Ni基催化剂上的乙烷部分氧化制合成气

There is abundant supply of light alkanes and relatively few routes of converting them to more valuable products. Although CH4 predominates in natural gas, it also contains C2H6, C3H8 and C4H10 (from 5 % to 30% ), and with C2H6 as the most abundant secondary component[1]. Partial oxidation of methane to syngas (CH4 +0.5O2 →CO + 2H2) over nickel-based catalysts has received intensive attention[2]and much research has been devoted to conversion of ethane to ethylene[3]. Ethylene has been shown to be formed from ethane by thermal dehydrogenation (C2H6 →C2H4 + H2) and oxidative dehydrogenation (C2H6 + 0. 5O2 →C2H4 + H2O). These processes are operated under severely fuel-rich conditions. The carbon-deposition and consequent deactivation of the catalysts are major problems, which leads to poor conversion of the above mentioned reactions. As an alternative strategy for the elaboration of ethane, little work on the partial oxidation of ethane (POE) to syngas over nickel-based catalysts has been reported. Provided it could be produced from C2H6with high selectivity and high conversion over nickel-based catalysts, syngas could be directly obtained from natural gas including CH4 and C2H6 with high selectivity and conversion. This may lead to better utilization of the light fractions from natural gas and refineries. In the present paper, POE to syngas over nickel-based catalysts was investigated.     

纳米Cr2O3系列催化剂上CO2氧化乙烷脱氢制乙烯反应

 采用溶胶－凝胶法和共沸蒸馏法耦合技术制备了纳米Cr2O3催化剂，并采用共沉淀法和共沸蒸馏法耦合技术制备了纳米Cr2O3／Al2O3，Cr2O3／ZrO2和Cr2O3／MgO复合催化剂．应用BET，XRD，XPS，TPR和TEM等物理化学方法对催化剂的结构和物化性质进行了表征，并考察了该系列催化剂上CO2氧化乙烷脱氢制乙烯的反应性能．结果表明，纳米Cr2O3催化剂上乙烷和CO2的转化率均明显高于常规Cr2O3催化剂，但乙烯的选择性低于常规Cr2O3催化剂；纳米复合催化剂中的复合成分显著影响催化剂的催化性能．其中，10％Cr2O3／MgO纳米复合催化剂在温度为973K时，乙烷转化率和乙烯选择性分别可达到61．54％和94．79％．纳米催化剂表面Cr的还原性以及Cr6＋／Cr3＋比值是影响乙烷转化率和乙烯选择性的重要因素．     

Surface Acidity／Basicity and Catalytic Reactivity of CeO2／γ—A12O3 Catalysts for the Oxidative Dehydrogenation of Ethane with Carbon Dioxide to Ethylene

Dehydrogenation of ethane to ethylene in CO2 was investigated over CeO2/γ-Al2O3 catalysts at 700℃ in a conventional flow reactor operating at atmospheric pressure. XRD, BET and microcalorimetric adsorption techniques were used to characterize the structure and surface acidity/basicity of the CeO2/γ-Al2O3 catalysts. The results show that the surface acidity decreased while the surface basicity increased after the addition of CeO2 to γ-Al2O3. Accordingly, the activity of the hydrogenation reaction of CO2 increased, which might be responsible for the enhanced conversion in the dehydrogenation of ethane to ethylene. The highest ethane conversion obtained was about 15% for the 25?O2/γ-Al2O3. The selectivity to ethylene was high for all the CeO2, γ-Al2O3 and CeO2/γ-Al2O3 catalysts.     

Deactivation of a mixed oxide catalyst of Mo–V–Te–Nb–O composition in the reaction of oxidative ethane dehydrogenation

The operational stability of a mixed oxide catalyst of Mo–V–Te–Nb–O composition in the oxidative dehydrogenation of ethane (ratio of C₂H₆: O₂ = 3: 1) is studied in a flow reactor at temperatures of 340–400°C, a pressure of 1 atm, and a WHSV of the feed mixture of 800 h^?1. It is found that the selectivity toward ethylene is 98% at 340°C, but the conversion of ethane at this temperature is only 6%; when the temperature is raised to 400°C, the conversion of ethane is increased to 37%, while the selectivity toward ethylene is reduced to 85%. Using physical and chemical means (XPS, SEM), it is found that the lack of oxidant in the reaction mixture leads to irreversible changes in the catalyst, i.e., reduced selectivity and activity. Raising the reaction temperature to 400°C allows the reduction of tellurium by ethane, from the +6 oxidation state to the zerovalent state, with its subsequent sublimation and the destruction of the catalytically active and selective phase; in its characteristics, the catalyst becomes similar to the Mo–V–Nb–O system containing no tellurium.     

Experimental investigation of fluidized-bed reactor performance for oxidative coupling of methane

Performance of the oxidative coupling of methane in fluidized-bed reactor was experimentally investigated using Mn-Na2WO4/SiO2,La2O3/CaO and La2O3-SrO/CaO catalysts.These catalysts were found to be stable,especially Mn-Na2WO4/SiO2 catalyst.The effect of sodium content of this catalyst was analyzed and the challenge of catalyst agglomeration was addressed using proper catalyst composition of 2%Mn2.2%Na2WO4/SiO2.For other two catalysts,the effect of Lanthanum-Strontium content was analyzed and 10%La2O 3-20%SrO/CaO catalyst was found to provide higher ethylene yield than La2O3/CaO catalyst.Furthermore,the effect of operating parameters such as temperature and methane to oxygen ratio were also reviewed.The highest ethylene and ethane (C2) yield was achieved with the lowest methane to oxygen ratio around 2.40.5% selectivity to ethylene and ethane and 41% methane conversion were achieved over La2O3-SrO/CaO catalyst while over Mn-Na2WO4 /SiO2 catalyst,40% and 48% were recorded,respectively.Moreover,the consecutive effects of nitrogen dilution,ethylene to ethane production ratio and other performance indicators on the down-stream process units were qualitatively discussed and Mn-Na2WO4/SiO2 catalyst showed a better performance in the reactor and process scale analysis.     

Niobium-containing catalysts for oxydehydrogenation of hydrocarbons and alcohols

The first methods are developed for introducing niobium(V) into Mg-Al hydrotalcites used as precursors of oxide catalysts for oxydehydrogenation (OD) of alkanes and alcohols. Samples of niobium(V)-containing oxide catalysts are synthesized. Their catalytic properties are studied in oxydehydrogenation of ethane and ethylbenzene to styrene, oxidation dehydrocyclization of octane into ethylbenzene and styrene, and oxydehydrogenation of sec-butanol to ketone (octane-(2)-one). It is ascertained that ethane transformation into ethylene is highly a selective highly process (92–97%) at low temperatures (450–500°C) in the presence of a niobium-containing catalyst; the catalyst is appreciably efficient in ethylbenzene transformation to styrene and dehydrocyclization of n-octane to ethylbenzene and styrene, and in oxydehydrogenation of secbutanol to octane-(2)-one. All the catalysts studied operate stably in OD reactions; no decrease in their activity or selectivity was detected after 50 h operation.     

Copper-containing catalysts for the oxidative dehydrogenation of organic compounds

A method of doping magnesium aluminum hydrotalcites, which are precursors for oxidative dehydrogenation oxide catalysts of various compositions, with copper(II) was developed, and copper(II)-containing oxide catalyst samples were synthesized. The catalytic properties of these catalysts were studied in the oxidative dehydrogenation of ethane, propane, and hexane. The conversion of ethane into ethylene on the copper-containing catalysts was established to proceed with high selectivities (90?C97%) and at low temperatures (400?C450°C).     

Oxidative dehydrogenation of ethane with carbon dioxide over sulfated zirconia supported metal oxides catalysts

Several metal oxides supported on sulfated zirconia catalysts were tested for the oxidative dehydrogenation of ethane into ethylene by carbon dioxide. It is found that the catalytic behavior of supported oxide catalysts differ depending on the nature of metal oxides. Chromium oxide-sulfated zirconia exhibits the highest ethane conversion and medium level of ethylene selectivity, producing 38% ethylene yield at 50% ethane conversion at 650°C.     

负载型Co-Cr氧化物催化剂上CO2氧化乙烷脱氢制乙烯反应的研究

制备了一系列不同Co／Cr比例的Co-Cr／SiO2和Co-Cr／γ-Al2O3催化剂，并应用XRD等技术对所制样品进行了表征．在常压连续流动固定床石英反应器中考察了它们对CO2乙烷氧化脱氢反应的催化性能．实验结果表明，Co-Cr／SiO2和Co-Cr／γ-Al2O对CO2乙烷脱氢制乙烯都有较高的催化活性，其活性都明显高于负载单一组分的催化剂．以γ-Al2O为载体的催化剂活性明显比以SiO2为载体的催化剂活性高．1％Co-5％Cr／γ-Al2O活性最高，973K乙烷的转化率达25．57％，乙烯的选择性和收率分别达94．28％、24．10％．     

Kinetic study of oxidative coupling of methane over Mn and/or W promoted Na_2SO_4/SiO_2 catalysts

A comprehensive kinetic model for oxidative coupling of methane(OCM)over Mn and/or W promoted Na2SO4/SiO2 catalysts was developed based on a micro-catalytic reactor data.The methane conversion and ethylene,ethane,carbon monoxide and carbon dioxide selectivities were obtained in a wide operating condition range of 750 - 825-C,CH4/O2=2.5 - 10 and contact time=267 - 472 kg s m-3.Reaction networks of six models with different rate equation types were compared together.The kinetic rate parameters of each reaction network were estimated using linear regression or genetic algorithm optimization method(GA).A reaction network suggested by Stansch et al.for OCM was found to be the best one and was further used in this work.The suggested model could predict the experimental results of OCM reaction within a deviation range of ± 20%.     

用于乙烷氨氧化反应的高效Sb2O3/Co-ZSM-5催化剂

低碳烷烃（C1～C4）广泛存在于石油气、天然气、焦炉气及石油裂解气中，因其容易获得且成本低廉，以它们为原料直接转化合成其它化工产品无论在技术上还是在商业方面都有很大的吸引力．低碳烷烃的催化氨氧化是对其有效利用的途径之一．目前对低碳烷烃氨氧化的研究主要集中在丙烷上，对乙烷氨氧化制乙腈的反应研究尚处在探索阶段．与丙烷相比，乙烷的化学活性较低，一般需在较为苛刻的条件下才能反应，且对主产物的选择性较低．     

Hydrothermal Synthesis of Mo-Based Oxide Catalysts and Selective Oxidation of Alkanes

Mo-V-M(=Al, Ga, Bi, Sb and Te)–O mixed oxide catalysts were synthesized hydrothermally for the first time, characterized structurally, and tested for ethane and propane oxidation after activation by various ways. These catalysts were black solids of rod-shaped (fiber like) crystals, which had a layer structure in the direction of fiber axis and a high dimensional arrangement of metal octahedra in the cross-section plane. These fresh crystalline materials became active for catalytic oxidation of alkanes after heat-treatment at 600 °C and subsequent grinding in order to increase exposed plane of the cross-section. The resulting catalysts were very active for an oxidative dehydrogenation of ethane with 80% of the ethylene selectivity in the reaction temperature range of 300 to 400 °C and also showed about 50% selectivity to acrylic acid in the propane oxidation. Multi-functional character which derived from the high dimensional structure of the catalysts and mechanism of the selective alkane oxidation were discussed.     

Tantalum-containing catalysts for oxydehydrogenation of hydrocarbons and alcohols

The first methods were developed for introducing tantalum(V) into Mg-Al hydrotalcites, which are precursors of oxide catalysts for oxydehydrogenation of hydrocarbons and alcohols. Samples of oxide tantalum(V)-containing catalysts were synthesized. Their catalytic properties were studied in the oxydehydrogenation of ethane to ethylene and ethylbenzene to styrene, oxydehydrocyclization of octane to ethylbenzene and styrene, and oxydehydrogenation of sec-butanol to ketone (octan-2-one). The transformation of ethane to ethylene over the tantalum-containing catalyst occurs with a high selectivity (92–97%) at relatively low temperatures (500°C), and the catalyst is quite efficient in conversion of ethylbenzene to styrene, dehydrocyclization of n-octane to ethylbenzene and styrene, and oxydehydrogenation of sec-butanol to octan-2-one. Comparison with a niobium-containing catalyst showed that it ensures higher yields and selectivities in similar reactions than its tantalum-containing analogue does.     

甲烷在SrO-La_2O_3/CaO催化剂上的氧化偶联 Ⅰ.SrO对La_2O_3/CaO催化剂的助催化作用

在常压流动反应装置上评价了一系列La_2O_3/CaO催化剂和SrO-La_2O_3/CaO催化剂。实验表明:La_2O_3/CaO体系是很好的甲烷氧化偶联催化剂。在1073K和CH_4:O_2:He=4:1:5(总流速120ml/min)的实验条件下,20％La_2O_3/CaO催化剂上的甲烷转化率为26％,C_2选择性为53％;加入助剂SrO(15—20％)后,在同样实验条件下,甲烷转化率为29％,C_2选择性为66％。表明SrO对La_2O_3/Cao催化剂有明显的促进作用。用XRD,XPS和TPD(CO_2-TPD和O_2-TPD)技术表征了SrO-La_2O_3/CaO催化剂体系,结合反应评价结果,认为SrO的促进作用可以归结为:(1)调变了催化剂的碱性强度分布,提高了催化剂表面强碱中心的数目;(2)提高了La_2O_3的分散度;(3)抑制了催化剂的低温氧吸附物类。     

Enhanced NiO Dispersion on a High Surface Area Pillared Heterostructure Covered by Niobium Leads to Optimal Behaviour in the Oxidative Dehydrogenation of Ethane

A Nb-containing siliceous porous clay heterostructure (PCH) with Nb contents from 0 to 30 wt %) was prepared from a bentonite and used as support in the preparation of supported NiO catalysts with NiO loading from 15 to 80 wt %. Supports and NiO-containing catalysts were characterised by several physicochemical techniques and tested in the oxidative dehydrogenation (ODH) of ethane. The characterisation studies on Nb-containing supports showed the presence of well-anchored Nb⁵⁺ species without the formation of Nb₂O₅ crystals. High dispersion of nickel oxide with low crystallinity was observed for the Nb-containing PCH supports. In addition, when NiO is supported on these Nb-containing porous clays, it is more effective in the ODH of ethane (ethylene selectivity of ca. 90 %) than NiO supported on the corresponding Nb-free siliceous PCH or on Nb₂O₅ (ethylene selectivities of ca. 30 and 60 %, respectively). Factors such as the NiO–Nb⁵⁺ interaction, the NiO particle size and the properties of surface Niⁿ⁺ species were shown to determine the catalytic performance.     

Effect of Brønsted/Lewis Acid Ratio on Conversion of Sugars to 5‐Hydroxymethylfurfural over Mesoporous Nb and Nb‐W Oxides

A series of mesoporous Nb and Nb‐W oxides were employed as highly active solid acid catalysts for the conversion of glucose to 5‐hydroxymethylfurfural (HMF ). The results of solid state ³¹P MAS NMR spectroscopy with adsorbed trimethylphosphine as probe molecule show that the addition of W in niobium oxide increases the number of Brønsted acid sites and decreases the number of Lewis acid sites. The catalytic performance for Nb‐W oxides varied with the ratio of Brønsted to Lewis acid sites and high glucose conversion was observed over Nb₅W₅ and Nb₇W₃ oxides with high ratios of Brønsted to Lewis acid sites. All Nb‐W oxides show a relatively high selectivity of HMF , whereas no HMF forms over sulfuric acid due to its pure Brønsted acidity. The results indicate fast isomerization of glucose to fructose over Lewis acid sites followed by dehydration of fructose to HMF over Brønsted acid sites. Moreover, comparing to the reaction occurred in aqueous media, the 2‐butanol/H₂O system enhances the HMF selectivity and stabilizes the activity of the catalysts which gives the highest HMF selectivity of 52% over Nb₇W₃ oxide. The 2‐butanol/H₂O catalytic system can also be employed in conversion of sucrose, achieving HMF selectivity of 46% over Nb₅W₅ oxide.     

MnCl2-H4SiW12O40/SiO2催化氧化二甲醚制取甲缩醛

 采用浸渍法制备了H4SiW12O40/SiO2杂多酸催化剂,分别使用MnCl2, SnCl4和CuCl2对其进行修饰,并在常压连续流动固定床反应器中考察了催化剂对二甲醚选择氧化制取甲缩醛的催化活性. 结果表明, MnCl2修饰的H4SiW12O40/SiO2催化剂的活性和甲缩醛选择性均高于SnCl4和CuCl2修饰的催化剂. 进一步考察了不同MnCl2含量及反应温度对反应的影响. 在MnCl2含量为5%, 反应温度为593 K时, MnCl2-H4SiW12O40/SiO2催化剂的活性和甲缩醛选择性最佳,二甲醚转化率为8.6%, 甲缩醛选择性为36.3%. X射线衍射结果显示, MnCl2与H4SiW12O40相互作用并均匀地分散在载体上. 用红外光谱研究了MnCl2-H4SiW12O40/SiO2催化剂的结构,发现改性后的催化剂基本保持了杂多酸的Keggin结构. NH3程序升温脱附结果显示, MnCl2的加入较明显地降低了催化剂的酸强度和酸中心数目.     

沉积-沉淀法和沉积-还原法制备Nb2O5负载的金纳米粒子及其催化CO氧化活性

采用不同的沉积法制备了氧化铌(Nb2O5)负载的金纳米粒子催化剂,即沉积-沉淀(DP)法、尿素辅助的DP法、沉积-还原(DR)法和一步法制备了1 wt%Au/Nb2O5催化剂.在众多类型Nb2O5(包括商业Nb2O5)中,采用水热法制备的层间型Nb2O5(Nb2O5(HT))最适合用作载体.结果表明,较大比表面积的Nb2O5(HT)使得金以纳米颗粒形式分散于其上.在优化的条件下,以DP和DR法沉积于Nb2O5(HT)上的金纳米粒子平均粒径为5 nm.采用DR法制备的Au/Nb2O5(HT)催化剂上CO转化率为50%时的温度为73oC.不沉积金的条件下,即使在250oC, Nb2O5(HT)对CO氧化反应也没有催化活性.因此,金的沉积对活性的促进作用非常明显.该简易Au/Nb2O5催化剂将金催化剂的类型扩展到酸性载体,这将增加新的应用.     

Synthesis and characterization of niobium-promoted cobalt/iron catalysts supported on carbon nanotubes for the hydrogenation of carbon monoxide

Bimetallic Co /Fe catalysts supported on carbon nanotubes( CNTs) were prepared,and niobium( Nb) was added as promoter to the 70 Co ∶30Fe /CNT catalyst. The physicochemical properties of the catalysts were characterized,and the catalytic performances were analyzed at the same operation conditions( H_2 ∶CO( volume ratio) = 2 ∶1,p = 1 MPa,and t = 260 ℃) in a tubular fixed-bed microreactor system. The addition of Nb to the bimetallic catalyst decreases the average size of the oxide nanoparticles and improves the reducibility of the bimetallic catalyst. Evaluation of the catalyst performance in a Fischer-Tropsch reaction shows that the catalyst results in high selectivity to methane,and the selectivity to C_(5+) increased slightly in the bimetallic catalyst unlike that in the monometallic catalysts. The addition of 1% Nb to the bimetallic catalyst increases CO conversion and selectivity to C_(5+). Meanwhile,a decrease in methane selectivity is observed.     

氧化镍与载体相互作用对乙烷氧化脱氢的影响

研究了担载型催化剂NiO／γ－Al2O3的乙烷氧化脱氧（ODHE）性能,发现在400－500℃的考察温区内,担载型NiO较纯NiO的乙烯选择性有较大提高,保持在80％～90％之间,其中含17％Ni的样品500℃时乙烷的转化率为31％,乙烯选择性达82％．XRD、H2-TPR及原位磁测量结果表明：催化剂的活性相是与载体相互作用较小的、处于表层的微晶态NiO,NiO中非化学计量氧仍为活性氧物种．催化剂焙烧温度的提高,一方面降低了活性相中非化学计量氧量,同时加剧了NiO与载体γ－Al2O3的相互作用,二者均使活性降低．O2－TPD研究表明：与纯NiO相比,在Nio／γ－Al2O3中,其非化学计量氧的脱附温度发生变化,其中,α氧脱附温度向低温移动约50℃,而对乙烯选择性有关的β氧的脱出则向高温区移动了约200℃,正好与反应温区对应,进一步证实非化学计量氧与ODHE反应之间存在对应关系,上述结果表明那些对氧化镍还原有一定的阻碍作用,尤其阻碍镍深度还原（Ni2 →Nio）的载体对促进反应的乙烯选择性是有利的．