Selective oxidation of ethane and propane over sulfated zirconia‐supported nickel oxide catalysts

The oxidative dehydrogenations of ethane and propane were investigated over a series of zirconia and nickel‐oxide supported on zirconia catalysts. It was found that zirconia, sulfated zirconia as well as NiO‐based zirconia catalysts showed high catalytic activities for oxidative dehydrogenation of ethane and propane. However, conversion and selectivity differed depending on the nature of the catalysts. Zirconia, sulfated zirconia (SZ) and their supported NiO catalysts showed high ethane conversions but lesser selectivities to olefins while NiO/Li₂ZrO₃ exhibited high selectivities to ethylene and propylene. Addition of an LiCl promoter in the NiO/SZ catalyst increased the catalytic activity and olefin selectivity, thus resulting in a higher olefin yield. In the oxidative dehydrogenations of ethane and propane NiO–LiCl/SZ exhibited 79% ethylene selectivity at 93% ethane conversion at 650 °C and 52% selectivity to propylene at 20% propane conversion at 600 °C, respectively. Characterization showed that the physico‐chemical properties of the catalysts determine the catalytic activity and selectivity. © 2001 Society of Chemical Industry     

Study of Mn-based Catalysts for Oxidative Dehydrogenation of Cyclohexane to Cyclohexene

The gas-phase oxidative dehydrogenation (ODH) of cyclohexane to cyclohexene in the presence of molecular oxygen has been studied over various Mn-based catalysts. It is found that LiCl/MnO_x/PC (Portland cement) catalyst exhibits the highest catalytic performance, and a 42.8% cyclohexane conversion, 58.8% cyclohexene selectivity and 25.2% cyclohexene yield can be achieved under 600 °C, 20,000 h⁻¹ and C₆H₁₂/O₂/N₂=14/7/79. There are good correlations between the selectivities to cyclohexene and the electrical conductivities of Li doped Mn-based catalysts, from which it is deduced that the non-fully reduced oxygen species (O₂⁻, O₂²⁻, O⁻) involved in a new phase of LiMn₂O₄ might be responsible for the high selectivity toward cyclohexene, whereas the Mn₂O₃ crystal phase results in the CO_x formation. The selectivity to cyclohexene increases with increasing molar ratio of Li to Mn in LiCl/MnO_x/PC.     

Oxidative Dehydrogenation of Ethane Over Zirconia‐Supported Lithium Chloride Catalysts

A series of Li‐doped catalysts on zirconia or sulfated zirconia were prepared and investigated in the catalytic reaction of ethane oxidative dehydrogenation into ethylene. It is found that zirconia and sulfated zirconia supports prepared by different methods show varying nature and thus influence the catalytic performance of their supported Li catalysts in this reaction. Li catalysts doped on the sulfated zirconia prepared by a two‐step method can exhibit high ethane conversion, selectivity towards ethylene and ethylene yield as well as a stable catalytic performance. The Li precursors also affect the catalytic behavior. LiCl doped on sulfated zirconia can give high ethane conversion and ethylene selectivity. Addition of transitional and lanthanide metal oxides to the LiCl/SZ system significantly improves the activity and yield of ethylene in the oxidative dehydrogenation of ethane. Among the oxides studied, NiO and Nd₂O₃ demonstrate the best promoting effect in terms of catalytic conversion and ethylene yield.     

Oxidative dehydrogenation of propane over magnesium molybdate catalysts

Catalytic activities of magnesium molybdates were investigated for the oxidative dehydrogenation of propane with and without molecular oxygen under atmospheric pressure. Catalytic properties drastically changed with the catalyst composition, and it turned out that Mg_0.95MoO_x catalysts having slight excess molybdenum showed the highest activity in the oxidative dehydrogenation of propane, which gave 61% selectivity to propene at 22% conversion of propane at 515°C. The catalytic activities strongly depended on the acidic properties of the catalysts. It was also revealed that the lattice oxide ions of the catalysts participated as an active oxygen in the oxidative dehydrogenation of propane.     

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.     

Performance of metal‐oxide‐promoted LiCl/sulfated‐zirconia catalysts in the ethane oxidative dehydrogenation into ethene

The effects of some transition‐ and lanthanide‐metal oxides in LiCl/sulfated‐zirconia (SZ) catalysts on catalytic behavior in the oxidative dehydrogenation of ethane were investigated. It is found that modification of LiCl/SZ by metal oxides significantly improves the catalytic activity and ethene yield. Among those additives, Ni and Nd oxides show the best promoting effect in terms of ethane conversion and ethene yield. 93% ethane conversion with 83% selectivity to ethene has been achieved over the Nd₂O₃–LiCl/SZ catalyst at 650°C. In addition, those oxide‐promoted LiCl/SZ catalysts are also found to exhibit a longer stability in catalytic performance. Metal‐oxide additives change the chemical structure and surface redox properties, which accounts for the enhancement of activity. This revised version was published online in July 2006 with corrections to the Cover Date.     

Selective conversion of propane to propene by the catalytic oxidative dehydrogenation over cobalt and magnesium molybdates

Catalytic performances of various metal molybdates were tested in the oxidative dehydrogenation of propane to propene with molecular oxygen under an atmospheric pressure. Most of the molybdates tested promoted the selective oxidative conversion of propane to propene and among them cobalt and magnesium molybdates were found highest in the activity and selectivity. It was also found that their catalytic activities were highly sensitive to the catalyst composition, and it turned out that Co_0.95MoO _x and Mg_0.95MoO _x catalysts which have slightly excess molybdenum showed the highest activity in the oxidative dehydrogenation of propane. Under the optimized reaction conditions, higher reaction temperatures and lower partial pressures of oxygen, these catalysts gave 60% selectivity to propene at 20% conversion of propane. Since the molybdates having the surface enriched with molybdenum oxide tended to show high activity for the propane oxidation, surface molybdenum oxide clusters supported on metal molybdate matrix seem to be the active sites for the selective oxidative dehydrogenation of propane.     

Catalytic composites based on yttria stabilized zirconia for oxidative dehydrogenation of ethane

LiCl/YSZ is found to be a very effective catalyst for the oxidative dehydrogenation of ethane. LiCl supported on YSZ-MgO composite shows increase in catalytic activity and ethylene selectivity. Addition of Mn and Sn as promoters to this system leads to 85% ethane conversion, 77% ethylene selectivity and 65% ethylene yield at 662 °C. Use of Li₂O in the place of LiCl results in lower ethylene yields. Further modification is needed to improve the catalyst stability.     

乙烷脱氢催化剂研究进展

乙烯是重要的有机化工原料,随着乙烯需求量的不断增加以及石油资源的日益匮乏,乙烷脱氢已成为乙烯增产的重要途径。乙烷脱氢制乙烯受到越来越多的关注,乙烷脱氢催化剂逐步改善。本文首先介绍了近年来国内外乙烷脱氢制乙烯的研究现状,然后从催化剂制备方法、性能以及应用等方面对乙烷催化脱氢催化剂和乙烷氧化脱氢催化剂的研究进行了总结,并对其进行了系统分类。催化脱氢是低碳烷烃转化为烯烃的有效途径,烯烃选择性高,受到热力学平衡限制,能耗较高。氧化脱氢由于氧化剂的引入打破了热力学平衡限制,能够有效抑制焦炭的生成,减少能量消耗。然而,深度氧化反应难于控制,乙烯的选择性低。因此,选取合适的催化脱氢催化剂,尽可能提高乙烷单程转化率、降低能耗是乙烷脱氢的关键。     

Oxidative Dehydrogenation of Light Alkanes on Supported Molten Alkali Metal Chloride Catalysts

Potential and limitations of molten alkali metal (Li, Na, and K) chlorides supported on Dy₂O₃/MgO were explored for the oxidative dehydrogenation of lower alkanes, such as ethane and propane. The catalysts have high activity and selectivity to olefins compared to conventional catalysts. Optimum performance is obtained with catalysts on which the alkali metal chloride phase is molten under reaction conditions. Lower chloride melting point correlates with higher selectivity. The high selectivity to ethene or propene is attributed to the high mobility of cations and anions, which facilitates desorption of alkene (limiting further oxidation) and the generation of spatially isolated hypochloride anions acting as the active sites for the primary C–H bond activation.     

Novel nitrogen containing heterogeneous catalysts for oxidative dehydrogenation of light paraffins

Novel nitrogen contained catalyst CoN_x/Al₂O₃ yielded high performance in the oxidative dehydrogenation of propane and n-butane. 47.6 and 37.4 wt% yield of olefins at 82% butane and 76.7% propane conversion were measured at 600 °C. Ethylene and propylene were mainly formed at >400 °C via oxidative cracking of paraffins. XRD and XPS studies of the novel catalytic system indicate an essential modification of cobalt by nitrogen.     

Lithium-chloride-promoted sulfated zirconia catalysts for the oxidative dehydrogenation of ethane

The oxidative dehydrogenation of ethane over sulfated-zirconia-supported lithium chloride catalysts has been systematically investigated. The optimal experimental parameters were obtained. It is found that sulfation of zirconia increases the catalytic activity. 2–3.5 wt% lithium chloride on sulfated zirconia catalysts exhibit high catalytic activity for oxidative dehydrogenation of ethane, with particularly high activity for ethene production. 70% selectivity to ethene at 98% ethane conversion, giving 68% ethene yield, is achieved over 3.5 wt% LiCl/SZ at 650°C.     

New Integrated Catalytic Membrane Processes for Enhanced Propylene and Polypropylene Production

Newly reported integrated processes are discussed for aliphatic (paraffin) hydrocarbon dehydrogenation into olefins and subsequent polymerization into polyolefins (e.g., propane to propylene to polypropylene, ethane to ethylene to polyethylene). Catalytic dehydrogenation membrane reactors (permreactors) made by inorganic or metal membranes are employed in conjunction with fluid bed polymerization reactors using coordination catalysts. The catalytic propane dehydrogenation is considered as a sample reaction in order to design an integrated process of enhanced propylene polymerization. Related kinetic experimental data of the propane dehydrogenation in a fixed bed type catalytic reactor is reviewed which indicates the molecular range of the produced C₁-C₃ hydrocarbons. Experimental membrane reactor conversion and yield data are also reviewed. Experimental data were obtained with catalytic membrane reactors using the same catalyst as the non-membrane reactor. Developed models are discussed in terms of the operation of the reactors through computational simulation, by varying key reactor and reaction parameters. The data show that it is effective for catalytic permreactors to provide streams of olefins to successive polymerization reactors for the end production of polyolefins (i.e., polypropylene, polyethylene) in homopolymer or copolymer form. Improved technical, economic, and environmental benefits are discussed from the implementation of these processes.     

Cr/SSZ-13催化二氧化碳氧化乙烷脱氢反应的研究

通过脱氢反应将低碳烷烃转化为同碳数的烯烃是烷烃高值化利用和烯烃原料多元化的重要途径。烷烃氧化脱氢制烯烃的反应具有不受反应平衡限制、积炭少、反应温度低等优点,一直是研究的热点。通过利用浸渍法制备不同铬（Cr）负载量的Cr_x/SSZ-13系列催化剂,采用氮气物理吸附、氨程序升温脱附（NH₃-TPD）、二氧化碳程序升温脱附（CO₂-TPD）、氢气程序升温还原（H₂-TPR）、紫外-可见吸收光谱（UV-Vis）以及高角度环形暗场-扫描透射电镜（HAADF-STEM）与耦合能谱分析（EDX-Mapping）等方法对催化剂进行了物性表征,并用微型固定床反应器评价催化剂对乙烷氧化脱氢制乙烯的催化性能,最终建立了Cr/SSZ-13催化剂的构效关系。研究发现,当n（二氧化硅）/n（氧化铝）=10时,Cr_1.5/SSZ-13-10催化剂上含有丰富的Cr³⁺物种,其中配位不饱和Cr³⁺是优异的脱氢活性位,有利于二氧化碳氧化乙烷脱氢反应的进行。因此,Cr_1.5/SSZ-13催化剂在650 ℃时表现出优异的催化性能,即二氧化碳转化率和乙烷转化率分别达到26.41%和53.2%,乙烯产率为38.83%。     

An evidence of active surface MoOx over MgMoO4 for the catalytic oxidative dehydrogenation of propane

In order to clarify whether MgMo_xO_y catalysts with slight excess of molybdenum relative to the stoichiometric MgMoO₄ compound showed increased activities for propene formation in the propane oxidative dehydrogenation, we investigated the catalytic properties of MoO₃ supported on MgMoO₄ and of MgMo_xO_y catalysts treated with acid or base. Supporting MoO₃ on magnesium-rich MgMo_0.99O_y catalysts which are poorly active, or treating them with acetic acid to remove excess magnesium, resulted in drastic activity increases. On the other hand, the ammonia treatment of molybdenum-rich MgMo_1.05O_y catalysts which are highly active turned out to give a remarkable decrease in activity, because surface MoO_x dissolved in ammonia water. A clear correlation was observed between the catalytic activities for propane oxidation and the dehydration of 2-propanol to propene over the supported catalyst and the treated catalysts. Since the bulk structures were unchanged by supporting or by the treatments, the existence of MoO_x clusters formed on the surface of MgMoO₄ are responsible for the activities in the oxidative dehydrogenation of propane. This revised version was published online in July 2006 with corrections to the Cover Date.     

Advanced Catalytic Dehydrogenation Technologies for Production of Olefins

Catalytic dehydrogenation is a critical and growing technology for the production of olefins, especially for propylene production. This paper will give an overview of advances in the catalysis science and technology for production of olefins by catalytic dehydrogenation, including the concomitant removal of H₂ by selective oxidation. For light paraffin dehydrogenation, UOP has licensed the Oleflex? process widely for production of polymer-grade propylene as well as isobutylene with over 12 million metric tons of capacity announced. Today there are nine UOP C₃ Oleflex? units in operation accounting for 55?% of the installed world-wide propylene production capacity from propane dehydrogenation technology. The heart of the process is a noble metal multi-metallic catalyst and the continuous catalyst regeneration (CCR) process. The coupling of catalytic dehydrogenation with selective oxidation of hydrogen allows one to design a process, which greatly improves equilibrium conversions while maintaining very high selectivity to olefin. The Lummus/UOP SMART? SM process (Styrene Monomer Advanced Reheat Technology) allows 30?C70?% capacity expansion, achieves a higher per-pass ethylbenzene conversion, and provides the most cost-effective revamp for higher capacity. Styrene Monomer Advanced Reheat Technology (SMART?) uses an oxidation catalyst and novel reactor internals to allow oxidative reheating between dehydrogenation stages. In the case of selective oxidation catalysts containing dispersed metal active sites, the role of diffusion and pore architecture is as important as the active metal sites.     

Oxidative dehydrogenation of ethane and propane: How far from commercial implementation?

This review examines the recent literature on the oxidative dehydrogenation (ODH) of ethane and propane, which aims for the synthesis of the corresponding alkenes. The following aspects are discussed: (a) the main features affecting the catalytic properties of systems based on supported vanadium oxide and molybdenum oxide; (b) the characteristics of catalysts producing outstanding olefin yields; (c) advantages in selectivity gained by means of either special reactor configurations or non-conventional conduction of the reaction; (d) the contribution of homogeneous reactions to the formation of olefins during the oxidation of alkanes.     

Oxidative Dehydrogenation of Propane on V2O5/ZrO2 Catalyst

The performance of zirconia supported vanadia catalyst has been investigated for the oxidative dehydrogenation of propane. Vanadia loading was varied from 1.6 to 22.7 wt%, both below and well above monolayer coverage. The turnover frequency was highest for the catalyst with a vanadia surface density of 5 VO _x /nm². The effect of vanadia loading on the redox behavior of the catalysts was investigated by temperature-programmed reduction and temperature-programmed oxidation. The specific activity increased with ease of reducibility of the catalyst. The extent of reduction and ease of reoxidizability of the catalysts were also found to depend on the surface vanadia structure and to influence the catalytic activity. The effect of vanadia loading on the basicity of the catalysts was also investigated.     

Manganese‐containing redox catalysts for selective hydrogen combustion under a cyclic redox scheme

Selective hydrogen combustion (SHC) in the presence of light hydrocarbons was demonstrated with a series of Mn‐containing mixed oxide redox catalysts in the context of a chemical looping‐oxidative dehydrogenation scheme. Unpromoted and 20 wt % Na₂WO₄‐promoted Mg₆MnO₈, SrMnO₃, and CaMnO₃ exhibited varying SHC capabilities at temperatures between 550 and 850°C. Reduction temperature of unpromoted redox catalysts increased in the order Mg₆MnO₈ < SrMnO₃ < CaMnO₃. Promotion with 20 wt % Na₂WO₄ resulted in more selective redox catalysts capable of high‐temperature SHC. XPS analysis revealed a correlation between suppression of near‐surface Mn and SHC selectivity. Na₂WO₄/CaMnO₃ showed steady SHC performance (89% H₂ conversion, 88% selectivity) at 850°C over 50 redox cycles. In series with a Cr₂O₃/Al₂O₃ ethane dehydrogenation catalyst, Na₂WO₄/CaMnO₃ combusted 84% of H₂ produced while limiting CO_x yield below 2%. The redox catalysts reported can be suitable for SHC in a cyclic redox scheme for the production of light olefins from alkanes. © 2018 American Institute of Chemical Engineers AIChE J, 64: 3141–3150, 2018     

Kinetic modeling of oxidative dehydrogenation of propane with CO2 over MoOx/La2O3–Al2O3 in a fluidized bed

A 4-step kinetic model of CO₂-assisted oxidative dehydrogenation (ODH) of propane to C₂/C₃ olefins over a novel MoO_x/La₂O₃–γAl₂O₃ catalyst was developed. Kinetic experiments were conducted in a CREC Riser Simulator at various reaction temperatures (525–600 °C) and times (15–30 s). The catalyst was highly selective towards propylene at all combinations of the reaction conditions. Langmuir-Hinshelwood type kinetics were formulated considering propane ODH, uni- and bimolecular cracking of propane to produce a C₁-C₂ species. It was found that the one site type model adequately fitted the experimental data. The activation energy for the formation of propylene (67.8 kJ/mol) is much lower than that of bimolecular conversion of propane to ethane and ethylene (303 kJ/mol) as well as the direct cracking of propane to methane and ethylene (106.7 kJ/mol). The kinetic modeling revealed the positive effects of CO₂ towards enhancing the propylene selectivity over the catalyst.