SiO_2气凝胶钼尾矿金属催化剂的应用研究

利用商洛钼尾矿与亲水型Si O2气凝胶结合制成的气凝胶钼尾矿催化剂对甲醇与乙醇一步合成异丁醛、仲丁醇的氧化反应的催化活性进行考察。通过改变催化剂的用量和反应时间考察催化剂的催化活性。用傅立叶变换红外光谱仪对产物进行分析。结果表明:甲醇与乙醇一步合成异丁醛的反应在2 h时有醛基吸收峰;仲丁醇氧化反应在2 h时有羰基吸收峰;说明此催化剂对这两个反应均有一定活性。     

甲醇氧化羰化合成碳酸二甲酯催化剂研究进展

碳酸二甲酯的合成是近年来国内外的一个研究热点.氧化羰化法已经成为一种有效的合成碳酸二甲酯的方法.综述了甲醇氧化羰基化合成碳酸二甲酯催化剂的研究和开发现状.深入探讨了液相氧化羰化合成中铜基催化剂的研究进展及其反应机理,并比较了不同的铜催化剂在氧化羰化中的催化效果.为进一步提高催化剂的活性、选择性、延长催化剂寿命、减少腐蚀性,开发出性能更好的工业催化剂,则需要深入研究其作用机理,并通过添加助剂和载体的方式来实现.     

Preparation of Cu/ZnO/Al2O3 catalysts in a solvent-free routine for CO hydrogenation

The synthesis of methanol and dimethyl ether (DME) from CO hydrogenation has been investigated on Cu-based catalysts. A series of Cu/ZnO/Al₂O₃ catalysts were prepared using a solvent-free routine which involved a direct blend of copper/zinc/aluminum salts and citric acid, followed by calcination at 450 °C. The calcination processes were monitored using thermogravimetry differential scanning calorimetry (TG-DSC). Catalysts were further characterized using N₂ adsorption, scanning electronic microscopy (SEM), X-ray diffraction (XRD), N₂O oxidation followed by H₂ titration, and temperature-programmed reduction with H₂ (H₂-TPR). The reduction processes were also monitored with in-situ XRD. The physicochemical properties of catalysts depended strongly on the types of precursor salts, and catalysts prepared using Al acetate and Cu nitrate as starting materials had a larger surface area, larger exposed metallic copper surface area, and lower reduction temperature. The CO hydrogenation performances of these catalysts were compared and discussed in terms of their structures. Catalysts prepared with copper nitrate, zinc and aluminum acetates exhibited the highest catalytic activity.     

合成氨催化剂的研究进展

综述了合成氨工业催化剂从Fe3O4基到Fe1-xO体系和钌催化剂的发展,表明Fe1-xO催化剂体系的发明,使氨合成催化剂的活性有了长足的进步,而钌催化剂有望突破近一个世纪的铁催化剂的历史。结合氨合成的发展现状,提出合成氨催化剂的发展建议。     

CaF2-doped ZrO2： A base catalyst for synthesis of dimethyl carbonate

The effect of CaF2-doped ZrO2 catalyst for the synthesis of dimethyl carbonate （DMC） was studied by X-ray diffraction （XRD）, CO2-temperature programmed desorption （TPD）, Raman spectra, and X-ray photoelectron spectroscopy （XPS）. Catalytic performance was evaluated in the bath and distillation reactors. Results showed that the CaF2/ZrO2 catalysts had activity and stability for DMC synthesis.     

Modification of acidity in HZSM-5 zeolite for methane-methanol co-reaction

A co-reaction of methane with methanol over zeolite catalysts has emerged as a new approach to the long-standing challenge of methane transformation. However, the effect of catalyst acid properties on the co-reaction has been rarely studied. In this study, a series of HZSM-5 zeolites with comparable diffusion abilities and various acidities were synthesized directly through steaming with 100% water vapor at 693 K. The co-reaction of methane and methanol was subsequently evaluated. Br?nsted acidity at 0.262 mmol/g was detected to reach the maximum methane conversion of 5.42% at 673 K, which was also the odd point in the relationship between acid concentration and C4 hydrogen transfer index. Moreover, the influence of methanol feed was investigated over parent and steamed ZSM-5 catalyst, with results showing that excessive acid sites or methanol molecules reduce methane conversion. It is proposed that acid sites adsorbed with methanol molecules construct the methane activation sites. Hence, a proper design of zeolite acidity should be achieved to obtain higher methane conversion in the co-reaction process.     

ClO-4/TiO2固体超强酸催化合成乙酸异戊酯

对ClO4^-／TiO2型固体超强酸催化剂的制备进行了研究，并应用于乙酸异戊酯的合成,考察了HClO4浓度和焙烧温度等条件对催化剂活性的影响．通过改变催化剂用量、反应时间、反应物物质的量等对产品收率影响的考察，结果表明，ClO4^-／TiO2型固体超强酸催化剂对合成乙酸异戊酯具有较好的催化性，具有一定的推广价值．     

Synthesis of Dimethyl-2,6-Naphthalene Dicarboxylate by Esteriflcation Catalyzed by Sodium Tungstate

The process of synthesis of dimethyl-2,6-naphthalene dicaboxylate from esterification of 2,6-naphthalene dicarboxylic acid (2,6-NDCA) by methanol using sodium tungstate as catalyst was investigated. The orthogonal tests method was used for optimizing the process factors. The effects of reaction temperature, mass percentaga of catalyst, reaction time and mass ratio of methanol to 2,6-NDCA on the 2,6-NDCA conversion were investigated. It was found that all the four factors had significant effect on the conversion. The optimum reaction conditions were reaction temperature 215 °C ,mass percentage of catalyst 3%, reaction time 3 h, mass ratio of methanol to 2,6-NDCA 6: 1. The 2,6-NDCA conversion at above condition was 92.80%.     

合成吡啶催化剂的研究

醛(酮)氨法合成吡啶可用ZSM-5作催化剂, 本文研究了ZSM-5催化剂的表面酸性与催化合成吡啶活性之间的关系. 合成了硅铝质量比为120的ZSM-5, 并用钴、铁对其进行改性, 用吡啶红外光谱技术测定了ZSM-5的表面酸性. 研究表明用Co2 ,Fe3 离子对HZSM-5进行改性, Lewis酸中心明显减少, 对氨的吸附能力下降, 这种现象保证了足够多的酸中心暴露和醛反应, 有利于吡啶碱的形成, 吡啶碱产率可达78%. 该研究为制备高活性、高选择性的合成吡啶催化剂提供了理论依据.     

TiSiW_(12)O_(40)/TiO_2的合成、表征及催化性能研究

本文报道了非均相固载型杂多酸盐催化剂ＴｉＳｉＷ１２Ｏ４０／ＴｉＯ２的制备方法,并用ＩＲ、ＸＲＤ谱对该催化剂进行了表征,研究了该催化剂催化酯化合成邻苯二甲酸二丁的醇酸比、催化剂用量、带水剂等因素对酯收率的影响。实验表明,在以苯为带水剂时,催化剂的用量为反应液的１．１％,醇酸摩尔比为３．５∶１,酯化反应时间为２．５ｈ,邻苯二甲酸二丁酯的收率达９８．８％,超过硫酸、磷钨酸的催化水平     

SO4^2-/TiO2催化剂在甲醇制烯烃的应用研究

采用溶胶一凝胶法制备SO4^2-/TiO2催化剂的基体,用不同浓度的硫酸对催化剂基体进行浸渍,考察催化剂性能。选出制备催化剂的硫酸浓度。考察反应温度、甲醇流量对催化剂性能的影响;探讨了催化剂失活的原因。实验结果表明,催化剂S10活性最好;甲醇制烯烃的反应温度为410-430℃,具有98．8％的甲醇转化率和90．65％的乙烯选择性：反应时甲醇的流量为0．05mol·s^-1。     

合成甲醇催化剂的发展综述

介绍了甲醇合成催化剂由最初的含铬催化剂，经铜基催化剂，发展到现在非铜基催化剂的发展过程．其中铜基催化剂在甲醇合成中占有主导地位，并从活性位和添加助剂钾和锆三方面做了详细的说明．     

TiSiW_(12)O_(40)/TiO_2催化合成邻苯二甲酸二丁酯

报道了新型催化剂ＴｉＳｉＷ１２Ｏ４０／ＴｉＯ２催化酯化合成邻苯二甲酸二丁酯的醇酸比、催化剂用量、带水剂等因素对酯收率的影响．实验表明，在以苯作带水剂，催化剂的用量为反应液的１．１％，醇酸摩尔比为３．５：１，酯化反应时间为２．５ｈ，邻苯二甲酸二丁酯的收率达９８．８％，超过硫酸、磷钨酸、ＳｎＳｉＷ１２Ｏ４０／ＳｎＯ２的催化水平．     

La_(1-X)Sr_xMnO_3催化剂的制备及其催化甲烷燃烧性能研究

以催化甲烷燃烧为目标反应,采用共沉淀法制备一系列Sr2+部分掺杂La3+的钙钛矿型催化剂La1-XSrXMnO3(x=0.0,0.2,0.4,0.6,0.8,1.0),通过XRD,BET,DSC-TG和TPR等实验技术,对催化剂的结构和性质进行了考察,制备出催化性能好的催化剂。考察了Sr掺杂量多少对催化剂结构及催化甲烷燃烧活性的影响。结果表明:催化剂在600℃焙烧6h后可以形成完整的钙钛矿晶型,同时具有较高的催化性能。不同量的Sr掺杂对于催化剂的性能有较大的影响,Sr离子对Mn离子存在着一定程度的协同作用。由于Sr的加入使催化剂的活性降低。     

Novel Pt–Ni Bimetallic Catalysts Pt(Ni)–LaFeO3/SiO2 via Lattice Atomic-Confined Reduction for Highly Efficient Isobutane Dehydrogenation

In this study, a series of novel Pt-Ni bimetallic catalysts supported on LaFeO_3/SiO_2 with different amounts of Ni were prepared by the lattice atomic-confined reduction of LaFe_(1-x)(Ni, Pt)_xO_3/SiO_2 perovskite precursors and applied in isobutane dehydrogenation to isobutene reaction. The catalysts were characterized by X-ray diffraction, H_2-temperature-programmed reduction, Brunauer-Emmett-Teller analysis, transmission electron microscopy, energy dispersive X-ray, CO chemisorption, X-ray photoelectron spectroscopy, and thermogravimetric analysis. The as-synthesized Pt-Ni bimetallic catalysts possessed smaller most probable particle size with tunable Pt-Ni interaction, depending on the Ni content. The catalyst with Ni content of 3.0 wt% showed excellent activity and stability(the isobutane conversion and isobutene selectivity remained at about 38% and 92%, respectively, after 310 min) for the isobutane dehydrogenation reaction. It also provided approximately six times turnover frequency of the catalyst without Ni. The excellent activity and stability of the 3.0 wt% Ni-containing catalyst can be attributed to its small metal nanoparticles with high dispersion and suitable Pt-Ni interaction. Moreover, the Pt(Ni)-LaFeO_3/SiO_2 catalyst with Ni content of 3.0 wt% had been run for more than 35 h without obvious loss of activity,indicating its long-term stability, and the decrease in the Pt-Ni interaction that accompanied the formation of the FeNi alloy phase was thought to be responsible for the slight decrease in activity.     

几种稀土固体超强酸催化合成异戊酸异戊酯的研究

采用稀土元素对SO2-4／TiO2固体超强酸的改性，制备出一系列稀土固体超强酸催化剂，用于合成异戊酸异戊酯的反应中，筛选出最佳催化剂为：SO2-4／TiO2/Sm^3 ，并研究了SO2-4／TiO2/Sm^3 的再生及合成异戊酸异戊酯的催化性能。     

制备方法对镍催化剂重整活性影响研究

利用XRD,TPR和活性评价等手段,研究了NiO/γ-Al2O3催化剂的制备方法对CH4与CO2转化制合成气催化活性的影响.在本实验条件下,采用浸渍法和焙烧温度为400℃制备的NiO/γAl2O3(ω=0.113)催化剂,在反应温度为750℃和空速为2500h-1下,对CH4和CO2重整反应会显示良好的催化活性.本文还对催化剂抗积炭性能作初步讨论.     

烟用三醋酸甘油酯的合成研究

将混合稀土硝酸盐用于催化冰醋酸与甘油的酯化反应 ,研究了催化剂用量、酸醇比、反应时间等因素对酯化率的影响 ,确定了最佳工艺条件 .结果表明 :混合稀土硝酸盐具有很好的催化活性 .该反应具工艺流程短 ,无设备腐蚀 ,产品色泽度好 ,酯化率高等优点     

Effect of support calcination temperature on the Ru-Ce-B/ZrO_2 catalysts for benzene selective hydrogenation to cyclohexene

The effect of support calcination temperature on the benzene selective hydrogenation performance of the Ru-Ce-B/ZrO2 catalysts was investigated.It was found that with increasing calcination temperature,the surface area decreased,on the contrary,the pore size and the amount of monoclinic phase increased.With increasing support calcination temperature,the activity of the catalyst roughly decreased and cyclohexene selectivity increased.The activity decreased due to the decrease of the surface areas.The increase of the cyclohexene selectivity was correlated not only with the decrease of the surface areas but also with the increase of monoclinic phases,rich in surface hydroxyl,and the enlarged pore size of zirconia.This suggests the monoclinic zirconia with a medium surface area,rather than a big one,and a mesoporous structure,even including some macropores,is an ideal support of the catalyst for benzene selective hydrogenation.     

用于生物柴油生产的固体碱催化剂CaO的低温活化

分别研究了甲醇、甘油和水三种不同的活化剂对固体碱催化剂CaO在制备生物柴油中的活化作用,考察了活化时间对CaO活性的影响以及三种活化方式在空气中的耐失活能力,同时也探讨了三种活化方式的活化机理。结果发现：甲醇的活化效果不是很好,而甘油和水则对CaO有较好的活化效果,并且用水活化时不需要预先活化就有较高的活化作用;甘油活化后的CaO在空气中放置15d活性没有明显降低。无论是用甲醇、甘油还是用水来活化,它们对CaO活性的提高除了对酯交换反应体系的加速作用外,甲醇和水还有对CaO表面的去碳酸化作用,同时甘油还有去羟基化和去碳酸化作用。