改性VOx/MSU-1催化剂上CO2氧化异丁烷脱氢反应

以MSU-1为载体制备了一系列改性的VOx/MSU-1催化剂,并在CO2氧化异丁烷脱氢制异丁烯的反应中评价了催化剂的性能,发现稀土元素La、Ce的加入能提高催化剂的活性。采用XRD、H2-TPR及NH3-TPD方法对催化剂La2O3-VOx/MSU-1进行了深入的表征,发现La2O3的加入提高了载体MSU-1上活性组分VOx的分散度,同时也改善了催化剂表面的酸碱性,更加有利于异丁烷氧化脱氢反应的进行。优化了反应条件,在最佳反应条件下,异丁烷的转化率为63.6%,异丁烯的产率为52.3%。最后,通过8 h的稳定性实验,发现与VOx/MSU-1相比,催化剂La2O3-VOx/MSU-1具有更好的催化稳定性。     

钒基MSU-1催化剂上二氧化碳氧化异丁烷脱氢反应条件的优化研究

以介孔材料MSU-1为载体,不同金属氧化物为活性组分,分别制备负载型催化剂并研究其在CO<,2>气氛中异丁烷脱氢的催化活性.结果证明VOx/MSU-1催化剂有最好的异丁烷氧化脱氢催化活性.基于此,对影响CO<,2>氧化异丁烷脱氢的温度、空速和氧烷比等工艺条件进行了考察,结果显示,当温度为853 K,空速为7200 mL...     

VOx／SiO2催化剂上异丁烷催化脱氢制异丁烯

研究了使用负载法制备的VOx／SiO2催化剂上的异丁烷催化脱氢制异丁烯的反应。使用XRD和Raman光谱技术表征了催化剂的表面结构,考察了催化剂的钒氧化物负载量、反应温度和H2／n-C4H10比对反应性能的影响。研究结果表明：钒氧化物最大单层覆盖量为9％左右,大于9％催化剂表面开始形成V2O5晶体,堵塞载体孔道,使催化剂活性位减少;V2O5负载量9％为最佳钒氧化物负载景;反应温度在590-620℃,氢烷比为1-3为最佳反应条件。同时C1-C3裂解收率受反应温度影响较大,而与氢烷比及钒氧化物负载量影响不大。     

VO_x/SBA-16催化CO_2氧化乙苯脱氢性能

采用等体积浸渍法制备了不同钒负载量的VOx/SBA-16催化剂,通过XRD、N_2吸附、H_2-TPR和TGA表征和催化剂性能评价,研究了VO_x/SBA-16催化剂对CO_2氧化乙苯脱氢制苯乙烯的催化性能。结果表明,VO_x/SBA-16催化剂具有良好的乙苯脱氢活性,钒负载量为1.2 mmol/g的催化剂活性最佳,乙苯转化率可达57.6%,苯乙烯选择性98.6%。VO_x/SBA-16催化剂上的乙苯脱氢活性和稳定性明显高于VO_x/MCM-41,是由于SBA-16载体畅通的三维孔道结构更有利于钒物种的高度分散和反应介质的扩散,提高了催化剂的可还原性能,减缓了积炭的生成。     

W/Ni比对NiO-WO_3/γ-Al_2O_3催化剂异丁烷氧化脱氢性能的影响

采用分步浸渍法制备了Ni O-WO3/γ-Al2O3系列催化剂,运用X射线衍射(XRD),激光拉曼光谱(Raman),程序升温还原(TPR),氨气程序升温脱附(NH3-TPD),紫外-可见漫反射光谱(UV-vis DRS)等方法考察了n(W)/n(Ni+W)比例对Ni O-WO3/γ-Al2O3催化剂的表面结构、氧化还原性能、酸碱性以及异丁烷氧化脱氢制异丁烯性能的影响。研究结果表明,n(W)/n(Ni)比例对Ni OWO3/γ-Al2O3系列催化剂的表面活性物种种类有较大影响,当W含量较高时,其表面主要形成WO3晶粒和Ni-Al尖晶石,而当W含量较少时,表面主要形成聚钨酸盐、Ni WO4和Ni-Al尖晶石物种;适量的W存在有利于提高Ni O-WO3/γ-Al2O3催化剂的氧化还原性能和可还原晶格氧数量,并且增加W的比例能够提高催化剂表面强酸中心的数量。n(W)/n(Ni)存在最适宜比例,当n(W)/n(Ni+W)=0.2,Ni O-WO3/γ-Al2O3催化剂具有最佳的异丁烷氧化脱氢性能,这与催化剂表面的活性物种具有较好的脱氢性能、可还原晶格氧物种的增多以及表面强酸中心数量的提高有关。     

VO_x/SBA-16催化CO_2氧化乙苯脱氢性能

采用等体积浸渍法制备了不同钒负载量的VOx/SBA-16催化剂,通过XRD、N_2吸附、H_2-TPR和TGA表征和催化剂性能评价,研究了VO_x/SBA-16催化剂对CO_2氧化乙苯脱氢制苯乙烯的催化性能。结果表明,VO_x/SBA-16催化剂具有良好的乙苯脱氢活性,钒负载量为1.2 mmol/g的催化剂活性最佳,乙苯转化率可达57.6%,苯乙烯选择性98.6%。VO_x/SBA-16催化剂上的乙苯脱氢活性和稳定性明显高于VO_x/MCM-41,是由于SBA-16载体畅通的三维孔道结构更有利于钒物种的高度分散和反应介质的扩散,提高了催化剂的可还原性能,减缓了积炭的生成。     

沉淀剂对SrCO_3/La_2O_2CO_3上低温甲烷氧化偶联反应的影响及反应中的热点效应

用共沉淀法制备了系列SrCO3/La2O2CO3催化剂,制备中沉淀剂的选择影响催化剂的物理化学性质,并最终决定其在低温甲烷氧化偶联(OCM)中的催化性能,其中以n(NaOH)∶n(Na2CO3)=2∶1的NaOH/Na2CO3为复合沉淀剂效果最好,对应的催化剂中检测到两种La2O2CO3的组分,分别为四方晶相的(Ⅰ-)和六方晶相的(Ⅱ-)La2O2CO3。这两种晶相的共存为OCM的低温反应提供所需要的活性位。助剂SrCO3抑制了甲烷的过度氧化,提高了C2的选择性。所得到的最佳催化剂能在100℃炉温下维持OCM反应至少24 h,使CH4转化率达25.6%,C2选择性达43.4%。伴随OCM的甲烷氧化生成COx的副反应产生的热点效应为OCM温和反应提供了热源。     

异丁烷脱氢过程催化剂结焦与焦性质研究

在固定床反应装置上,采用YBD型Cr/Al_2O_3催化剂催化异丁烷脱氢,通过热分析技术研究结焦催化剂,考察反应条件对催化剂结焦量及焦性质的影响。结果表明,Cr/Al_2O_3催化剂对异丁烷脱氢有较好的催化活性,当反应温度580℃,空速800 h^(-1)时,异丁烷转化率60%以上,异丁烯选择性90%以上,异丁烯收率约60%。反应温度、空速以及异丁烯对结焦催化剂的焦含量有明显影响,当反应温度超过580℃,随着原料气中异丁烯含量的增加,催化剂的结焦量迅速增加。     

新型异丁烷脱氢催化剂性能

对异丁烷脱氢催化剂YBD-101和国外某催化剂L进行性能比较。采用XRD和BET研究催化剂的物相结构和比表面积,固定床反应器考察两种催化剂的异丁烷脱氢催化活性和产物选择性。结果表明,催化剂YBD-101较催化剂L具有Cr2O3颗粒细小和比表面积大等特点。在反应温度(500~620)℃和空速(1.0~2.0)h-1条件下,催化剂YBD-101的异丁烷转化率高于催化剂L8个百分点,产物选择性高于催化剂L 3个百分点。催化剂YBD-101的活性稳定性优于催化剂L,再生周期明显延长,具有较好的经济效益和社会效益。     

Mg改性Silicalite-1分子筛负载Pt-Sn催化剂对异丁烷脱氢性能的影响

利用等体积浸渍法制备不同镁含量的Mg-Silicalite-1 (Mg-SC-1)分子筛,以该分子筛为载体负载Pt-Sn双金属组分催化异丁烷脱氢反应,采用固定床连续反应器评价催化剂性能,并利用X-射线粉末衍射(XRD)、N2吸附-脱附、程序升温还原(H2-TPR)、扫描电镜(SEM)和碳含量分析等方法研究不同MgO含量的Pt-Sn/Mg-SC-1催化剂的催化性能。实验结果表明,添加w(MgO)=7%到SC-1载体,再负载Pt-Sn组分制备的催化剂异丁烷脱氢效果较好,相比于以纯硅SC-1分子筛为载体的催化剂具有高的反应稳定性和活性。而且经Mg改性后的SC-1载体与助剂SnOx物种之间存在较强的相互作用,导致SnOx物种不易被还原,并促进Pt粒子的分散度。在反应12 h后含w(MgO)=7%的Pt-Sn/Mg-SC-1催化剂仍保留较多的活性Pt粒子。     

Deactivation of VMgO x Catalysts by Coke in the Process of Isobutane Dehydrogenation with Carbon Dioxide

The process of isobutane dehydrogenation in the presence or absence of carbon dioxide was carried out over VMgO _x catalysts with different vanadium loading. The performed tests show that both the reaction atmosphere and physicochemical properties of the catalysts (related to vanadium content) have a great influence on the activity decrease and the carbonaceous deposit formation. Despite small ability of carbon dioxide to remove coke in the Boudouard reaction, the amounts of carbonaceous species deposited on the catalysts after the isobutane dehydrogenation under CO₂ atmosphere were even twice greater in comparison to those deposited in helium stream. Moreover, the rate of coke deposition during the dehydrogenation in the inert gas flow was only slightly dependent on the reaction time, in contrast to the process in carbon dioxide atmosphere. The results show that the coke formation on VMgO _x is enhanced predominantly by surface acidity of the catalysts, which grows with the vanadium content and the presence of CO₂ in the feed.     

Oxidative Dehydrogenation of Propane with CO2 Over Cr/H[B]MFI Catalysts

Abstract  

Cr/silicalite-1 and Cr/H[B]MFI catalysts were prepared by the impregnation method, and Cr/H[B]MFI were further treated by steaming. The catalysts were employed for the oxidative dehydrogenation of propane to propylene with CO₂ as the oxidant. Cr/H[B]MFI showed significantly higher catalytic activity than Cr/silicalite-1, and steamed Cr/H[B]MFI was superior in the reaction stability to Cr/H[B]MFI. The nature of the supported chromium species have been characterized by a number of physicochemical techniques, such as Raman, UV–vis and NMR. It is concluded that the steaming led to the auto-reduction of some Cr⁶⁺ to Cr³⁺, and resultant Cr³⁺ species might be located near the boron center in the borosilicate framework to counterbalance the negative charge of the framework. The transformation of Cr⁶⁺ species to Cr³⁺ species, facilitated by the steaming process and the presence of boron in the catalyst, is responsible for the enhanced stability of oxidative dehydrogenation of propane to propylene with carbon dioxide as the oxidant.     

铁酸盐系列丁烯氧化脱氢催化剂研究进展

综述了铁酸盐系列催化剂(Fe系催化剂)在丁烯氧化脱氢反应中的应用研究进展,介绍了Fe系催化剂的活性中心和氧化脱氢机理,分析了催化剂的失活原因,详述了助剂对Fe系催化剂催化性能的影响,并对Fe系催化剂的发展方向进行了展望。开发出高反应活性、高选择性和高强度的新一代Fe系丁烯氧化脱氢制丁二烯的高效催化剂,是今后的主要研究方向,同时,开发资源利用率高、低投资、低生产成本和废水量少的丁烯氧化脱氢工艺也非常关键。     

Dehydrogenation and Isomerization of n-Butane or Isobutane Over Cr Catalysts Supported on Zeolites

Dehydrogenation and isomerization of n-butane or isobutane into isobutene over Cr catalysts supported on zeolites were investigated. We found that Cr catalyst supported on H-SSZ-35-type zeolite, having one-dimensional cage-type channel structure, was very effective for this reaction and the yield of isobutene was 5.44% from n-butane and 9.57% from isobutane. In this reaction, it is suggested that dehydrogenation of butanes is accelerated by Cr₂O₃ loading, and solid acidity of the zeolite support favors isomerization.     

Oxidative Dehydrogenation of Cyclohexane to Cyclohexene over Mg-V-O Catalysts

The oxidative dehydrogenation of cyclohexane was studied over Mg-V-O catalysts with different Mg/V atomic ratios. Catalysts were prepared via citric acid complexation and characterized by N₂-adsorption, XRD, FT-IR, Raman spectroscopy, NH₃-TPD and H₂-TPR techniques. Among the pure magnesium vanadates, Mg₃(VO₄)₂ has the isolated active sites, weakly basic surface and lower reducibility of the metal cations, and could be recognized as the catalytic active phase. Furthermore, a series of mechanically mixed catalysts were studied in the reaction in attempting to investigate the synergetic effect. The finding revealed synergetic effects in the conversion, in the yield, and in the selectivity were observed in Mg₃(VO₄)₂ mixing with a suitable amount of MgO and Mg₂V₂O₇ due to a solid solution of MgO in the Mg₃(VO₄)₂ phase and the remote control mechanism, respectively. Among the biphasic catalysts, (7/4)MgVO catalyst exhibited a better catalytic performance, on which a cyclohexene selectivity of 45.7% at cyclohexane conversion of 13.9% was obtained.