction using equimolar amounts of NO and NO₂ is a powerful means to enhance the NO_x conversion over a given SCR catalyst. NO₂ fractions in excess of 50% of total NO_x should be avoided because the reaction with NO₂ only is slower than the standard SCR reaction.

At temperatures below 200 °C, due to its negative temperature coefficient, the ammonium nitrate reaction gets increasingly important. Half of each NH₃ and NO₂ react to form dinitrogen and water in analogy to a typical SCR reaction. The other half of NH₃ and NO₂ form ammonium nitrate in close analogy to a NO_x storage-reduction catalyst. Ammonium nitrate tends to deposit in solid or liquid form in the pores of the catalyst and this will lead to its temporary deactivation.

The various reactions have been studied experimentally in the temperature range 150–450 °C for various NO₂/NO_x ratios. The fate of the deposited ammonium nitrate during a later reheating of the catalyst has also been investigated. In the absence of NO, the thermal decomposition yields mainly ammonia and nitric acid. If NO is present, its reaction with nitric acid on the catalyst will cause the formation of NO₂.     

Reforming of methane and coalbed methane over nanocomposite Ni/ZrO2 catalyst

Nanocomposite Ni/ZrO₂-AN catalyst consisting of comparably sized Ni metal and ZrO₂ nanoparticles is studied in comparison with zirconia- and alumina-supported Ni catalysts (Ni/ZrO₂-CP and commercial Ni/Al₂O₃-C) for steam reforming of methane (SRM) and for combined steam and CO₂ reforming of methane (CSCRM). The reactions are performed under atmospheric pressure with stoichiometric amounts of H₂O and CH₄ or (H₂O + CO₂) and CH₄ at 1073 K. Under a wide range of methane space velocity (gas hourly space velocity of methane GHSV_CH4 = 12,000–96,000 ml/(h g_cat.), the nanocomposite Ni/ZrO₂-AN catalyst always shows higher activity and stability for both SRM and CSCRM reactions. The two supported Ni catalysts (Ni/ZrO₂-CP and Ni/Al₂O₃-C) exhibit fairly stable catalysis under low GHSV_CH4 but they are easily deactivated under high GHSV_CH4 and become completely inactive when they are reacted for ca.100 h at GHSV_CH4 = 48,000 ml/(h g_cat.). The CSCRM reaction is carried out with different H₂O/CO₂ ratios in the reaction feed while keeping the molar ratio (H₂O + CO₂)/CH₄ = 1.0, the results prove that the nanocomposite Ni/ZrO₂-AN catalyst can be highly promising in enabling a catalytic technology for the production of syngas with flexible H₂/CO ratios (ca. H₂/CO = 1.0–3.0) to meet the requirements of various downstream chemical syntheses.