Catalytic removal of methane over thermal-proof nanostructured catalysts for CNG engines

Five spinel-type catalysts AB₂O₄ (Co_0.8Cr₂O₄, CoCr₂O₄, MnCr₂O₄, MgFe₂O₄ and CoFe₂O₄) were prepared and characterized by XRD, BET and FESEM techniques. The activity of these catalysts towards the combustion of methane was evaluated in a Temperature Programmed Combustion (TPC) apparatus. The half conversion temperature of methane over the Co_0.8Cr₂O₄ catalyst was 369 °C with a W/F = 0.12 g s/cm³. On the basis of Temperature Programmed Desorption (TPD) of oxygen as well as of catalytic combustion runs, the prevalent activity of the Co_0.8Cr₂O₄ catalyst could be explained by its higher capability to deliver suprafacial chemisorbed oxygen species. This catalyst, promoted by the presence of 1 wt% of Pd, deposited by wet impregnation, was lined on cordierite monoliths and then tested in a lab-scale test rig. The combination of Pd and Co_0.8Cr₂O₄ catalysts enables half methane conversion at 340 °C (GHSV = 10,000 h⁻¹), a performance similar to that of conventional 4 wt% Pd-γ Al₂O₃ catalysts but guaranteed with just a four-fold lower amount of noble metal. Both the catalysts in powder and the monolith hosting the Co_0.8Cr₂O₄ + 1 wt% Pd catalyst, submitted to a thermal ageing treatment in air at 700 °C for 12 h, displayed a negligible deactivation.     

An examination of the role of plasma treatment for lean NOx reduction over sodium zeolite Y and gamma alumina Part 2: Formation of nitrogen

NO_x reduction with NO₂ as the NO_x gas in the absence of plasma was compared to plasma treated lean NO_x exhaust where NO is converted to NO₂ in the plasma. Product nitrogen was measured to prove true chemical reduction of NO_x to N₂. With plasma treatment, NO as the NO_x gas, and a NaY catalyst, the maximum conversion to nitrogen was 50% between 180 and 230 °C. The activity decreased at higher and lower temperatures. At 130 °C a complete nitrogen balance could be obtained, however between 164 and 227 °C less than 20% of the NO_x is converted to a nitrogen-containing compound or compounds not readily detected by gas chromatograph (GC) or Fourier transform infrared spectrometer (FT-IR) analysis. With plasma treatment, NO₂ as the NO_x gas, and a NaY catalyst, a complete nitrogen balance is obtained with a maximum conversion to nitrogen of 55% at 225 °C.

For γ-alumina, with plasma treatment and NO₂ as the NO_x gas, 59% of the NO_x is converted to nitrogen at 340 °C. A complete nitrogen balance was obtained at these conditions. As high as 80% NO_x removal over γ-alumina was measured by a chemiluminescent NO_x meter with plasma treatment and NO as the NO_x gas.

When NO is replaced with NO₂ and the simulated exhaust gases are not plasma treated, the maximum NO_x reduction activity of NaY and γ-alumina decreases to 26 and 10%, respectively. This is a large reduction in activity compared to similar conditions where the simulated exhaust was plasma treated. Therefore, in addition to NO₂, other plasma-generated species are required to maximize NO_x reduction.     

ZSM-5分子筛负载金属氧化物催化剂催化燃烧含丙烯腈废气的性能

采用等体积浸渍法将过渡金属Cu负载到ZSM-5分子筛上,并与其他金属(Fe、Co、Ag、Pd、Ce)共浸渍得到负载型催化剂,将其用于全组分丙烯腈废气的催化脱除过程。催化活性评价结果表明,丙烯腈在Cu/ZSM-5催化剂上320℃可以实现完全转化;掺杂质量分数2%Ce后,丙烯腈的完全转化温度降低到300℃,高选择生成N2的温度窗口也变宽,催化剂稳定性高。通过X射线衍射、氮气吸附-脱附、氢气-程序升温还原、氨气-程序升温脱附和X射线光电子能谱等对催化剂的物化性能进行表征,结果表明,催化剂催化氧化丙烯腈尾气的性能依赖于Cu^2+的还原能力、催化剂表面弱酸与中强酸含量以及表面Cu^2+丰度。     

漆包机废气净化催化剂的研制

以γ-Al₂O₃、铈锆固溶体（Ce_0.67Zr_0.33O₂）、以及两者混合物为二载涂层,制备了3种蜂窝瓷漆包机废气净化Pd催化剂,评价其对苯、二甲苯与甲酚催化燃烧的活性。结果表明,γ-Al₂O₃ 与Ce_0.67Zr_0.33O₂混合涂层具有良好的催化活性。采用XRD与BET表征手段,分析了γ-Al₂O₃ 与Ce_0.67Zr_0.33O₂混合涂层具有较好的抗烧结能力,有助于保持活性组分高度分散。     

含氮化合物废气选择性催化氧化技术研究进展

通过对当前含氮化合物废气治理技术的对比分析,总结选择性催化氧化的相关技术优势。根据对含氮化合物的种类及来源分析,介绍氨气、腈类、胺类及其他含氮化合物的催化净化技术。重点总结催化剂的种类、研发进展和在实际使用中可能遇到的问题,同时展望含氮化合物废气选择性催化氧化技术的研发方向。     

Development of a catalytic burner with Pd/NiO catalysts

A catalytic burner was studied which can be used as a heater operated at medium temperature. The catalytic combustion was initiated by an igniter which was placed on the exit surface of the catalyst layer. Noble metal catalysts (Pd/NiO) which were supported on alumina washcoated honeycomb were used, whose maximum heat-resisting temperature is about 900°C. The optimal operating conditions for stable catalytic combustion were obtained by means of analyzing the catalytic combustion region, the temperature distribution, and the combustion efficiency.     

Hydroconversion kinetics of Marlim vacuum residue

A kinetic model was obtained for the Marlim crude vacuum residue (VR) hydroconversion. Marlim VR mixed with FCC decant oil in an 80%/20% weight basis was put in contact with a commercial NiMo on γ-alumina catalyst in a stirred batch reactor. Several temperatures and oil/catalyst ratios were used over different times (0–240 min), at a 110 bar pressure and constant hydrogen flow. The analysis of the collected product showed residua conversions of up to 70%. Hydroconversion kinetics involving thermal and catalytic cracking contributions was proposed to represent the obtained data. The resulting system of differential equations of the kinetic model was solved within reaction time, taking into account the experimental temperature profile. The chi-square objective function was minimized to adjust model parameters. A proposed effective hybrid minimization method was used, by applying a Newton-type method between certain simulated annealing minimization steps. The proposed kinetic model allowed the representation of thermal and catalytic cracking effects, in order to take into account different catalyst concentrations. Therefore it is possible to consider distinct reactor hydrodynamics, such as expanded or bubble column reactors.     

Potentialities and limitations of lean de-NOx catalysts in reducing automotive exhaust emissions

The performance of Pt–γ-Al₂O₃ and CuZSM5 de-NO_x catalysts was evaluated at the exhaust of a lean-burn gasoline engine. It is shown that durability for zeolite catalysts and N₂O formation for Pt catalysts are the main limitations which have to be still overcome to successfully apply the lean de-NO_x technology.     

用于机动车排气净化的含Pd催化剂初步研究

本文制备出一种含Pd催化剂,用于治理机动车排气中的CO、HC和NOx的排放,初步研究了其催化效果,包括空燃比特性和温度特性。实验结果表明,该催化剂具有较好的催化能力。     

NO SCR reduction by hydrogen generated in line on perovskite-type catalysts for automotive diesel exhaust gas treatment

This paper deals with the preparation (by solution combustion synthesis, SCS), characterization (by XRD, BET, FESEM and TPD/R analyses), catalytic activity evaluation (in a temperature-programmed reaction—TPRe apparatus), and the assessment of the reaction mechanism of NO reduction by H₂ in the presence of oxygen on a series of perovskite-type catalysts belonging to the LaFeO₃ family (LaFeO₃, La_0.8Sr_0.2FeO₃, Pd/La_0.8Sr_0.2FeO₃, La_0.8Sr_0.2Fe_0.9Pd_0.1O₃, La_0.7Sr_0.2Ce_0.1FeO₃, Pd/La_0.7Sr_0.2Ce_0.1FeO₃, La_0.7Sr_0.2Ce_0.1Fe_0.9Pd_0.1O₃). The catalysts have been studied in the 25-350 °C temperature range. Significant catalytic activities were measured at 150-250 °C. Among the catalysts screened, La_0.8Sr_0.2Fe_0.9Pd_0.1O₃, showed the best performance. Hence, it was deposited directly over a ceramic honeycomb monolith by in situ SCS and then tested in a lab-scale test rig. A mechanistic analysis is presented concerning the relationship between the observed activity and the reducibility of the B site, determined from TPR experiments, as well as the correlation between the observed oxygen inhibition and the proposed NO_x reduction mechanism.Some final conclusions are drawn on the perspective of the practical application of the investigated after-treatment route for diesel exhaust gases.     

橡胶行业标准废气治理技术方案

本文针对橡胶行业标准提出了密炼车间和压延/硫化车间的废气净化方案.废气治理设备预处理采用干式过滤净化废气.利用复合光催化主机对废气进行光氧催化和后处理,并注入低温等离子以降解异味污染物.蓄热式燃烧利用蓄热式热氧化焚烧炉RTO净化废气,三室RTO废气分解率高于99％,热回收率高于95％.     

稀土钙钛矿型复合氧化物汽车尾气处理催化剂研究现状

分析了近几年研究较多的几类稀土钙钛矿复合氧化物作为汽车尾气催化剂的研究现状、催化效果及优缺点,并展望了该类型催化剂的应用前景。     

Hydrogenation of dimethyl succinate over monolithic catalysts

Hydrogenation of dimethyl succinate over monolithic copper and nickel catalysts was studied using a semibatch reactor in which liquid was circulated, while hydrogen was continuously passed through the mixture. Flow rates of both phases were adjusted, so the system operated in the Taylor flow regime. The process was investigated at 150–240°C and 3–7 MPa. A nickel catalyst was active, but was insufficiently selective. Higher loaded copper catalysts were active and selective with respect to γ-butyrolactone at relatively low conversions. Catalyst activity (initial rates) was similar to that for the liquid phase hydrogenation of maleic anhydride over conventional catalysts previously reported. The catalysts deactivated, but unlike the nickel catalyst, activity of copper catalyst was easily restored by high temperature treatment in hydrogen.     

Synthesis of bulk and alumina-supported γ-Mo2N catalysts by a single-step complex decomposition method

A single-step complex decomposition method for the synthesis of bulk and alumina-supported γ-Mo₂N catalysts is described. The complex precursor (HMT)₂(NH₄)₄Mo₇O₂₄·2H₂O (HMT: hexamethylenetetramine) is converted to γ-Mo₂N under a flow of Ar in a temperature range of 823–1023 K. Furthermore, decomposition of the precursor in a NH₃ flow forms γ-Mo₂N in a temperature range of 723–923 K. Compared with direct decomposition of the precursor in Ar, the reaction in NH₃ shows obvious advantages that the nitride forms at a lower temperature. In addition, alumina-supported γ-Mo₂N catalysts with different nitride loadings can be prepared from the alumina-supported complex precursor in the Ar or NH₃ flow. The resultant catalysts exhibit good dibenzothiophene HDS activities, which are similar to the γ-Mo₂N/γ-Al₂O₃ prepared by traditional TPR method. The catalyst prepared by decomposition in an Ar flow exhibits highest activity. It proves that such a single-step complex decomposition method possesses the potential to be a general route for the preparation of molybdenum nitride catalysts.     

Synthesis, characterization and catalytic applications of mesoporous γ-alumina from boehmite sol

In this study, boehmite sols were used as aluminum precursors for preparing mesoporous alumina (MA) having crystalline framework walls in the presence of non-ionic surfactants as structure directing agents. Nitrogen physisorption showed that aluminas prepared in this way displayed very rich porosities with large mesopores, and both the pore volumes and the pore sizes increased with the surfactant concentration. The improved textural parameters in the samples should be attributed to the three-dimensional interconnected scaffold-like channels, which were formed by randomly ordered stacking and condensing of rigid boehmite nanoparticles with the aid of the surfactant. TEM observations revealed that the precursor morphology had an important effect on the textural properties of the mesoporous alumina. The sample with a corrugated platelet-like morphology exhibited a large surface area of 463 m²/g, which was reduced to 81 m²/g after calcination at 1200 °C, indicating a strong resistance to sintering. This material, with its improved textural properties, crystalline framework walls and high thermal stability, not only could increase the dispersion of the active catalytic species, but also could enhance the diffusion efficiency and mass transfer of reactant molecules when employed as catalyst supports. As examples, our MA samples demonstrated a remarkable enhancement in the catalytic performances for both reactions of SO₂ catalytic reduction by CO and catalytic combustion of methane.     

Ce1−xCuxO2−x/Al2O3/FeCrAl catalysts for catalytic combustion of methane

A series of the Ce_1−xCu_xO_2−x/Al₂O₃/FeCrAl catalysts (x = 0–1) were prepared. The structure of the catalysts was characterized using XRD, SEM and H₂-TPR. The catalytic activity of the catalysts for the combustion of methane was evaluated. The results indicated that in the Ce_1−xCu_xO_2−x/Al₂O₃/FeCrAl catalysts the surface phase structure were the Ce_1−xCu_xO_2−x solid solution, -Al₂O₃ and γ-Al₂O₃. The surface particle shape and size were different with the variety of the molar ratio of Ce to Cu in the Ce_1−xCu_xO_2−x solid solution. The Cu component of the Ce_1−xCu_xO_2−x/Al₂O₃/FeCrAl catalysts played an important role to the catalytic activity for the methane combustion. There were the stronger interaction among the Ce_1−xCu_xO_2−x solid solution and the Al₂O₃ washcoats and the FeCrAl support.     

过渡金属Ni对Pd/Al_2O_3催化剂甲烷催化燃烧性能的影响

考察过渡金属Ni对Pd/Al_2O_3催化剂甲烷催化燃烧活性的影响以及过渡金属负载量及循环条件对甲烷降解性能的影响,采用扫描电镜、N_2吸附-脱附以及H_2程序升温还原技术对催化剂进行表征。结果表明,过渡金属Ni的添加对催化剂在(375~475)℃下的甲烷催化燃烧活性产生影响。催化剂经多次重复使用后,催化燃烧活性提高。分析原因为经过渡金属Ni改性后,可与载体形成NiAl_2O_4尖晶石,促进活性组分形成较小晶粒,并改善活性组分分散度,提高催化剂催化活性。     

催化燃烧法处理聚酯工艺废气的实践

探索用催化燃烧方法处理聚酯生产工艺废气的可行性,并在生产装置上进行中试。介绍了废气处理装置的主要设计参数、处理工艺流程。对装置的安全运行,催化剂的寿命,运行经济性进行了讨论。结果表明:相对于目前的喷淋处理法,该法处理简单,不产生二次污染,成本较低,处理聚酯生产工艺废气是完全可行的。     

Catalytic hydrodehalogenation of halon 1211 (CBrClF2) over γ-alumina-supported Ni, Pd and Pt catalysts

The hydrodehalogenation of halon 1211 over Ni, Pd and Pt supported on γ-alumina was studied. The effect of reaction temperature and hydrogen/halon 1211 input ratio was examined. Steady state catalytic activities of Pd and Pt are very similar, and much higher than that of Ni. Hydrodehalogenation over Pd favours the formation of CH₂F₂, while Pt and Ni produce primarily CH₄ and CH₃F, respectively. Product profiles suggest that the hydrodehalogenation of halon 1211 over Pd and Pt follows a reaction mechanism which is similar to hydrodehalogenation of CFC-12. Over Ni catalysts, the primary hydrodehalogenation reactions are those which first remove one halogen (Cl or Br) and then remove two halogens (one F and either Br or Cl). The higher mobility of hydrogen atom on the surface of Pt is consistent with the observation that only trace amounts of C₂₊ hydrocarbons were detected when Pt was used compared with Pd and Ni. Increasing selectivity to CH₂F₂ with time on stream over Pd and Pt is mainly ascribed to the transformation of support alumina to partially fluorinated alumina.     

Combustion synthesis of perovskite-type catalysts for natural gas combustion

Combustion synthesis has been applied to LaMnO₃ production with a view to boosting its activity towards natural gas combustion by enhancing its specific surface area. With a highly exothermic and self-sustaining reaction, this oxide can be quickly prepared from an aqueous solution of metal nitrates (oxidisers) and urea (fuel).

The favourable conditions for LaMnO₃ formation were sought: only fuel-rich mixtures are effective, but carbonaceous deposits are formed when too much urea is used. In the field of operating conditions in which the combustion synthesis reaction takes place, the specific surface areas were not dramatically higher than those obtained with traditional methods; moreover, even short thermal treatments have been found to rapidly deactivate the catalysts by rapid sintering. With a view to tackling these problems, NH₄NO₃ was chosen as an additive for its low costs, highly exothermic decomposition and because it generates gaseous products only, without altering the proportion of the other elements in the catalysts. With ammonium nitrate, specific area was enhanced from 4 m²/g up to about 20 m²/g. A short thermal treatment at 900 °C partially deactivates also the NH₄NO₃-derived catalysts. It was found that NH₄NO₃-boosted mixtures produce materials whose activity, after a similar thermal treatment, behave practically as the perovskites obtained by the “citrates” method.

Combustion synthesis is though rather cheap—in terms of reactants employed—and quick, given that the process requires few minutes at low temperature without successive calcination. However, the main drawback of this method is that hazardous or polluting compounds are emitted during the synthesis (mainly NH₃ or NO_x).

The MgO introduction, which should act both as a structural promoter and as a sulphur poisoning limiting agent, has proved to be harmful: since MgO does not physically interpose between perovskite grains, it does not offer resistance to deactivation induced by high temperatures.