Dehydrogenation of Isobutane to Isobutene with Carbon Dioxide over SBA‐15‐Supported Chromia‐Ceria Catalysts

A series of SBA‐15‐supported chromia‐ceria catalysts with 3% Cr and 1%–5% Ce (3Cr‐Ce/SBA) were prepared using an incipient wetness impregnation method. The catalysts were characterized by XRD, N₂ adsorption, SEM, TEM‐EDX, Raman spectroscopy, UV–vis spectroscopy, XPS and H₂‐TPR, and their catalytic performance for isobutane dehydrogenation with CO₂ was tested. The addition of ceria to SBA‐15‐supported chromia improves the dispersion of chromium species. 3Cr‐Ce/SBA catalysts are more active than SBA‐15‐supported chromia (3Cr/SBA), which is due to a higher concentration of Cr⁶⁺ species present on the former catalysts. The 3Cr‐3Ce/SBA catalyst shows the highest activity, which gives 35.4% isobutane conversion and 89.6% isobutene selectivity at 570 °C after 10 min of the reaction.     

Influence of impregnation conditions on the activity of CrOx/Al2O3 catalysts in dehydrogenation of isobutane in fixed bed reactor

The development of catalysts for dehydrogenation of light paraffin hydrocarbons in a fixed bed reactor is of great importance for the world petrochemical industry. The preparation of granules (~3 mm in diameter) of CrO_x/Al₂O₃ catalysts is hindered by such problems as homogeneous distribution of active component and modifiers, high strength of granules, etc. In this paper, the alumina support dissolution in the impregnating solution containing chromic acid and the opportunity to apply vacuum impregnation to minimize this effect in the preparation of CrO_x/Al₂O₃ catalysts are discussed. A series of catalysts is synthesized at different impregnation pressures (1, 0.85, and 0.7 atm), characterized by a complex of physical–chemical methods (low-temperature N₂ adsorption, SEM, XRD, TPR-H₂), and tested in isobutane dehydrogenation. The use of vacuum impregnation is shown to lead to the reduction of the specific surface area of the catalysts from to 91 to 56 m²/g and the growth of content of CrO_x phases that decreases the catalytic activity in dehydrogenation. The isobutylene yield at 610 °C decreases from 68% to 54% for the catalyst prepared at P = 0.7 atm as compared with the one prepared at atmospheric pressure. The high activity and stability are connected with the hierarchical structure of the alumina support and homogeneous chromia distribution on its surface.     

Low temperature carbon monoxide catalytic oxidation at the Pd/Ce–Zr–Al–Ox catalyst

The homogeneous chemical composition ceria–zirconia–alumina (Ce–Zr–Al–O_x) nano-alloy were successfully synthesized by surfactant-assisted parallel flow co-precipitation method and applied as supports for low temperature CO oxidation. The experiment conditions were studied in detailed. At 0.92 wt% Pd loading, 30,000 ppm CO could be completely oxidized to CO₂ at 30 °C at a WHSV of 4,380 ml g^?1 h^?1 over the Pd/Ce–Zr–Al–O_x (n_Ce:n_Zr = 3:1) catalyst. Pd/Ce–Zr–Al–O_x catalysts were systematical studied by mean of BET, XRD and TEM analysis. XRD characterization showed that zirconium element entered into cubic structure of ceria and leaded to structure distortion. Addition of aluminum increased specific surface area of ceria–zirconia solid solution substantially. The average pore diameter of Ce–Zr–Al–O_x support palladium catalysts were the key impact factor for CO oxidation. When the Pd/Ce–Zr–Al–O_x catalysts had highly dispersed palladium nanoparticles, large average pore diameter, suitable surface area and pore volume, the activity of CO oxidation was the best.     

Influence of Method of Introduction of Cu- and Zn-Based Modifiers on the Properties of Chromia–Alumina Catalysts

Three methods of introduction of modifiers based on Cu and Zn compounds into the CrO_x/Al₂O₃ catalysts for dehydrogenation of light paraffin hydrocarbons are considered: Introduction from sol, introduction using successive impregnation technique and introduction of modifiers by impregnation along with precursor of chromium oxide. The obtained samples are studied by a complex of physical-chemical methods (XRD, UV-Vis spectroscopy, temperature-programmed reduction with hydrogen (TPR-H₂), X-ray fluorescent (XRF) spectrometry, low-temperature N₂ sorption). The catalytic properties of the samples are studied in kinetic mode in isobutane dehydrogenation. Cu- and Zn-modifiers are shown to influence on the peculiarities of reduction of Cr⁶⁺ and, hence, specify the state of active surface of CrO_x/Al₂O₃ catalysts formed in the reductive reaction medium. Not only do the states of modifiers influence on the initial activity of the catalyst, but also on its activity after oxidative regeneration. Introduction of modifiers by successive impregnation method results in formation of copper and zinc aluminates or defective spinels on the Al₂O₃ surface. When the active component is introduced, the modified surface of the support promotes formation and stabilization of Cr⁶⁺ sites that can undergo reversible reduction–oxidation and provide high activity and selectivity towards formation of isobutylene (>98%).     

介孔氧化铝负载Ni-Co氧化物催化剂上丙烷氧化脱氢制丙烯

以非离子型三嵌段共聚物作为模板剂, 异丙醇铝为氧化铝的前驱物, 采用一锅法合成了一系列介孔氧化铝负载镍氧化物、钴氧化物以及镍-钴双金属氧化物催化剂, 并以介孔氧化铝为载体, 采用浸渍法制备了负载Ni-Co 氧化物催化剂. 采用N₂吸附-脱附、高分辨透射电镜(HRTEM)、X射线粉末衍射(XRD)、H₂程序升温还原(H₂-TPR)以及激光拉曼光谱(LRS)等技术对催化剂的结构与性质进行表征, 并考察了催化剂的丙烷氧化脱氢反应性能. 结果表明: 一锅法制备的各催化剂均有大的比表面积和规整的孔道结构, 且负载的金属氧化物高度分散; 而浸渍法制备的催化剂, 其载体的介孔结构被破坏并有Co₃O₄晶相生成. 在考察的催化剂中, 一锅法合成的介孔氧化铝负载Ni-Co 氧化物催化剂表现出最佳的丙烷氧化脱氢性能. 在450 °C、C₃H₈:O₂:N₂的摩尔比为1:1:4和空速(GHSV)为10000 mL·g^-1·h^-1条件下, 该催化剂上丙烯产率为10.3%, 远高于浸渍法制备的催化剂上所获得的丙烯产率(2.4%). 关联催化剂表征和反应结果, 讨论了催化剂结构与性能之间的关系.     

Uncovering selective and active Ga surface sites in gallia–alumina mixed-oxide propane dehydrogenation catalysts by dynamic nuclear polarization surface enhanced NMR spectroscopy

Gallia–alumina (Ga,Al)₂O_3(x : y) spinel-type solid solution nanoparticle catalysts for propane dehydrogenation (PDH) were prepared with four nominal Ga : Al atomic ratios (1 : 6, 1 : 3, 3 : 1, 1 : 0) using a colloidal synthesis approach. The structure, coordination environment and distribution of Ga and Al sites in these materials were investigated by X-ray diffraction, X-ray absorption spectroscopy (Ga K-edge) as well as ²⁷Al and ⁷¹Ga solid state nuclear magnetic resonance. The surface acidity (Lewis or Brønsted) was probed using infrared spectroscopy with pyridine and 2,6-dimethylpyridine probe molecules, complemented by element-specific insights (Ga or Al) from dynamic nuclear polarization surface enhanced cross-polarization magic angle spinning ¹⁵N{²⁷Al} and ¹⁵N{⁷¹Ga} J coupling mediated heteronuclear multiple quantum correlation NMR experiments using ¹⁵N-labelled pyridine as a probe molecule. The latter approach provides unique insights into the nature and relative strength of the surface acid sites as it allows to distinguish contributions from Al and Ga sites to the overall surface acidity of mixed (Ga,Al)₂O₃ oxides. Notably, we demonstrate that (Ga,Al)₂O₃ catalysts with a high Al content show a greater relative abundance of four-coordinated Ga sites and a greater relative fraction of weak/medium Ga-based surface Lewis acid sites, which correlates with superior propene selectivity, Ga-based activity, and stability in PDH (due to lower coking). In contrast, (Ga,Al)₂O₃ catalysts with a lower Al content feature a higher fraction of six-coordinated Ga sites, as well as more abundant Ga-based strong surface Lewis acid sites, which deactivate through coking. Overall, the results show that the relative abundance and strength of Ga-based surface Lewis acid sites can be tuned by optimizing the bulk Ga : Al atomic ratio, thus providing an effective measure for a rational control of the catalyst performance.

Coordination geometry and Lewis acidity of Ga and Al (bulk and surface) sites in mixed oxide gallia–alumina nanoparticles is correlated with the performance in propane dehydrogenation.     

Genesis and activity of mo-based hydrotreating catalysts prepared by a sol-gel method

Molybdenum oxide-alumina catalysts used in hydrodesulfurization (HDS) with a wide range of Mo loadings (1–25% Mo) were prepared by the sol-gel process. Two different methods of adding the molybdenum oxide precursor to the support were used.In the first route, alumina is prepared by hydrolysis of aluminium tri sec-butylate in butanol and butanediol, and molybdenum is deposited by a classical dry impregnation with ammonium heptamolybdate (AHM). In the second route, the molybdenum oxospecies are dispersed in butanediol and added to the aluminium alkoxide before hydrolysis. The solids were calcined to obtain the oxide precursors which are then sulfided to give the active phase in hydrodesulfurization.The effect of preparation on the structural properties of alumina as well as on the state and dispersion of molybdenum in the dried, calcined and sulfided form was studied by various characterization techniques (XRD, XPS, Raman spectroscopy). Molybdenum appears to be present as well dispersed oxomolybdenum species in the oxide form even at high loadings. This good dispersion of molybdenum is preserved after sulfidation which induces the formation of MoS₂ crystallites whose morphology has been determined by HREM.The catalyst activities were evaluated in thiophene hydrodesulfurization and compared with that of catalysts prepared by dry impregnation of a commercial alumina. The observed performances are in agreement with the good dispersion of molybdenum at high loadings we were able to obtain owing to the sol-gel process.     

Mechanochemical-thermal preparation and structural studies of mullite-type Bi2(GaxAl1−x)4O9 solid solutions

A series of Bi₂(Ga_xAl_1−x)₄O₉ solid solutions (0≤x≤1), prepared by mechanochemical processing of Bi₂O₃/Ga₂O₃/Al₂O₃ mixtures and subsequent annealing, was investigated by XRD, EDX, and ²⁷Al MAS NMR. The structure of the Bi₂(Ga_xAl_1−x)₄O₉ solid solutions is found to be orthorhombic, space group Pbam (No. 55). The lattice parameters of the Bi₂(Ga_xAl_1−x)₄O₉ series increase linearly with increasing gallium content. Rietveld refinement of the XRD data as well as the analysis of the ²⁷Al MAS NMR spectra show a preference of gallium cations for the tetrahedral sites in Bi₂(Ga_xAl_1−x)₄O₉. As a consequence, this leads to a far from random distribution of Al and Ga cations across the whole series of solid solutions.     

Ammoxidation of ethylene to acetonitrile over chromium or cobalt alumina catalysts prepared by sol–gel method

A series of Cr/Al₂O₃ and Co/Al₂O₃ catalysts were tested in the selective ammoxidation of ethylene to acetonitrile. Catalysts were prepared either by sol–gel method or by impregnation with chromium or cobalt acetylacetonate salts. Physicochemical properties of catalysts were accomplished by several techniques such as chemical analysis, physisorption of N₂, X-ray diffraction (XRD), ²⁷Al MAS NMR, UV–Visible diffuse reflectance (DRS) and Raman spectroscopy and temperature programmed reduction of H₂ (H₂–TPR). Textural analysis reveals that mesoporous materials with pronounced surface areas were obtained using sol–gel procedure while impregnation of the support produces a moderate decrease of its surface area and pore volume. XRD analysis confirms the presence of highly dispersed metal species which reside essentially on the surface and measure less than 4 nm. Furthermore, ²⁷Al MAS NMR shows that for xerogels, part of metal species occupies sites on/in A1₂O₃ in close vicinity of octahedral ²⁷Al. This, apparently, is not the case for aerogels. For Cr/Al₂O₃ catalysts, isolated Cr⁶⁺, mono and polychromate species were identified using DRS, Raman Spectroscopy and H₂–TPR which seem to play a key role in the ammoxidation of ethylene. Furthermore, for cobalt doped catalysts, CoAl₂O₄ was identified as active phase on the basis of DRS and H₂–TPR results. From the supercritical drying, it results generally better catalysts than catalysts calcined by ordinary procedure which leads to inactive agglomerated Co₃O₄ and CoO–Al₂O₃ phase.     

Hydrodefluorination of non-activated C-F bonds by diisobutyl-aluminiumhydride via the aluminium cation [i-Bu2Al]

A novel system for the hydrodefluorination (HDF) of non-activated C-F bonds at room-temperature is described. The reaction of i-Bu₂AlH with [Ph₃C][B(C₆F₅)₄] (1), [Ph₃C][Al(C₆F₅)₄] (2) and [Ph₃C][Al{OC(CF₃)₃}₄] (3) as precatalysts leads under formation of triphenylmethane to the aluminium cation [i-Bu₂Al]⁺ and the non-coordinating anions [M(C₆F₅)₄]⁻ (M = B, Al) and [Al{OC(CF₃)₃}₄]⁻. The formed aluminium cation is very reactive towards C-F bonds and easily forms i-Bu₂AlF releasing a carbocation that abstracts the hydride of excess i-Bu₂AlH and yields the corresponding hydrocarbon. Thereby, the active species [i-Bu₂Al]⁺ is regenerated and can realize a catalytic cycle. For 1-fluorohexane as an example including non-activated C-F bonds different activities were found (TON: 1: 20; 2: 12; 3: 30) in cyclohexane as solvent.     

烷基膦酸促进负载磷钨酸催化异丁烷/丁烯烷基化反应

异丁烷/丁烯烷基化是生产高辛烷值汽油的重要反应,目前主要采用液体强酸为催化剂,而固体催化剂用于该反应的性能均不理想。我们设计合成出十六烷基膦酸(HDPA)修饰的氧化硅负载型磷钨酸纳米多级结构催化剂(HDPA-HPW/SiO2),其结构与悬铃木果实相似。通过X射线衍射(XRD)、傅里叶变换红外光谱(FT-IR)、透射电子显微镜镜(TEM)、氮气吸附-脱附、异丁烷吸附-脱附等对该催化剂进行了表征,并使用固定床微型反应器评价了其对异丁烷/丁烯烷基化反应的催化性能。结果表明,HDPA的外围修饰增强了催化剂对烃类反应物的吸附,减少了烯烃聚合副反应和催化剂表面积碳的产生,提高了高辛烷值产物的选择性,延长了催化剂的寿命。     

Coordination chemistry of the activation of [(triazacyclohexane)CrCl3] with [PhNMe2H][B(C6F5)4] and AlR3

Complexes of N-substituted 1,3,5-triazacyclohexanes with CrCl₃ form 1:1 adducts with [PhNMe₂H][B(C₆F₅)₄] with increased solubility in toluene. Addition of AlⁱBu₃ leads to free PhNMe₂ and a complex with [B(C₆F₅)₄]⁻ weakly coordinated to chromium via a meta-fluorine atom. This complex can polymerise and/or trimerise olefins similar to methyl aluminoxane activated complexes. Decomposition of the active complex involves transfer of the triazacyclohexane to aluminium leading to [(triazacyclohexane)AlⁱBu₂][B(C₆F₅)₄] and [(arene)₂Cr][B(C₆F₅)₄]. These chromium(I) complexes have been characterised by X-ray crystallography and prove that chromium is reduced to the oxidation state +I during the catalysis.     

Synthesis and Characterization of Some Unique Heterocyclic Derivatives Containing Aluminium(III) Atoms in 4- and 6-Co-Ordination States∶ Reaction of Bis(β-Diketonato) Aluminium (III)-DI-μ-Isopropoxo-DI-Isopropoxo Aluminium(III) with Triphenylsilanol and Diphenylsilanediol

Reactions of bis ( g -diketonato) aluminium(III)-di- w -isopropoxo-di-isopropoxo-aluminium (III), [CH₃COCHCOR)2Al( w -OPrⁱ)₂Al(OPrⁱ) ₂], with triphenylsilanol, Ph₃SiOH, in 1:1 and 1:2 molar ratios and with diphenylsilanediol, Ph₂Si(OH)₂, in a 1:1 molar ratio, have resulted in the synthesis of [(CH₃COCHCOR)₂Al( w -OPrⁱ)₂Al(OSiPh₃)(OPrⁱ)], [(CH₃COCHCOR)₂Al( w -OPrⁱ)₂Al(OSiPh₃)₂] and [(CH₃COCHCOR)₂Al( w -OPrⁱ)₂Al(OSiPh₂O], respectively. These are soluble in a variety of organic solvents ( e.g. , benzene, chloroform and dimethylsulfoxide) and show dinuclear behaviour in chloroform. These derivatives have been characterized by elemental analyses, molecular weight measurements, IR and NMR (¹H, ¹³C and ²⁷Al) studies.     

Characterization and Catalytic Properties of Aerogel Chromium Oxide Supported by Alumina or Silica

Alumina or silica supported chromium oxide catalysts prepared by sol-gel technique have been investigated by X-ray diffraction, BET analysis, combined diffuse reflectance spectroscopy, EPR and reduction-extraction by ethane 1,2 diol. The results reveal the presence of Cr³⁺, Cr⁵⁺ and Cr⁶⁺ ions. Chromium species Cr⁶⁺ are isolated and atomically dispersed on the alumina support as free chromate CrO ₄ ^2– while on silica, dichromate or polychromate species like Cr₂O ₇ ^2– or Cr₃O ₁₀ ^2– predominate. Chromium oxide exhibits a better catalytic properties for paraxylene partial oxidation, when it is supported on alumina. The difference of oxidation states and degree of oligomerisation of chromium on the two supports affects the catalytic properties.     

A Non-Hydrolytic Sol-Gel Approach for the Preparation of Mg x Al2(1−x)Ti(1+x)O5 Powders

The study of non-hydrolytic reactions for the synthesis of Mg _x Al_2(1?x)Ti_(1+x)O₅ solid solution with x = 0.6 is reported. The reagents chosen were Al(OsBu)₃, Ti(OiPr)₄, TiCl₄ and Mg(NO₃)₂·6H₂O in toluene. The reactions were followed using ¹³C Nuclear Magnetic Resonance (NMR) spectroscopy. Sol-gel synthesized powders were calcined in air at 300, 500, 1000, and 1200°C for 1 h. The powders were analysed by X-Ray Diffraction (XRD) demonstrating the formation of a Mg_0.6Al_0.8Ti_1.6O₅ phase in samples treated at the higher calcination temperature.     

Al(HSO4)3 and Al2O3-SO3H as Efficient Catalysts for Modified Preparation of 3,4-Dihydropyrimidin-2 (1H)-ones/thiones

An environmentally friendly procedure for the preparation of dihydropyrimidinone derivatives or their sulfur analogues under thermal solvent-free conditions in the presence of aluminium hydrogen sulfate [Al(HSO₄)₃] and alumina sulfuric acid (Al₂O₃-SO₃H) as heterogeneous catalysts was developed.     

Synthesis of novel termetallic isopropoxides

Novel termetallic isopropoxides are reported which may be represented by the general formulae: [(PrⁱO)₃M(μ-OPrⁱ)₂Be(μ-OPrⁱ)₂Al(OPrⁱ)₂], [(PrⁱO)₂M(μ-OPrⁱ)₂Be(μ-OPrⁱ)₂Al(OPrⁱ)₂]₂ [where M = Ti(IV), Zr(IV) and Hf(IV)] and [(PrⁱO)₄M(μ-OPrⁱ)₂Be(μ-OPrⁱ)₂Al(OPrⁱ)₂] [where M = Nb(V) and Ta(V)]. Attempts to synthesize derivatives with the general formula, [(PrⁱO)₇M₂(μ-OPrⁱ)₂Be(μ-OPrⁱ)₂Al(OPrⁱ)₂] [where M = Ti(IV), Zr(IV) or Hf(IV)], were unsuccessful and in all such cases a mixture of M(OPrⁱ)₄ and [(PrⁱO)₃M(μ-OPrⁱ)₂Be(μ-OPrⁱ)₂Al(OPrⁱ)₂] was obtained. All these derivatives are soluble in common organic solvents and with the exception of titanium(IV) derivatives, they can be volatilised without noticeable disproportionation. These products have been characterized by elemental analyses, molecular weights, IR, ¹H NMR and (in representative cases) mass spectral studies also.     

A new approach to the preparation of lanthanide catalysts for the synthesis of 2-propyl-3-ethylquinoline based on the reactions of LnCl3 · 6H2O crystalline hydrates with triisobutylaluminum

A new approach to the preparation of lanthanide catalysts for the synthesis of nitrogen heterocycles (exemplified by 2-propyl-3-ethylquinoline) was developed based on the reactions of LnCl₃ · 6H₂O crystalline hydrates with alkylaluminums. It was found that the interaction of LnCl₃ · 6H₂O (Ln = Ce, Pr, Tb, and Eu) with iso-Bu₃Al in aromatic solvents (20°C) resulted in the formation of soluble (isobutane and the alumoxane (iso-Bu₂Al)₂O) and insoluble products (with the empirical formula LnCl₃ · xH₂O · y(iso-Bu₂Al)₂O (x = 0.4–0.7; y = 0.04–0.07)). The physiochemical properties of LnCl₃ · xH₂O · y(iso-Bu₂Al)₂O were studied, and these compounds were found to be highly efficient catalysts for the reaction of aniline condensation with butyraldehyde to form 2-propyl-3-ethylquinoline.     

Effect of chelating agents on catalytic performance of Cr/γ-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> dehydrogenation catalysts

Chromia/alumina (Cr₂O₃/γ-Al₂O₃) catalysts with addition of chelating agents (citric acid or oxalic acid) were prepared by the incipient impregnation method. The resulting catalysts with different citric acid (CA) or oxalic acid (OA) contents were applied to the dehydrogenation of isobutane to isobutene. The influence of chelating agents on the catalysts was investigated by means of BET, SEM, H₂-TPR, NH₃-TPD, and TG-DTG. The results showed that the Cr₂O₃/γ-Al₂O₃ catalysts with addition of CA or OA exerted slightly increase on specific surface area. The addition of the chelating agents as expected, determined a general decrease in the surface acidity. The catalysts with CA or OA have a better anti-coking ability by inhibiting the side reaction of cracking and carbon formation. The addition of CA or OA for preparing these catalysts resulted in a beneficial effect on the reducibility of the Cr species to diminish the reduction temperature. The appropriate content of chelating agents could improve dispersion of metal species in the γ-Al₂O₃ support. The catalytic activity showed an important enhancement when the metal species was impregnated in the presence of CA or OA.