Rare earth oxides as carbon oxidation catalysts

The behavior of a number of rare earth oxides as catalysts for the oxidation of graphite in air has been investigated by the methods of thermal analysis. Of the oxides studied, only CeO₂ showed significant activity in accelerating the gasification of graphite by oxygen between 500 and 1000°C. Cerium salts, which decompose to a finely dispersed oxide phase at low temperatures, e.g. Ce (III) nitrate and ammonium Ce (IV) nitrate, were found to be very active catalysts. The catalytic effect may be due to a redox process involving the cyclic conversion of the oxide from the Ce (IV) to the Ce (III) oxidation state, or the oxide particles may provide sites for the dissociative chemisorption of oxygen.     

复合氧化物固体超强酸催化氧化正丁醇合成正丁酸

采用共沉淀法制备了复合二元金属氧化物固体超强酸SO₄^2-/ZrO₂-Fe₂O₃、SO₄^2-/ZrO₂-SnO、SO₄^2-/ZrO₂-SnO₂和SO₄^2-/ZrO₂-NiO,运用XRD和IR等分析技术对所合成的固体超强酸进行表征。并对其催化氧化正丁醇合成正丁酸的性能进行了研究。实验结果表明,NiO的加入明显提高了ZrO₂由四方相向单斜相转化的温度,焙烧温度923 K时,ZrO₂仍然保持四方相。并且发现,4种复合固体超强酸对正丁醇的催化氧化合成正丁酸均有一定的催化活性,且SO₄^2-/ZrO₂-NiO的催化活性最好。正丁醇催化氧化合成正丁酸的最佳反应温度为343 K,在此温度下,以NiO质量分数为10％经923 K焙烧的SO₄^2-/ZrO₂-NiO为催化剂时,产物中正丁酸质量分数最高可达85.5％,选择性99.1%。     

复合金属氧化物催化丙烷选择氧化制丙烯酸

采用溶液法制备Mo-V-Te-Nb-O催化剂,研究了焙烧次数对催化剂性能的影响,考察催化剂在普通密封条件下储存时间和连续反应过程中的稳定性。结果表明,二次焙烧制备的催化剂中M1和M2相增强,对丙烯酸生成有利,且晶相形态不随焙烧次数的增加而改变,而烧结现象逐渐增加。催化剂可在普通密封条件下储存24个月,性能不发生变化,催化剂活性和选择性随反应进行不断震荡升高,丙烯酸初期收率为24.7%,反应180 h左右达31.8%,随后催化剂迅速失活。XRD、BET表征及催化剂再生实验表明,其失活的主要原因是Te流失。     

Preparation of mesoporous copper cerium bimetal oxides with high performance for catalytic oxidation of carbon monoxide

A series of mesoporous copper cerium bimetal oxides with different copper contents were replicated from the KIT-6 silica using mixed solutions of Cu(II) and Ce(III) nitrates as metal sources. These bimetal oxides were characterized by XRD, TEM, nitrogen sorption at 77 K and XPS. Catalytic oxidation of CO as a standard reaction was used to test their activities. The optimized performance was achieved for the catalyst CuCeO₂-20 with 20 mol% copper contents and half CO conversion was reached at 350 K with a space velocity of 260,000 mL h⁻¹ g_cat⁻¹. No obvious deactivation was observed for over 10 h on stream at 373 K.     

Characterization study of CeO2 supported Pd catalyst for low-temperature carbon monoxide oxidation

Catalysts consisting of palladium supported on cerium dioxide (Pd/CeO₂) were prepared and used for carbon monoxide oxidation in a stoichiometric mixture of carbon monoxide and oxygen. Pd/CeO₂ exhibits high catalytic activity for the oxidation of CO, showing markedly enhanced catalytic activities due to the combined effect of palladium and cerium dioxide. The Pd/CeO₂ catalyst is superior to Pd/ZrO₂, Pd/Al₂O₃, Pd/TiO₂, Pd/ZSM-5 and Pd/SiO₂ catalysts with regard to the activity under the conditions examined. The catalysts were characterized by means of XRD and TPR. The position of the H₂-TPR peak shifts to lower temperature with increasing Pd loading from 0.25 to 2.0%. CeO₂ inhibits the hydrogen reduction of PdO. CO-TPR measurements have shown the existence of three peaks. The low-temperature peak (α) is due to the Pd hydroxide species. The β peak has been attributed to finely dispersed PdO. The high-temperature peak (γ) has been attributed to crystal phase PdO. Crystal phase PdO is more difficult to reduce by CO than finely dispersed PdO. On the basis of the catalytic activity and CO-TPR results, we conclude α species (Pd hydroxide) mainly contribute to the catalytic activity for low-temperature CO oxidation. This revised version was published online in July 2006 with corrections to the Cover Date.     

Catalytic oxidation of carbon monoxide under periodic operation

A growing literature demonstrates resonance of the rate of CO oxidation with frequency of composition switching and that a global increase in rate under composition modulation is possible. Differences are found for the various metal catalysts used: CO oxidation is stimulated at frequencies between 0.1 and 1.0 Hz over noble metals, whereas stimulation occurs at frequencies below 0.05 Hz with oxide catalysts. Multiple resonances with an apparent harmonic relationship, “wrong-way” response, or very slow relaxation to reproducible cycles have been observed. These differences suggest mechanisms through which rate improvements arise are not the same for all catalysts.     

钛铝复合氧化物催化材料的研究进展

钛铝复合氧化物催化材料的发展为研究选择加氢反应、氧化脱氢和加氢脱硫等化工工艺提供了新途径。钛铝复合氧化物由于制备简单、可操作性强等优点,引起了人们的广泛重视。本文综述了钛铝复合氧化物催化材料的制备研究进展,同时简要概述了Ti O2-Al2O3复合氧化物材料在酯化反应、选择加氢、催化选择还原NO、氧化脱氢、甲醇合成、光催化反应、加氢脱硫等方面的应用。简要比较了几种方法制得的Ti O2-Al2O3复合氧化物,提出了该复合材料在目前研究应用中存在的问题及解决途径,并展望了其应用前景。     

CO Oxidation Behavior of Copper and Copper Oxides

Carbon monoxide oxidation activities over Cu, Cu₂O, and CuO were studied to seek insight into the role of the copper species in the oxidation reaction. The activity of copper oxide species can be elucidated in terms of species transformation and change in the number of surface lattice oxygen ions. The propensity of Cu₂O toward valence variations and thus its ability to seize or release surface lattice oxygen more readily enables Cu₂O to exhibit higher activities than the other two copper species. The non-stoichiometric metastable copper oxide species formed during reduction are very active in the course of CO oxidation because of its excellent ability to transport surface lattice oxygen. Consequently, the metastable cluster of CuO is more active than CuO, and the activity will be significantly enhanced when non-stoichiometric copper oxides are formed. In addition, the light-off behaviors were observed over both Cu and Cu₂O powders. CO oxidation over metallic Cu powders was lighted-off because of a synergistic effect of temperature rises due to heat generation from Cu oxidation as well as CO oxidation over the partially oxidized copper species.     

Effect of the surface area of cobaltic oxide on carbon monoxide oxidation

Various surface area (S_BET) of cobaltic oxide (Co₃O₄) are prepared by different methods, i.e., precipitation–oxidation, impregnation and hydrothermal. The effect of S_BET of Co₃O₄ on the catalytic property toward CO oxidation is investigated. The results indicate that the optimum S_BET of Co₃O₄ could increase the catalytic activity. Characterization of the cobaltic oxide using X-ray diffraction (XRD), N₂-adsorption at –196 °C, infrared (IR) and temperature-programmed reduction (TPR) reveals that the increase of S_BET on Co₃O₄ can weaken the bond strength of Co–O and promote more lattice oxygen desorption from Co₃O₄ to cause the reduction become easy. We conclude that the S_BET effect, caused by various prepared methods and refined conditions, are responsible for the activity enhancement of Co₃O₄. The T₅₀ (the conversion of CO reached 50%) is decreased significantly when the S_BET is increased, i.e., PO-R230 > PO-C400 > I-C550 > H-150 ~D-Strem.     

Enhanced carbon monoxide oxidation activity over gold–ceria nanocomposites

The composites with nanosized gold loaded in nanoporous ceria were prepared on a large scale by a facial and environment-benign sol–gel process. These materials were characterized by XRD, ICP, BET, UV–vis absorption, XPS, HRTEM and EDX. The main factors such as size and surface state of the Au and defect in the ceria could be adjusted by acid treatment of the composites in ascorbic acid solution to improve the activity and decrease the content of noble metal Au in the materials. Enhanced catalytic activities were obtained for the CO oxidation reaction over the catalysts due to the small crystal sizes with narrow size distributions of gold nanoparticles, a large amount of defects in the nanoporous ceria support, as well as a high ratio of Au³⁺/Au⁰ in the nanocomposites.     

Selective production of methanol from syngas over LaTi1−xCuxO3 mixed oxides

Carbon monoxide hydrogenation was studied over partially substituted copper-containing LaTi_1–xCu_xO₃ oxides and on copper supported on La₂O₃. The unsubstituted (x = 0) oxide was weakly active for CO hydrogenation, whereas all the other oxides were more active and exhibited high selectivity to methanol. Particularly, for substitutions x = 0.5–0.6, where the perovskite structure was observed, CO conversions close to 22% and selectivity close to 80% were found. Cu/La₂O₃ was, however, less active and yielded CO₂ and hydrocarbons as the major products. Using X-ray photoelectron spectroscopy it was determined that under reaction conditions copper exists as reduced species. The L₃VV X-ray induced Auger transition at 1849.2 eV observed for a representative LaMn_0.5Cu_0.5O₃ catalyst prereduced and used in CO hydrogenation at 573 K, suggests that Cu⁺ species dominates in spent catalyst. These Cu⁺ species are believed to be stable under reaction conditions in the perovskite structure, only a slight Cu enrichment occurs on the topmost layer of catalysts.     

Catalytic oxidation of propane over molybdenum-based mixed oxides

Catalytic oxidation of propane to produce propene was investigated over molybdenum-based mixed oxide catalysts. Cobalt or magnesium oxide combined with molybdenum oxide exhibits the best catalytic performance for the oxidative dehydrogenation of propane. Catalytic activities of both Co-Mo-O and Mg-Mo-O vary drastically on the catalyst composition and Co(Mg)_0.95Mo_1.0O_x having small amounts of free MoO₃ on the Co(Mg)MoO₄ surface shows the highest catalytic activity keeping a considerably high selectivity to propene. The catalytic activity also depends strongly on the acidic properties of catalysts and MoO₃ clusters formed on the surface of Co(Mg)MoO₄ are responsible for the activities for the oxidative dehydrogenation of propane.     

Selective oxidation of ammonia to nitrogen on transition metal containing mixed metal oxides

The selective catalytic oxidation of ammonia to nitrogen (NH₃-SCO) has been studied over hydrotalcite derived mixed metal oxides containing Cu, Co, Fe or Ni. XRD, BET, NH₃-TPD and TPR techniques were used for catalysts characterization. Results of NH₃-SCO were compared with those of selective catalytic reduction of NO with NH₃ (NO-SCR). Reaction mechanism was studied by temperature-programmed surface reaction (TPSR) and activity tests with a various contact time. Catalytic performance of the studied samples depends on both kind and loading of transition metals in the mixed metal oxide system. The Cu-containing samples have been found to be the most active catalysts of the NH₃-SCO process. Transition metal loading strongly influences distribution of ammonia oxidation products. The highest selectivity to N₂ was measured for the catalysts with the lowest transition metal content.     

Catalytic combustion of toluene over mixed Cu–Mn oxides

The influence of the synthesis pH and of the Zn and/or Al additives on the Cu–Mn precursors, obtained by co-precipitation at a constant pH from aqueous solutions of appropriate nitrates at (Cu + Zn)/(Mn + Al) ratio equal 2, was investigated. The relative content of Mn increased with the pH of precipitation. Depending on the sample composition the identified crystalline phases included layered hydroxy double salt, hydrotalcite-like structure, CuO and ZnO. Some precursors had strongly amorphous character. Calcination of the precursors at 673 K resulted in mixed oxides, in which CuO of various degrees of crystallinity could be identified. The Mn-containing phases remained amorphous. All calcined materials proved extremely active in catalytic combustion of toluene. Some catalysts reached 100% conversion already at 403 K. High conversions observed in the low temperature regime were partially due to the strong sorption of toluene. In the catalysts containing Al additive this effect was suppressed.     

Aqueous‐phase ketonization of acetic acid over Zr/Mn mixed oxides

Aqueous‐phase ketonization possesses significant advantages over gas‐ or organic‐phase ketonization for improved conversion efficiency of aqueous fraction accompanied by algal bio‐oil production. In this study, synthetized ZrO₂ and Zr/Mn oxides are used for aqueous‐phase ketonization of acetic acid. ZrMn_0.5O_x shows the highest ketonization activity at 340°C for 12 h, achieving maximum acetone yield of 88.27%; and all catalysts exhibited selectivity higher than 96.75%. Apparent activation energy and acid reaction order are 161.2 kJ mol^?1 and 0.70, respectively. Results suggest high ketonization activity of poorly crystallized tetragonal ZrO₂. Addition of Mn results in ZrO₂/MnO_x solid solution and improves active sites. Acid property and Mn⁴⁺ content are important factors, and oxygen vacancy demonstrates relationship with ketonization activity for ZrO₂. Examination of recovered catalysts indicates that ZrMn_yO_x exhibits improved stability, and Mn leaching and crystal phase transformation are main causes of deactivation in aqueous‐phase ketonization. © 2017 American Institute of Chemical Engineers AIChE J, 63: 2958–2967, 2017     

Oxygen transfer in mixed oxides in the case of CO oxidation over oxides containing Cu, Mo and V

The combined measurement of reaction rate and oxygen activity in the catalyst by solid electrolyte potentiometry (SEP) can be used in principle to examine the concept of oxygen transfer in mixed oxides, often used to explain synergetic effects between different solid phases. This is shown in the case of copper molybdate and a Mo-V-O_x mixed oxide, using the oxidation of CO as a test reaction. Both the pure oxidic phases and a physical mixture are used in the study. The rate measurements show that the addition of Mo-V-O_x, inactive in CO oxidation, enhances the catalytic activity of CuMoO₄. On the other hand, SEP measurements indicate the existence of a gradient of oxygen activity between the two phases as the driving force of oxygen transfer from the Mo-V oxide to the copper molybdate. This revised version was published online in July 2006 with corrections to the Cover Date.     

The oxidation of carbon monoxide at ambient temperature over mixed copper–silver oxide catalysts

Cu₂Ag₂O₃ has been prepared by a precipitation method and evaluated for ambient temperature carbon monoxide oxidation. The Cu₂Ag₂O₃ catalyst demonstrated appreciable activity and a relationship with preparation ageing time was observed. An ageing time of 4 h produced a catalyst with the highest oxidation performance. The catalyst precursor materials, prepared by drying at room temperature, displayed initial high activity, which decreased with time on line. The precursors were transformed during CO oxidation to form the mixed oxide Cu₂Ag₂O₃ as the material was dried in situ. A comparison of the catalytic activity has been made with a representative sample of a high activity hopcalite, mixed copper/manganese oxide catalyst. On the basis of CO oxidation rate data corrected for the effect of catalyst surface area the Cu₂Ag₂O₃, aged for 4 h was at least as active as the hopcalite catalyst.     

Catalytic Oxidation of CO over Nanocrystalline La1–xCexNiO3 Perovskite‐Type Oxides

Nanocrystalline La_1–xCe_xNiO₃ (x = 0.1, 0.3, 0.5, 0.7, 0.9) perovskite‐type oxide catalysts prepared by the Pechini method were employed in catalytic CO oxidation and the effect of substitution of La by Ce on CO conversion was evaluated. The results indicated the remarkable effect of La substitution with Ce on the catalytic performance at low temperatures. The reaction temperature had a significant influence on the stability of the catalysts. The La_0.1Ce_0.9NiO₃ sample exhibited the highest activity among the prepared catalysts in CO oxidation reaction. In addition, the influence of different parameters including pretreatment condition, feed ratio, and gas hourly space velocity (GHSV) on the catalytic performance was examined. The optimum catalyst proved high stability under severe reaction conditions in the presence of water vapor and CO₂ in the feed stream.     

Cu-Zr-Ce-O复合氧化物催化剂上CO选择性氧化性能

将共沉淀法制备的Cu-Zr-Ce-O复合氧化物催化剂应用于富氢气体中CO的选择性氧化反应,研究了ZrO₂掺杂量及预处理方法对催化剂性能的影响,并通过H₂-TPR、CO-TPR等手段对催化剂进行了表征.结果表明,掺杂ZrO₂的Cu₁Zr₁Ce₉O_δ催化剂在160～200℃之间具有99％以上的CO转化率和相对较高的选择性.掺杂适量的ZrO₂能够提高催化剂的热稳定性和储氧能力,促进催化剂表面吸附氧向晶格氧的转化.经氧气预处理的Cu₁Zr₁Ce₉O_δ催化剂活性最高.催化剂上Cu⁺/Cu²⁺氧化还原离子对和表面的晶格氧含量均影响催化剂的活性,但在富氢气氛下,表面的晶格氧对催化剂的性能影响较大.