Transfer and Reaction Performances of Selective Catalytic Reduction of N2O with CO over Monolith Catalysts

This work tries to identify the relationship between geometric configuration of monolith catalysts, and transfer and reaction performances for selective catalytic reduction of N2O with CO. Monolith cat...     

Pd-Ba/Ce-Zr-La-Al2O3/堇青石催化剂对甲基丙烯酸尾气的催化燃烧

采用浸渍法制备Pd-Ba/Ce-Zr-La/堇青石催化剂,以甲基丙烯酸尾气为模型,考察Ba的引入对Pd催化剂催化燃烧活性的影响。并用XRD、BET、SEM和TPD等对催化剂进行了表征。研究表明,Ba的引入提高了催化剂的催化活性和热稳定性,经500 ℃焙烧的Pd-Ba/Ce-Zr-La/堇青石催化剂（Pd和Ba质量比为1∶7.5）具有很好的催化活性,起燃温度为130 ℃,完全燃烧温度仅为153 ℃,经1 000 ℃焙烧后,催化剂仍保持较高催化活性。     

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.     

Effective regeneration of thermally deactivated commercial V-W-Ti catalysts

An effective method for the regeneration of thermally deactivated commercial monolith SCR catalysts was investigated. Two types of regenerated solutions, namely NH₄Cl (1 mol/L) and dilute H₂SO₄ (0.5 mol/L), were employed to treat the used catalyst. The effects of temperature and the regeneration process on the structural and textural properties of the catalysts were determined by X-ray diffraction, scanning electron microscopy, N₂ adsorption/desorption, elemental analysis and Fourier transform infrared spectroscopy. The results suggest that the anatase phase of the used catalyst is maintained after exposure to high temperatures. Some of the catalytic activity was restored after regeneration. The catalyst regenerated by aqueous NH₄Cl had a higher activity than that of the catalyst treated by dilute H₂SO₄. The main reason is that the NH₃ generated from the decomposition of NH₄Cl at high temperatures can be adsorbed onto the catalyst which promotes the reaction. The aggregated V₂O₅ were partially re-dispersed during the regeneration process, and the intrinsic oxidation of ammonia with high concentrations of O₂ is a factor that suppresses the catalytic activity.     

Competition between NO reduction and NO decomposition over reduced V–W–O catalysts

The SCR of NO and NO decomposition were investigated over a V–W–O/Ti(Sn)O₂ catalyst on a Cr–Al steel monolith. The conversions of NO and NH₃ over the reduced and oxidised catalysts were determined. The higher conversion of NO than of NH₃ was observed in SCR over the reduced catalyst and very close conversions of both substrates were found over the oxidised one. The increase of the pre-reduction temperature was found to cause an increase in catalyst activity and its stability in direct NO decomposition. The surface tungsten cations substituted for vanadium ones in vanadia-like active species are considered to be responsible for the direct NO decomposition. The results of DFT calculations for the 10-pyramidal clusters: V₁₀O₃₁H₁₂ (V–V) and V₉WO₃₁H₁₂ (V–W) modelling (0 0 1) surfaces of vanadia and WO₃–V₂O₅ solid solution (s.s.) active species, respectively, show that preferable conditions for NO adsorption exist on W sites of s.s. species and that reduction causes an increase in their ability for electron back donation to the adsorbed molecule. Electron back donation is believed to be responsible for the electron structure reorganisation in the adsorbed NO molecule resulting in its decomposition. The high selectivity of NO decomposition to dinitrogen was considered to be connected with the formation of the tungsten nitrosyl complexes solely via the W–N bond.     

Catalytic decomposition of N2O over monolithic supported noble metal-transition metal oxides

The decomposition of nitrous oxide to nitrogen and oxygen using a series of monolithic (ceria-alumina washcoated cordierite) supported transition metal (Cu, Fe, Co, Ni, Mn) and noble metal (Ir, Rh) oxide catalysts has been studied using gas chromatography. The effect of combining a transition metal with a noble metal has also been investigated. A synergetic effect was observed between transition metal and noble metal oxides in the presence of a small amount of water for some of the catalysts. The synergy between Fe-Ir and Ni-Ir was also verified under dry conditions. X-ray photoelectron spectroscopic measurements on these catalysts indicate that Fe, Rh and Ir are present predominantly as Fe₂O_3, RhO₂ and IrO₂, while significant amounts of Co and Ni ions may migrate inside the support to form cobalt and nickel aluminate. Only the Fe-Ir catalyst showed a significant interaction between the noble metal and the transition metal. The effect of water, oxygen and carbon monoxide on the catalytic behaviour of the five most active catalysts (Ni-Ir, Ni-Rh, Fe-Ir, Co-Ir, Ir) has also been investigated. Oxygen and water were found to inhibit the catalytic activity, although the extent of oxygen inhibition is limited, presumably due to the presence of ceria in the monolith washcoat support. Conversely, carbon monoxide greatly enhances catalytic activity.     

Catalytic oxidation of trichloroethylene in two-component mixtures with selected volatile organic compounds

The activity of two noble metal catalysts (Pt and Pd) on metallic monolithic support and one perovskite (La_0.5Ag_0.5MnO₃) on cordierite monolith was tested in the oxidation of selected volatile organic compounds (VOCs) and trichloroethylene (TCE), oxidized alone and in two-component mixtures of TCE with a non-halogenated compound. Only over the Pt catalyst each compound in the reaction mixtures strongly enhanced TCE oxidation. Over Pd, promoting effect on TCE oxidation was observed for toluene and ethanol only. Over perovskite, each non-chlorinated compound was found to inhibit TCE oxidation. The presence of TCE was found to inhibit the oxidation of each compound added over both noble metal catalysts, but it had no influence on the oxy-derivatives oxidation over the perovskite catalyst.     

Enhanced methanation stability of nano-sized MoS2 catalysts by adding Al2O3

A series of unsupported MoS₂ catalysts with or without Al₂O₃ modification was prepared using a modified thermal decomposition approach. The catalysts were tested for the methanation of carbon monoxide and the optimum one has 25.6 wt-% Al₂O₃ content. The catalysts were characterized by nitrogen adsorption measurement, X-ray diffraction and transmission electron microscopy. The results show that adding appropriate amount of Al₂O₃ increases the dispersion of MoS₂, and the increased interaction force between MoS₂ and Al₂O₃ can inhibit the sintering of active MoS₂ to some extent.     

Analysis and Modeling of a Monolithic Reactor

This work reports the results of experimental and theoretical investigations of NO decomposition in a catalytic monolith reactor. Monolithic catalysts are composed of a commercial cordierite substrate (Corning Inc.) and copper containing ZSM‐5 zeolite (Si/Al = 40; 1.92 % Cu). Laboratory scale activity tests were carried out in the integral monolith reactor, operating under atmospheric pressure at different temperatures (573–773 K) and at various space times. The reactor performance was modeled using several mathematical models. The kinetics of NO decomposition was described by a LHHW type rate equation. The parameters of the monolith reactor models were estimated from experimental data using a modified differential method and Nelder‐Mead method of non‐linear optimization. It was found that the behavior of the experimental monolithic reactor was mainly limited by interphase mass transfer. The 2D heterogeneous model with distributed parameters was determined to be the most suitable mathematical model for detailed consideration of physico‐chemical processes occurring in the catalytic monolith reactor.     

单分散Co3O4@SiO2核壳催化剂的制备及N2O催化分解性能

N₂O是一种重要的温室气体,且对臭氧层有很大的破坏作用,而直接催化分解法是除去N₂O最经济有效的方法之一。针对目前报道较多的钴氧化物催化剂活性较差的问题,将包覆型Co₃O₄核壳材料引入N₂O直接催化分解反应,利用核壳结构的限域特性与壳层的多孔孔道使Co₃O₄分散性增加,粒径减小,金属载体相互作用与接触反应界面增强,从而提高了催化剂在N₂O直接催化分解反应中的低温活性。此外,还制备了一系列不同金属含量的Co₃O₄@SiO₂球形核壳催化剂来研究包覆结构对催化剂性能的影响,通过X射线荧光光谱（XRF）、透射电镜（TEM）、X射线衍射（XRD）、N₂物理吸附、H₂-程序升温还原（H₂-TPR）等表征,证实在保证稳定单分散核壳结构的前提下,活性Co₃O₄位点越多,催化剂反应活性越好。     

Promotion effect of residual K on the decomposition of N2O over cobalt–cerium mixed oxide catalyst

A series of cobalt–cerium mixed oxide catalysts (Co₃O₄–CeO₂) with a Ce/Co molar ratio of 0.05 were prepared by co-precipitation (with K₂CO₃ and KOH as the respective precipitant), impregnation, citrate, and direct evaporation methods and then tested for the catalytic decomposition of N₂O. XRD, BET, XPS, O₂-TPD and H₂-TPR methods were used to characterize the catalysts. Catalysts with a trace amount of residual K exhibited higher catalytic activities than those without. The presence of appropriate amount of K in Co₃O₄–CeO₂ may improve the redox property of Co₃O₄, which is important for the decomposition of N₂O. When the amount of K was constant, the surface area became the most important factor for the reaction. The co-precipitation-prepared catalyst with K₂CO₃ as precipitant exhibited the best catalytic performance because of the presence of ca. 2 mol% residual K and the high surface area. We also discussed the rate-determining step of the N₂O decomposition reaction over these Co₃O₄–CeO₂ catalysts.     

Preparation of niobates of rhodium and nickel and their catalytic behaviors during calcination and reduction treatments

Double oxides of Rh and Ni have been prepared by chemical mixing methods. Silica-supported and unsupported RhNbO₄ and NiNb₂O₆ catalysts exhibited strong metal-oxide interaction behaviors in ethane hydrogenolysis activities after the decomposition of the double oxides by H₂ reduction at 500°C. Silica-supported and zeolite-supported RhVO₄ catalysts showed high activity and selectivity for dehydrogenation of cyclohexane after the decomposition in H₂. The double-oxide catalyst systems can be used as starting materials to obtain high-performance metal catalysts (redispersion of metals by H₂ reduction and regeneration of catalysts by calcination at a high temperature).     

Study of Ag/La0.6Ce0.4CoO3 catalysts for direct decomposition and reduction of nitrogen oxides with propene in the presence of oxygen

Perovskite-type oxide La_0.6Ce_0.4CoO₃ and its doped Ag catalysts were prepared and their catalytic performances were evaluated for the direct decomposition of NO and the selective reduction of NO with propene in the presence of oxygen. A noticeable enhancement in activity was achieved by doping Ag and the optimum Ag loading was 1%. The effects of H₂O, SO₂, CO₂ and O₂ on the performances of Ag/La_0.6Ce_0.4CoO₃ catalysts for NO decomposition were also investigated. The resistance against H₂O and SO₂ appears satisfactory. The inhibition by CO₂ is strong, although it is reversible. Oxygen did not inhibit the NO decomposition reaction but significantly promoted it. Compared with other perovskite-type oxides reported previously, higher conversions were obtained over the present catalysts for the NO reduction by propene. We speculate that the decomposition of NO is the predominant process even in the presence of propene. The catalysts were characterized by N₂-adsorption, XRD, XPS and NO-TPD and some explanations were put forward.     

Hurdles and solutions for reactions between gas and liquid in a monolithic reactor

In this paper, proof of principle experiments and exploratory work that solves the problem of ensuring that a gaseous and a liquid reactant are available at the catalytically active site at the same time by separating the reaction and the transport of the gaseous reactant. The equipment consisted of an autoclave in which a feed was saturated with hydrogen, a reactor with a catalyst coated on a monolith, a pump to circulate the feed/product stream, and devices to control and monitor the process.

A lot of information of how the process can be practised was gathered during the work. Conversion per pass should be below the amount of hydrogen that can be dissolved in the liquid to avoid coke deposition (and hence deactivation) of the catalyst. The effectiveness of the catalyst coated on the monolith was found to be 100%.

Several variations of the process design and catalysts used were explored. Integration of the monolith with a heat exchanger will obviously allow for the use of the process for very exothermic reactions like (nitro)benzene hydrogenation. A monolith to which Rh-cyclooctadiene-1,2-bis-diphenylfosfino-ethane (a homogeneous catalyst) was tethered was equally active in hydrogenation of 1-hexene as Rh-cyclooctadiene-1,2-bis-diphenylfosfino-ethane tethered to a standard alumina. This allows (fine)chemical producers to repeatedly use the expensive homogeneous catalysts without the need for separation of the catalyst from the reaction mixture.     

Ag-modified H-Beta, H-MCM-41 and SiO2: Influence of support, acidity and Ag content in ozone decomposition at ambient temperature

Silver-modified H-MCM-41-50, H-Beta-11 and SiO₂ catalysts were synthesized by incipient wet impregnation method using aqueous solution of silver nitrate. The catalysts were characterized using X-ray powder diffraction, scanning electron microscope, X-ray fluorescence, nitrogen physisorption and FTIR spectroscopy. The catalysts were tested in the heterogeneous catalytic decomposition of ozone at ambient temperature. The highest degree of ozone decomposition was observed over the mild acidic 5 wt.% Ag-H-MCM-41-50 (98%) mesoporous molecular sieve catalyst followed by 5 wt.% Ag-SiO₂ (90%). It was found that the most acidic catalyst 5 wt.% Ag-H-Beta-11 showed the lowest ozone decomposition. The content of Ag was also observed to influence the ozone decomposition. The 5 wt.% Ag-H-MCM-41-50 mesoporous molecular sieve catalyst exhibited higher catalytic activity than 2 wt.% Ag-H-MCM-41-50. The acidic properties, structure of catalyst supports and the metal content were found to be important for the ozone decomposition reaction.     

甲烷催化燃烧与十二烷脱氢反应的间接热耦合

将甲烷催化燃烧的Pd-Zr/SBA-15/Al2 O3/FeCrA1金属整体式催化剂和十二烷催化脱氢的Pt-Sn-Li/Al2 O3/FeCrA1金属整体式催化剂分别填充在套管式反应器的内管和环隙中,在电炉伴温条件下研究了这两个反应的热耦合.实验结果表明,炉温略低于催化剂床层温度,说明吸热反应所需的热量来源于放热反应,...     

Catalytic decomposition of N2O over CeO2 promoted Co3O4 spinel catalyst

A series of CeO₂ promoted cobalt spinel catalysts were prepared by the co-precipitation method and tested for the decomposition of nitrous oxide (N₂O). Addition of CeO₂ to Co₃O₄ led to an improvement in the catalytic activity for N₂O decomposition. The catalyst was most active when the molar ratio of Ce/Co was around 0.05. Complete N₂O conversion could be attained over the CoCe0.05 catalyst below 400 °C even in the presence of O₂, H₂O or NO. Methods of XRD, FE-SEM, BET, XPS, H₂-TPR and O₂-TPD were used to characterize these catalysts. The analytical results indicated that the addition of CeO₂ could increase the surface area of Co₃O₄, and then improve the reduction of Co³⁺ to Co²⁺ by facilitating the desorption of adsorbed oxygen species, which is the rate-determining step of the N₂O decomposition over cobalt spinel catalyst. We conclude that these effects, caused by the addition of CeO₂, are responsible for the enhancement of catalytic activity of Co₃O₄.     

Effect of Mn/Al ratio in Co–Mn–Al mixed oxide catalysts prepared from hydrotalcite-like precursors on catalytic decomposition of N2O

The Co–Mn–Al mixed oxide catalysts were prepared by thermal decomposition of hydrotalcite-like precursors with Co/(Mn + Al) molar ratio of 2 and Mn/Al molar ratio varying from 0 to 2. The obtained catalysts were characterized by powder XRD, XPS, BET surface area and TPR measurements and tested in N₂O decomposition. The most active Co4MnAl catalyst exhibited both the optimum Mn/Al molar ratio and the optimum amount of components reducible in the temperature region in which the catalytic reaction proceeds (350–450 °C).     

CoMnO_x/Al_2O_3/monolith整体催化剂的制备及其催化臭氧分解性能

以铝胶为粘结剂,采用浆料涂覆法制备整体式臭氧分解催化剂CoMnO_x/Al_2O_3/monolith。考察固体颗粒性质、浆料流变性质和焙烧温度对整体催化剂机械稳定性的影响。结果表明,当Al_2O_3与CoMnO_x投料质量比为1∶4、球磨时间2 h、浆料pH=3.5～4.0、分散剂聚乙二醇用量6%(质量分数)和焙烧温度400℃时,制备的催化剂机械稳定性好,超声30 min,涂层脱落率为2.5%。评价该催化剂的臭氧催化分解性能,在臭氧浓度为15×10~(-6)(体积分数),空速为60 000 h~(-1),反应温度为90℃,催化剂反应670 h后臭氧转化率仍维持在99.8%,将反应温度降为80℃,继续反应400 h后转化率仍维持在99.0%。     

不同前体制备Ni催化剂及其在硫碘制氢中催化分解HI的性能

硫碘制氢是目前最有潜力的大规模低成本制氢方法之一。HI催化分解是硫碘制氢的关键步骤。本文采用4种具有代表性的镍盐前体--硝酸镍[Ni（NO₃）₂]、乙酸镍[Ni（CH₃COO）₂]和两种有机金属络合镍（乙酰丙酮镍[Ni（acac）₂]和亚硝酸三乙二胺合镍（[Ni（en₃）]（NO₂）₂）制备Ni催化剂,考察了不同镍盐前体对制备的Ni催化剂特性的影响规律以及Ni催化剂在HI催化分解中的性能。采用了BET、XRD和TEM等分析测试技术对制备的Ni催化剂进行了表征。研究结果表明,镍盐前体对制备的Ni催化剂的分散度、催化活性以及催化稳定性有重要的影响。以Ni（NO₃）₂和[Ni（en₃）]（NO₂）₂为前体制备的Ni催化剂具有良好的Ni金属分散度,Ni颗粒分散均匀且尺寸较小。由于高温和强腐蚀的反应环境（HI-I₂-H₂O体系）,Ni催化剂经过反应都会出现不同程度的失活。以[Ni（en₃）]（NO₂）₂为前体制备的Ni催化剂表现出最好的催化活性和稳定性,有望成为未来大规模硫碘制氢系统中HI分解的催化剂。