Oxidative dehydrogenation of propane over vanadium oxide based catalysts Effect of support and alkali promoter

The oxidative dehydrogenation of propane was investigated using vanadia type catalysts supported on Al₂O₃, TiO₂, ZrO₂ and MgO. The promotion of V₂O₅/Al₂O₃ catalyst with alkali metals (Li, Na, K) was also attempted. Evaluation of temperature programmed reduction patterns showed that the reducibility of V species is affected by the support acid–base character. The catalytic activity is favored by the V reducibility of the catalyst as it was confirmed from runs conducted at 450–550°C. V₂O₅/TiO₂ catalyst exhibits the highest activity in oxydehydrogenation of propane. The support’s nature also affects the selectivity to propene; V₂O₅ supported on Al₂O₃ catalyst exhibits the highest selectivity. Reaction studies showed that addition of alkali metals decreases the catalytic activity in the order non-doped>Li>Na>K. Propene selectivity significantly increases in the presence of doped catalysts.     

助催化剂Sn、Ga、In和K对丙烷脱氢催化剂Pt/Al2O3

用廉价的丙烷脱氢制丙烯是解决丙烯供应紧张问题的途径之一,研究优异性能的丙烷脱氢催化剂具有重要意义。采用分步浸渍法制备不同类型的丙烷脱氢催化剂Pt/Al₂O₃,在固定床反应器中考察助催化剂Sn、Ga、In和K对催化剂性能的影响。结果表明,Pt-Sn/Al₂O₃催化剂性能略优于Pt-Ga/Al₂O₃和Pt-In/Al₂O₃,并且比较稳定。在Pt-Sn/Al2O3催化剂中加入适量K,可有效改善催化剂性能,但高温条件下积炭严重,有待深入研究和改进。     

PtSn负载量对PtSn/Al2O3催化剂上丙烷脱氢性能的影响

由丙烷直接催化脱氢制取丙烯已经成为增产丙烯的重要手段之一。以水热法制备Al_2O_3载体,采用等体积浸渍法制备不同PtSn负载量的PtSn/Al_2O_3催化剂。通过XRD、N2-吸附、拉曼光谱和H2-TPR等对其进行表征,并考察不同PtSn负载量对催化剂催化丙烷脱氢性能的影响。结果表明,在制备的催化剂中,Pt1.5Sn3/Al_2O_3具有最高的催化丙烷脱氢活性和稳定性,丙烷初始转化率高达55.6%,丙烯选择性98.1%。反应330 min后,丙烷转化率仅降约10%,选择性保持不变。     

Total oxidation of propene and propane over gold–copper oxide on alumina catalysts: Comparison with Pt/Al2O3

Oxidation of propene and propane to CO₂ and H₂O has been studied over Au/Al₂O₃ and two different Au/CuO/Al₂O₃ (4 wt.% Au and 7.4 wt.% Au) catalysts and compared with the catalytic behaviour of Au/Co₃O₄/Al₂O₃ (4.1 wt.% Au) and Pt/Al₂O₃ (4.8 wt.% Pt) catalysts. The various characterization techniques employed (XRD, HRTEM, TPR and DR-UV–vis) revealed the presence of metallic gold, along with a highly dispersed CuO (6 wt.% CuO), or more crystalline CuO phase (12 wt.% CuO).

A higher CuO loading does not significantly influence the catalytic performance of the catalyst in propene oxidation, the gold loading appears to be more important. Moreover, it was found that 7.4Au/CuO/Al₂O₃ is almost as active as Pt/Al₂O₃, whereas Au/Co₃O₄/Al₂O₃ performs less than any of the CuO-containing gold-based catalysts.

The light-off temperature for C₃H₈ oxidation is significantly higher than for C₃H₆. For this reaction the particle size effect appears to prevail over the effect of gold loading. The most active catalysts are 4Au/CuO/Al₂O₃ (gold particles less than 3 nm) and 4Au/Co₃O₄/Al₂O₃ (gold particles less than 5 nm).     

水热处理对氧化铝载体物化性质及丙烷脱氢性能的影响

采用水热处理对γ-Al2O3载体改性,并进行XRD、N2物理吸附-脱附、热重、NH3-TPD及H2-TPR表征。结果表明,γ-Al2O3经过"再水合-焙烧"过程,晶型变好,表面总酸量降低,Pt-Al2O3相互作用增加,提高了Pt Sn K/Al2O3催化剂的丙烷脱氢转化率、选择性及稳定性。其中,140℃处理4 h时,氧化铝负载的Pt Sn K催化剂表现出最优的丙烷脱氢性能,100 h内平均转化率为33.6%,平均选择性97.3%,失活参数为15.9%。     

Niobium oxide as support material for the oxidative dehydrogenation of propane

The ability of using niobium oxide (Nb₂O₅) as a support for preparing surface metal oxide species and testing the catalyst for the ODH of propane was done in the present study. Chromium oxide was used as the representative surface metal oxide species. To test the objective several loadings of Cr₂O₃/Nb₂O₅ were prepared by the incipient wetness impregnation technique. Surface area analysis, Raman, X-ray photoelectron spectroscopy (XPS) and electron paramagnetic resonance (EPR) spectroscopy and TPR studies were used to characterize the sample. It was observed that surface chromium oxide species are formed similar to those on other oxide supports and similar monolayer coverages were achieved. However, the reduction characteristic (T_max temperature) was different due to the change in the Cr–O–support bond. The ODH of propane over the Cr₂O₃/Nb₂O₅ catalysts revealed that the activity increased up to monolayer coverage and then decreased due to the presence of Cr₂O₃ crystals. Similar observations were seen for the V₂O₅/Nb₂O₅ and MoO₃/Nb₂O₅ catalysts. The turnover frequency (TOF) was independent of coverage for the surface chromium, vanadium and molybdenum oxide species on Nb₂O₅. The constant TOF suggests the structure insensitivity of this type of reaction. The propene selectivities were high and relatively constant for the Cr₂O₃/Nb₂O₅ catalysts revealing the higher yields that can be obtained on this series of catalysts compared to the Cr₂O₃/Al₂O₃ and Cr₂O₃/TiO₂ catalysts. Additional studies involving tungsten and molybdenum oxide additives on 1% Cr₂O₃/Nb₂O₅ reveal the effect of exposed support surface on the propene selectivities.     

Synthesis of cyclic carbonates from epoxides: Use of reticular oxygen of Al2O3 or Al2O3-supported CeOx for the selective epoxidation of propene

Reticular oxygen of Al₂O₃ or CeO_x supported on Al₂O₃ was used for the epoxidation of propene without any double bond cleavage. In batch reaction, Al₂O₃ alone was able to convert propene into propene oxide (PO) with 100% selectivity and 2% conversion of propene with a close to 3:1 ratio with respect to the number of Al(III) reduced to elemental Al. When Ce₂O₃/Al₂O₃ or CeO₂/Al₂O₃ was used, Al remained in its +3 oxidation state, while the Ce oxide was the oxidant as demonstrated by XPS analyses. CeO_x/Al₂O₃ was more active (propene conversion yield of 4–5%) but the selectivity was lower (70%) as PO was isomerized into acetone and propionaldehyde.

Interestingly the use of reticular oxygen very much improves the selectivity with respect to the use of pure O₂. In fact, while propene was more efficiently oxidized (10%) with O₂ in presence of Al₂O₃ or CeO_x/Al₂O₃, the selectivity was as low as 40% because C1 and C2 products were formed. However, the use of reticular oxygen represents a selective two-step technique for the use of molecular oxygen as oxidant of propene. The used oxides can be re-oxidized and the whole process can be further improved towards higher yields.

PO is quantitatively converted into propene carbonate by reaction with CO₂ in presence of Nb₂O₅.     

Activity enhancement of SnO2-doped Ga2O3–Al2O3 catalysts by coexisting H2O for the selective reduction of NO with propene

Catalytic reduction of NO by propene in the presence of oxygen was studied over SnO₂-doped Ga₂O₃–Al₂O₃ prepared by sol–gel method. Although SnO₂-doped Ga₂O₃–Al₂O₃ gave lower NO conversion than Ga₂O₃–Al₂O₃ in the absence of H₂O, the activity was enhanced considerably by the presence of H₂O and much higher than that of Ga₂O₃–Al₂O₃. The presence of SnO₂ and Ga₂O₃–Al₂O₃ species having intimate Ga–O–Al bondings was found to be essential for the promotional effect of H₂O. The promotional effect of H₂O was interpreted by the following two reasons. The first one is the removal of carbonaceous materials deposited on the catalyst surface by H₂O. The other is the selective inhibition by H₂O of the reaction steps resulting in propene oxidation to CO_x without reducing NO.     

Dehydrogenation of light alkanes over oxidized diamond-supported catalysts in the presence of carbon dioxide

Oxidized diamond demonstrated excellent support for the dehydrogenation of light alkanes to alkenes in the presence of CO₂. Oxidized diamond-supported Cr₂O₃ and V₂O₅ catalysts exhibited comparatively higher catalytic activities in the dehydrogenation of lower alkanes in the presence of CO₂. In the dehydrogenation of propane, the oxidized diamond-supported Cr₂O₃ and V₂O₅ catalysts in the presence of CO₂ afforded nearly twofold higher activities than that in the absence of CO₂. The activity of the oxidized diamond-supported V₂O₅ catalyst in the dehydrogenation of propane increased with increasing reaction temperatures. Furthermore, in the dehydrogenation of n-butane and iso-butane, a promoting effect of CO₂ on butane conversion and butenes yields was observed over the oxidized diamond-supported Cr₂O₃ and V₂O₅ catalysts, though the promotion effect was small.

UV-Vis analyses of the fresh and the reacted catalysts in the presence and absence of CO₂ revealed that CO₂ kept the surface V₂O₅ and Cr₂O₃ in a state of oxidation slightly higher than that in the absence of CO₂.     

Other catalytic properties

The behavior of fresh and aged EUROCAT V₂O₅–WO₃/TiO₂ SCR catalysts in the (I) oxidative dehydrogenation of light alkanes, and conversion of (ii) propan-2-ol, (iii) NO in the presence of propene and oxygen, (iv) propane and propene and (v) chloropropane is reported to analyse possible modifications of the catalyst properties during use and give a more comprehensive general picture of its surface and reactivity properties.     

Ethanol steam reforming over Ni/La–Al2O3 catalysts: Influence of lanthanum loading

Hydrogen production from ethanol reforming over nickel catalysts supported on lanthanum loaded Al₂O₃ substrates was studied. Activity results revealed the enhancement in the reforming stability of the Ni catalysts with the increase in the lanthanum loading on Al₂O₃ substrates. Catalytic behavior of Ni/La–Al₂O₃ catalysts in the ethanol steam reforming was found to be the contribution of the activity of the La–Al₂O₃ supports for the ethanol dehydration reaction and the activity of the nickel metallic phase that catalyzes both dehydrogenation and CC bond rupture. Physicochemical characterization of catalysts revealed that acidity, nickel dispersion and nickel-support interaction depend on the La-loading on Al₂O₃. The better reforming stability of catalysts with the increase in La content was explained in terms of the ability of nickel surface and/or La–Ni interactions to prevent the formation of carbon filaments.     

催化剂上丙烷氧化脱氢制丙烯

以浸渍法制备VMo/γ-Al₂O₃和VMoMg/γ-Al₂O₃催化剂,考察其催化丙烷氧化脱氢制丙烯的反应活性,采用XRD、UV-Vis DRS和In suit IR对催化剂进行表征。结果表明,V负载质量分数为3%、Mo负载质量分数为7%时的3V7Mo/γ-Al₂O₃催化剂表现出较好的催化性能;添加Mg后催化剂的催化性能有所改善,反应温度500 ℃时,丙烷转化率为18.19%,丙烯选择性74.76%。丙烷和丙烯在3V7Mo/γ-Al₂O₃和3V₇Mo₄Mg/γ-Al₂O₃催化剂上吸附后,C—H键的H与催化剂活性中心的晶格氧发生作用形成H—O键,且3V₇Mo₄Mg/γ-Al₂O₃催化剂上出现C—O键的温度比3V₇Mo/γ-Al₂O₃催化剂高,表明加入Mg有利于提高丙烯选择性。     

Factors controlling the selectivity of V2O5 supported catalysts in the oxidative dehydrogenation of propane

The surface properties of a series of V₂O₅ catalysts supported on different oxides (Al₂O₃, H–Na/Y zeolite, MgO, SiO₂, TiO₂ and ZrO₂) were investigated by transmission electron microscopy and FTIR spectroscopy augmented by CO and NH₃ adsorption. In the case of the V₂O₅/SiO₂ system TEM images evidenced the presence of V₂O₅ crystallites, whereas such segregated phase was not observed for the other samples. VO_x species resulted widely spread on the surface of Al₂O₃, H–Na/Y zeolite, MgO and SiO₂, whereas on TiO₂ and ZrO₂ they are assembled in a layer covering almost completely the support. Furthermore, evidences for the presence in this layer of V–OH Brønsted acid sites close to the active centres were found. It is proposed that propene molecules primarily produced by oxydehydrogenation of propane can be adsorbed on this acid centres and then undergo an overoxidation by reaction with redox centres in the neighbourhood. This features could account for the low selectivity of V₂O₅/TiO₂ and V₂O₅/ZrO₂ catalysts.     

Ultrahigh temperature water gas shift catalysts to increase hydrogen yield from biomass gasification

Noble metal (Rh, Pt, Pd, Ir, Ru, and Ag) and Ni catalysts supported on CeO₂–Al₂O₃ were investigated for water gas shift reaction at ultrahigh temperatures. Pt/CeO₂–Al₂O₃ and Ru/CeO₂–Al₂O₃ demonstrated as the best catalysts in terms of activity, hydrogen yield and hydrogen selectivity. At 700 °C and steam to CO ratio of 5.2:1, Pt/CeO₂–Al₂O₃ converted 76.3% of CO with 94.7% of hydrogen selectivity. At the same conditions, the activity and hydrogen selectivity for Ru/CeO₂–Al₂O₃ were 63.9% and 85.6%, respectively. Both catalysts showed a good stability over 9 h of continuous operation. However, both catalysts showed slight deactivation during the test period. The study revealed that Pt/CeO₂–Al₂O₃ and Ru/CeO₂–Al₂O₃ were excellent ultrahigh temperature water gas shift catalysts, which can be coupled with biomass gasification in a downstream reactor.     

A pilot plant study for catalytic decomposition of PCDDs/PCDFs over supported chromium oxide catalysts

Chromium oxide catalysts supported on TiO₂ and Al₂O₃ were examined in a fixed-bed flow reactor system for the removal of PCE (perchloroethylene), a simulant of 2,3,7,8-TCDD (2,3,7,8-tetrachlorodibenzo-p-dioxin), and in a pilot plant employing actual flue gas from a sintering plant for the removal of PCDDs/PCDFs (poly-chlorinated dibenzo-dioxin/poly-chlorinated dibenzo-furan). The 12.5 wt.% chromium oxides supported on TiO₂ and Al₂O₃ revealed excellent stability and performance of PCE removal in the feed gas stream containing water vapor. In a pilot plant study, the catalysts washcoated on the honeycomb reactor revealed 93–95% of PCDDs/PCDFs removal activity over CrO_x/Al₂O₃-HC20 (CrO_x/Al₂O₃ catalyst washcoated on 20 cell-honeycomb), and more than 99% of the decomposition activity over CrO_x/TiO₂-HC20 (CrO_x/TiO₂ catalyst washcoated on 20 cell-honeycomb) at 325 °C and 5000 h⁻¹ of reactor space velocity without the de novo synthesis of PCDDs/PCDFs. In particular, CrO_x/TiO₂-HC20 showed 94% of PCDDs/PCDFs decomposition activity even at 280 °C reaction temperature. The catalyst also exhibited significant NO removal activity. The chromium oxide seems to be a promising catalyst for the removal of PCDDs/PCDFs and NO_x contained in the flue gas.     

Dehydrogenation of i-butane on CrOx/Al2O3 catalysts prepared by ALE and impregnation techniques

Atomic layer epitaxy (ALE), a technique relying on saturating gas–solid reactions, was applied in the preparation of CrO_x/Al₂O₃ catalysts using Cr(acac)₃ vapor and air as source materials for CrO_x. Vaporized Cr(acac)₃ was reacted with preheated Al₂O₃, and the surface complex formed was treated with air to remove the ligand residues. The Cr loading increased from 1.3 to 12.5 wt.% as the number of saturating Cr(acac)₃ and air reactions was increased from one to 10. CrO_x/Al₂O₃ catalysts were also prepared from solution by incipient wetness impregnation (0.3–21 wt.%). XPS and UV–VIS measurements of the catalysts revealed the presence of both Cr⁶⁺ and Cr³⁺. Although the oxidation state distribution was similar, H₂-temperature programmed reduction (TPR) and solubility measurements indicated that Cr⁶⁺ surface sites were in stronger interaction with Al₂O₃ and more uniformly distributed in the catalysts prepared by ALE than by impregnation. On the basis of the activity of the catalysts in the dehydrogenation of i-butane, we propose that the dehydrogenation reaction uses both reduced Cr⁶⁺, i.e. redox Cr³⁺, and exposed non-redox Cr³⁺ sites. Furthermore, the dehydrogenation reaction must be insensitive to the size of the CrO_x ensembles since activities were similar for the catalysts prepared by ALE and impregnation. The decay of the dehydrogenation activity in successive prereduction–reaction–regeneration cycles was attributed to a decrease in the number of redox Cr³⁺ sites.     

IR studies on the activation of C–H hydrocarbon bonds on oxidation catalysts

The total oxidation of propane and its oxy-dehydrogenation to propene have been studied on spinel-type catalysts Mn₃O₄, Co₃O₄ and MgCr₂O₄ in a flow reactor and in an IR cell. Analogous studies have been performed on the oxy-dehydrogenation of n-butenes to 1,3-butadiene over MgFe₂O₄. Information on the reaction mechanism have been reached. The activation of the hydrocarbons is thought to occur by abstraction of a hydrogen from the weakest C–H bond, with a simultaneous reduction of a surface site and with the formation of a surface alkoxy-group.     

Physico-chemical properties of V-Sb-oxide systems and their catalytic behaviour in oxidative dehydrogenation of light paraffins

Catalysts prepared as bulk VSb_0.1O_x and supported V₂O₅/Al₂O₃, V₂O₅-Sb₂O₃/Al₂O₃ and Sb₂O₃/Al₂O₃ (containing 0.5, 1 or 2 theoretical monolayers of V₂O₅ or Sb₂O₃) were tested in the oxidative dehydrogenation of iso-butane at 550°C in i-C₄H₁₀:O₂:He=20:10:70 gas mixture. Fresh and used catalysts were characterised by BET, XRD and XPS. Reactivity and thermochemistry of active oxygen taking part in the redox cycle with ethane and hydrogene were studied using in situ differential scanning calorimetry. Temperature-programmed desorption of O₂ in He flow was also investigated and in situ DRIFT was applied to investigate surface species of the catalysts in flows of i-C₄H₁₀, O₂ and i-C₄H₁₀/O₂ mixture. Supported VSb_yO_x catalysts are more active and selective than bulk one. V-only supported catalysts display a high efficiency due to the high reactivity of VOX-species. In bulk catalyst, the surface is enriched with antimony. In supported samples, the surfaces V/Sb are close to the calculated ones. In the presence of antimony, the amount of active oxygen species and their reactivity in redox transformation is improved. The rates of vanadium reduction and reoxidation are also higher. Compared to V-only catalysts, supported V-Sb-catalysts display a lower coking activity and higher on-stream stability.     

氯的脱除对丙烷脱氢PtSnNa/Al2O3催化剂结构的影响

考察了氯的脱除对丙烷脱氢铂锡催化剂结构和反应性能的影响,并采用XRD、N₂吸脱附、TPR、NH₃-TPD、TEM和Raman等方法进行表征。结果表明,氯的脱除温度显著影响催化剂的酸性、孔体积、比表面积、孔径和Pt颗粒尺寸。随着处理温度的提高,催化剂酸性、比表面积、孔体积都呈现下降的趋势,平均孔径增加,Pt颗粒的烧结程度加剧。随着处理温度的增加,催化剂初活性逐渐降低,丙烯选择性增加,稳定性出现先增加后降低趋势。研究表明,氯的较佳的脱除温度为540℃,催化剂具有很好的脱氢性能和稳定性,收率最高。     

Role of CeO2 in Ni/CeO2–Al2O3 catalysts for carbon dioxide reforming of methane

Ni catalysts supported on γ-Al₂O₃, CeO₂ and CeO₂–Al₂O₃ systems were tested for catalytic CO₂ reforming of methane into synthesis gas. Ni/CeO₂–Al₂O₃ catalysts showed much better catalytic performance than either CeO₂- or γ-Al₂O₃-supported Ni catalysts. CeO₂ as a support for Ni catalysts produced a strong metal–support interaction (SMSI), which reduced the catalytic activity and carbon deposition. However, CeO₂ had positive effect on catalytic activity, stability, and carbon suppression when used as a promoter in Ni/γ-Al₂O₃ catalysts for this reaction. A weight loading of 1–5 wt% CeO₂ was found to be the optimum. Ni catalysts with CeO₂ promoters reduced the chemical interaction between nickel and support, resulting in an increase in reducibility and stronger dispersion of nickel. The stability and less coking on CeO₂-promoted catalysts are attributed to the oxidative properties of CeO₂.