Propane oxidative dehydrogenation on silica based oxide catalysts

The oxidative dehydrogenation of propane to propylene with molecular O₂ (PPD) has been investigated on commercial bare SiO₂ and medium loaded V₂O₅ and MoO₃ catalysts at 450–525°C. The direct relationship between the density of reduced sites (, 10¹⁶ s_r g _cat– ¹ ), evaluated in steady-state conditions by O₂ chemisorption, and the POD reaction rate proves the occurrence of a concerted reaction mechanism involving the activation of gas-phase O₂ on the reduced sites of the catalyst surface. A straight-line correlation between the activity of such silica based catalysts in POD and methane partial oxidation to formaldehyde (MPO) at 525°C has been disclosed.     

Optimization of V2O5–MgO/TiO2 catalyst for the oxidative dehydrogenation of propane effect of magnesia loading and preparation procedure

The effect of magnesia loading and preparation procedure of vanadia on titania catalysts on the physicochemical characteristics and the performance in propane oxidative dehydrogenation were investigated. A series of magnesia promoted vanadia catalyst (5 wt% V₂O₅) with varying amounts of MgO (1.9--10 wt%) were synthesized by synchronous and sequential deposition on titania support. The catalysts were characterized using several techniques (BET, XRD, H₂-TPR and NH₃)-TPD). Both MgO loading and preparation procedure affect the catalyst surface properties and the behavior in the oxidative dehydrogenation of propane. Magnesia addition results in drastic increase in propene selectivity, while the effect on activity is negative. The activity is inversely related with the magnesia loading. Deposition of V₂O₅ on previously prepared MgO/TiO₂ presents a beneficial effect in the activity of the sample. The role of acidity and reducibility is explored. There is no correlation between reducibility and activity of the catalysts, whereas the acidity seems to influence the catalytic performance. Catalyst containing 5 wt% V₂O₅ and 1.9 wt% MgO prepared by sequential deposition of V₂O₅ on already doped with MgO titania exhibits the most interesting results.     

The selective oxidative dehydrogenation of propane on vanadium aluminophosphate catalysts

VAPO-5 and V/ ALPO-5 catalysts have been tested for the oxidative dehydrogenation of propane. Depending on the vanadium contents and the preparation procedure, different vanadium species and different catalytic behavior are observed. The catalyst containing V⁵⁺ species with a tetrahedral coordination presents the higher yield of propene in the oxidative dehydrogenation of propane. The same yields of CO₂ are observed on all vanadium aluminophosphate catalysts, while the higher the yield of propene the lower the yield of CO is.     

How oxide carriers affect the reactivity of V2O5 catalysts in the oxidative dehydrogenation of propane

The catalytic pattern of several oxide carriers (MgO, Al₂O₃, ZrO₂, TiO₂, SiO₂, HY zeolite) and supported V₂O₅ (4.7–5.3 wt%) catalysts in the oxidative dehydrogenation of propane to propylene (PODH) has been comparatively investigated. The fundamental role of the oxide support on both reducibility and reactivity of vanadia catalysts has been assessed. A direct relationship between the specific surface activity of oxide carriers and that of vanadia catalysts is discussed. The inverse relationship between the specific activity and the onset temperature of reduction marks the prevailing redox behaviour of V₂O₅ catalysts in the PODH reaction. This revised version was published online in July 2006 with corrections to the Cover Date.     

Sn掺杂量对Pt/Sn-MFI催化剂的丙烷脱氢性能影响

随着对丙烯需求的日渐增加,由丙烷催化脱氢制丙烯来实现对丙烯的增产,已成为增产丙烯的重要手段之一。利用水热法制备一系列不同Sn掺杂量的Sn-MFI载体,采用等体积浸渍法制备相同Pt负载量的Pt/Sn-MFI催化剂,通过XRD、N2吸附-脱附、FT-IR和H2-TPR等表征考察不同Sn掺杂量的催化剂对丙烷催化脱氢性能的影响。结果表明,Pt/Sn1. 3%-MFI催化剂具有最高的催化丙烷脱氢活性和稳定性,丙烷初始转化率为43. 3%,丙烯选择性为98. 9%。反应360 min后,丙烷转化率为25. 1%,选择性保持不变。     

Effect of alkali metals additives to V2O5/TiO2 catalyst on physicochemical properties and catalytic performance in oxidative dehydrogenation of propane

The effect of alkali metal additives Li, K, and Rb to V₂O₅/TiO₂ catalyst on the rate of catalyst reduction with propane and reoxidation with oxygen, sorption of propene, and the electron work function has been examined. The results have been correlated with the catalytic performance in oxidative dehydrogenation, ODH, of propane. It has been found that the rates of reduction, reoxidation and the ODH of propane decrease in the order: VTi>LiVTi>KVTi>RbVTi. The activation energies of the reduction and reoxidation are not, however, affected by the presence of the alkali metals. The same sequence has been observed for the work function values of the catalysts. It is argued that alkali metal poisons the centres of the hydrocarbon activation. The yield and selectivity to propene in the ODH of propane increase, however, for the promoted catalysts, following the above sequence. This effect is ascribed to the decrease in the heat of the propene adsorption, which is due to the increase in the basicity and decrease in acidity on the promoted catalysts.     

柱撑型钒基催化剂的制备及其丙烷氧化脱氢催化性能

以人工合成的3种不同层板组成的层状双羟基金属氢氧化物MgAl-CO₃-LDHs、CoAl-CO₃-LDHs和NiCr-CO₃-LDHs为载体,以偏钒酸钠NaVO₃为柱撑剂和钒前体,采用离子交换法制备了钒柱撑的催化剂样品（MgAlVO、CoAlVO和NiCrVO）,通过XRD、FTIR、XPS和Raman等手段表征了样品的物相、钒物种的存在形态以及钒的价态,以丙烷氧化脱氢制丙烯为模型反应,表征了所制备的催化剂样品的催化性能,着重探讨了LDHs载体的层板组成以及钒的含量对催化剂样品中的钒氧物种存在形态及其丙烷氧化脱氢催化性能的影响。结果表明：以20%理论含量的钒柱撑MgAl-CO₃-LDHs所制备的催化剂样品20%MgAlVO对丙烷氧化脱氢反应的催化性能较好,当反应温度为560℃时,丙烯收率可以达到11.3%,Raman光谱显示该催化剂样品中的钒以Mg₃V₂O₈和α-Mg₂V₂O₇两种形式共存,且晶格氧O^2-和吸附氧O^-所占的比例较为均衡,有利于获得较好的丙烷氧化脱氢催化性能,而在同样条件下制备的催化剂样品20%CoAlVO和20%NiCrVO中的钒物种只观察到分别以Co₃V₂O₈和Ni₃V₂O₈存在的正钒酸盐,前者对丙烯的收率不到8%,后者甚至完全得不到丙烯。     

丙烷氧化脱氢制丙烯的钒基介孔催化材料研究进展

介绍了近年来丙烷氧化脱氢催化技术的最新研究进展,针对其中应用最广泛的钒基介孔催化剂,对其反应机理、载体性能和制备方法进行了综述,并比较了不同催化体系的丙烷氧化脱氢性能,提出了改善钒基介孔催化剂催化活性与选择性的途径。通过比较已经报道的同类研究结果,着重阐述了载体的孔结构对于氧化脱氢过程的影响,比表面积和孔径的优化对于提高催化剂的活性组分分散度以及活性位的数量效果明显。今后研究应着重提高催化剂孔道结构在高温下的稳定性以及使用寿命。     

Oxidative dehydrogenation of ethane and propane over Mn-based catalysts

The catalytic performances of Mn-based catalysts have been investigated for the oxidative dehydrogenation of both ethane (ODE) and propane (ODP). The results show that a LiCl/MnO_x/PC (Portland cement) catalyst has an excellent catalytic performance for oxidative dehydrogenation of both ethane and propane to ethylene and propylene, more than 60% alkanes conversion and more than 80% olefins selectivity could be achieved at 650°C. In addition, the results indicate that Mn-based catalysts belong to p-type semiconductors, the electrical conductivity of which is the main factor in influencing the olefins selectivity. Lithium, chlorine and PC in the LiCl/MnO_x/PC catalyst are all necessary components to keep the excellent catalytic performance at a low temperature. This revised version was published online in July 2006 with corrections to the Cover Date.     

Catalytic dehydrogenation of propane over cluster-derived Ir–Sn/SiO2 catalysts

The dehydrogenation of propane was studied in gas-phase at 773 K over two series of silica-deposited Ir–Sn systems: the bimetallic catalysts obtained from Ir–Sn carbonyl clusters precursors and the ones prepared by deposition of a metallorganic Sn precursor onto preformed Ir nanoparticles. In the comparison, cluster-derived catalysts showed good propane conversion, optimal selectivity to propene and high stability under the severe reaction conditions.     

负载型MoO3/β分子筛催化剂的丙烷氧化脱氢性能

以β分子筛为载体,通过浸渍法负载钼制备MoO₃/β分子筛催化剂,对其进行XRD、FT-IR、BET和NH₃-TPD物化性能表征,考察其对丙烷氧化脱氢制丙烯的催化性能。结果表明,样品具有活性组分MoO₃存在,也有不同酸性能的活性位存在。负载量对催化剂的表面积和孔径有影响。单纯β分子筛载体有催化活性,不同钼负载量对催化性能有影响,负载钼质量分数为20%时,转化率达到极大值。     

Cr系丙烷脱氢催化剂研究进展

综述了Cr系丙烷脱氢催化剂的研究状况,介绍了使用Cr系丙烷脱氢催化剂的工艺和催化剂脱氢机理,探讨了Cr系催化剂的活性中心和失活原因,总结了影响铬铝催化剂催化性能的因素,包括制备、载体、助剂、积炭及工艺条件,对Cr系催化剂的研究前景进行了展望。     

Effect of calcium and potassium on V2O5/ZrO2 catalyst for oxidative dehydrogenation of propane: a comparative study

The effect of calcium and potassium on the physiochemical properties and performance of V₂O₅/ZrO₂ catalyst for oxidative dehydrogenation of propane was studied in the temperature range of 385–400 °C. The vanadia loading was kept constant at 5 VO_x/nm² and the atomic ratio A/V (A=Ca, K) was varied from 0.05 to 0.75. The vanadia surface structure was investigated using X-ray diffraction analysis (XRD), electron paramagnetic resonance (EPR), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). The redox property of the catalysts was studied by temperature programmed reduction (TPR) and temperature programmed oxidation (TPO) whereas surface acidity was measured by temperature programmed desorption (TPD) of ammonia. Calcium and potassium both interact with the surface V=O and stabilize the +5 oxidation state of vanadium. Interaction between calcium and vanadium was more intense though surface concentration of calcium was lower than that of potassium. For doped catalysts, the activity was lower due to an increase in reduction temperature as well as a lower extent of reduction and increased resistance to undergo redox cycles. On the other hand, removal of surface acidic sites by the dopants increased the propene selectivity. Potassium was more effective in decreasing the activity and increasing the propene selectivity.     

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.     

铂系丙烷脱氢催化剂助剂研究进展

铂基催化剂用于丙烷催化脱氢的主要缺点是稳定性差、选择性低,通过添加助剂可以大大改善该催化剂的脱氢性能.针对催化剂助剂,综述了铂基丙烷脱氢催化剂的研究现状,分别介绍了碱金属、碱土金属、稀土金属和过渡金属作为助剂对铂基催化剂的影响,探讨了所添加助剂的作用机制,并对铂基催化剂研究前景进行了展望.     

Catalytic behavior of vanadium-containing mesoporous silicas in the oxidative dehydrogenation of propane

Three series of vanadium-containing silica catalysts (2–7.6 wt% V) have been prepared by varying the synthesis method. In all cases, conversion values in the oxidative dehydrogenation of propane increase with the temperature, vanadium loading and reducibility. For impregnated and anchored catalysts, a relationship between the selectivity towards propene and the effective acidity, as determined in the dehydration of 2-propanol, can be established. This revised version was published online in July 2006 with corrections to the Cover Date.     

溶胶-凝胶法制备丙烷脱氢Pt-Sn/Al2O3催化剂性能

采用溶胶-凝胶法和浸渍法制备了不同Sn组分含量的Pt-Sn/Al₂O₃催化剂, 通过XPS、TEM和H₂吸附等物化表征手段对催化剂进行了表征,考察了无H2存在下的催化剂丙烷脱氢性能。结果表明,采用溶胶-凝胶法导致一部分Sn组分被包埋,减少高温还原条件下Sn组分的析出而提高催化脱氢活性。在550 ℃反应 6.5 h的条件下,丙烯收率36.3%,丙烯选择性达98.8%。     

MoO3/ZrO2催化剂的丙烷氧化脱氢制丙烯催化性能

以十六烷基三甲基溴化铵为表面活性剂,采用溶剂热法制备系列MoO_3/ZrO_2催化剂,采用H2-TPR、N_2吸附-脱附、X射线衍射等对其进行表征,并评价MoO_3/ZrO_2催化剂的丙烷氧化脱氢制丙烯催化性能。结果表明,MoO_3负载于ZrO_2载体上制备的催化剂催化活性增加,MoO_3负载质量分数为20%的MoO_3/ZrO_2催化剂,在反应温度为600℃时,丙烷转化率27.45%,丙烯选择性44.78%,丙稀收率12.29%。     

CeO2‐CrOy/γ‐Al2O3 redox catalyst for the oxidative dehydrogenation of propane to propylene

CeO₂‐CrO_y loaded on γ‐Al₂O₃ was investigated in this work for the oxidative dehydrogenation (ODH) of propane under oxygen‐free conditions. The ODH experiments of propane were conducted in a fluidized bed at 500°C‐600°C under 0.1 Mpa. The prepared catalyst was characterized by N₂ adsorption‐desorption measurements, H₂‐temperature‐programmed reduction, O₂‐temperature‐programmed desorption, NH₃‐temperature‐programmed desorption, x‐ray photoelectron spectroscopy, and x‐ray diffraction. The change in the selectivity of propylene resulted from the thermal cracking of the propane and the competition for lattice oxygen in the catalyst between propylene formation and propane and propylene combustion. Therefore, to achieve higher propylene yield in the industry, the reaction temperature should be 550°C‐575°C for the 17.5Cr‐2Ce/Al catalyst. The results of H₂‐TPR (from 0.2218 mmol/g‐0.3208 mmol/g) revealed that the addition of CeO₂ can enhance the oxygen capacity of CrO_y. Compared with that for 17.5Cr/Al, the conversion can be enhanced from 22.4% to 28.5% and the selectivity of propylene can be improved from 72.2% to 75.9% for the 17.5Cr‐2Ce/Al catalyst. In addition, CeO₂ can inhibit the evolution of lattice oxygen (O^2?) to electrophilic oxygen species (O₂^?), causing the average CO_x (CO and CO₂) selectivity to decrease from 9.64% to 6.31%.