钴的引入对双环戊二烯氢甲酰化担载Rh催化剂的性能影响

以双环戊二烯(DCPD)氢甲酰化反应为探针反应,系统考察了无机氧化物担载的Rh催化剂上引入Co后对性能的影响。实验结果表明:Co的引入不仅可以大幅度的提高DCPD氢甲酰化产物三环癸烷二甲醛(DFTD)的选择性,而且可以加快DFTD的生成速率;相对于Rh催化剂,引入Co之后,DFTD的选择性可以提高20%以上,DFTD的选择性最高可达88.7%。为研究Rh催化剂上引入Co对催化剂活性和目标产物选择性大幅提高的原因,分别对催化剂进行了程序升温还原(TPR)和程序升温脱附(TPD)的表征。TPR的结果显示Co和Rh发生了相互作用,Rh的还原峰明显发生了一定的位移;TPD的结果显示Rh在载体表面的分散性有降低的趋势,表面的Rh活性物种有一定的减少。结合实验数据和表征数据,Rh催化剂上引入Co使催化活性和产物选择性提高的原因可归结为:Co和Rh发生了相互作用;Co的引入虽然造成了表面Rh含量降低,但是形成了高于Rh的活性的新物种,从而导致了催化剂活性和目标产物选择性大幅提高。     

Characteristics of the Photocatalytic Oxidation of Methane into Methanol on V-Containing MCM-41 Catalysts

V-containing MCM-41 catalysts were prepared by a direct synthesis method under acidic and basic conditions and impregnation. Their photocatalytic reactivity was evaluated for the selective photocatalytic oxidation of methane with NO under UV irradiation at 295 K. Selective methanol formation was observed on V-MCM-41 prepared in acidic solution and imp-V/MCM-41, while only coupling reaction products were obtained on V-MCM-41 prepared in basic solution. The photocatalytic reactivity of the catalysts for the partial oxidation of methane was found to strongly depend on the local structure of the V-oxide species including the coordination and loading sites, i.e., the charge transfer excited states of the isolated tetrahedral V⁵⁺-oxide species supported on the catalyst surface act as the active sites for the selective photocatalytic oxidation of methane into methanol.     

A Facile and Effective Method for the Distribution of Mo/HZSM-5 Catalyst Active Centers

Post-steaming treatment of Mo/HZSM-5 catalysts results in more molybdenum species migrating into and residing in the HZSM-5 zeolite channels. This is confirmed by XRF and XPS measurements. ¹H MAS NMR and ²⁹Si MAS NMR also demonstrate that the number of free Brönsted acid sites decreases in the Mo/HZSM-5 catalysts that underwent post-steaming treatment, compared to untreated Mo/HZSM-5 catalysts. As a result, the deactivation rate constant (k _d) on the Mo/HZSM-5 catalyst after post-steaming treatment for 0.5h is much smaller, and the catalyst therefore shows remarkable stability in the probe reaction of methane dehydro-aromatization. The results suggest that a more beneficial bi-functional balance between active Mo species for methane activation and acid sites for the following aromatization is developed over those Mo/HZSM-5 catalysts that have experienced post-steaming treatment for 0.5h, in comparison with the untreated Mo/HZSM-5 catalysts.     

载体酸性对Pt/USY菲加氢制烷基金刚烷的影响

以Pt为活性组分、经不同浓度草酸铝处理的USY分子筛为载体,制备了Pt/USY催化剂,并用于菲一步加氢饱和反应和加氢异构反应体系。由于金属活性位点Pt上易发生加氢反应,USY载体酸性位点上易发生异构反应和裂解反应,实验分别考察了Pt颗粒、载体的酸强度和酸量对菲转化率和产物分布的影响。结果表明,活性金属Pt颗粒尺寸及分散度直接影响菲加氢饱和产物分布;草酸处理后制备的催化剂Pt/0.05-USY、Pt/0.1-USY较未经酸处理的Pt/USY更利于菲加氢反应。全氢蒽是菲向目标产物烷基金刚烷转化的关键中间产物,异构产物烷基金刚烷生成需在USY分子筛Br?nsted酸位点完成;随着催化剂载体酸量和酸强度的降低,裂解反应程度迅速减弱;菲加氢反应最终产物以加氢饱和反应产物为主;使用Pt/0.1-USY催化剂异构反应产物烷基金刚烷收率为2.3%。     

Fischer–Tropsch synthesis over cobalt catalysts supported on zirconia-modified alumina

The effect of adding zirconia to the alumina support on supported cobalt Fischer–Tropsch catalysts has been studied. At 5 bar and H₂:CO ratio 9:1 zirconia addition to the support leads to a significant increase in both activity and selectivity to higher hydrocarbons as compared to the unmodified catalysts. Reducibility and cobalt dispersion on the other hand are not improved by the presence of zirconia compared to the unmodified catalysts. SSITKA measurements have been performed in order to determine the intrinsic activity per active site. At constant temperature, zirconia-modified and unmodified catalysts showed basically the same intrinsic activity. Similar results were obtained with a noble metal (Pt) promoted catalyst. The promoting effect appears to be mainly due to coverage effects rather than a change in the intrinsic activity of the active sites. The turnover frequencies were found to be independent of pressure but strongly temperature dependent. However, the increase in turnover frequency did not account for the entire increase in reaction rate with temperature. This indicates that also the coverage of reactive intermediates increases with increasing temperature.     

Methane partial oxidation to synthesis gas using nickel on calcium aluminate catalysts

Nickel was supported on calcium aluminate carriers that were obtained with varying CaO to Al₂O₃ molar ratios and calcination temperatures. The variations of the supports lead to catalysts of different surface properties and catalytic performance. Metallic nickel (Ni⁰) was proven to be the active species for the methane partial oxidation reaction. The presence of filamentous carbon on used catalysts was also suggested. The differences in the catalytic activity and selectivity for the methane partial oxidation reaction was ascribed to a varying degree of reducibility of the surface nickel species.     

Carbon Dioxide Reforming of Methane over Nickel Catalyst Supported on MgO(111) Nanosheets

MgO nanosheets possessing the (111) facet as the main surface were synthesized and the Ni catalyst supported on MgO(111) nanosheets was investigated for the carbon dioxide reforming of methane. The catalytic activity and carbon deposition were compared between Ni/MgO(111) and Ni/MgO(commercial) catalysts. The results showed that Ni/MgO(111) performed at a higher activity as well as a longer stability. From the characterization results, the improved catalytic performances of Ni/MgO(111) were suggested to be closely associated with both the high dispersion of active Ni particles owing to the strong metal-support interaction and the large amount of basic sites of MgO(111) due to its unusual surface properties.     

合成氯乙酸酯催化剂的研究进展

文章详细介绍了目前国内不同的催化剂合成氯乙酸酯。这些催化剂主要包括:磺酸类、固载杂多酸、固体超强酸、无机盐、负载型催化剂,这些催化剂在化学反应中的使用改善了反应条件,提高了产品的收率,各有自己的优缺点。     

Carbon dioxide reforming of methane over nickel catalysts supported on mesoporous MgO

In this paper, ordered mesoporous MgO nanocrystals [MgO(M)] were synthesized, and the nickel catalysts supported on MgO(M) were facilely prepared by impregnation method. The obtained Ni/MgO(M) catalysts with advantageous textural properties were investigated as the catalysts for the carbon dioxide reforming of methane reaction. It was found that compared with the Ni/MgO(C) catalyst [MgO(C): commercial MgO], the mesoporous pore structure of MgO(M) could effectively limit the growth of the activity metal, and the Ni/MgO(M) catalysts showed high catalytic activities as well as long catalytic stabilities toward this reaction. The results showed that the conversions of CH₄ and CO₂ were only decreased <5 % after 100 h of reaction at 650 °C. The improved catalytic performance was suggested to be closely associated with both the advantageous structural properties, such as large specific surface area, uniform pore size, and the “confinement effect” of the mesoporous matrixes contributed to stabilize the Ni active sites during the reaction. The carbon species deposited on the spent Ni/MgO(M) catalyst were analysized by TG and Raman, and the results exhibited that the carbon species after 100 h of reaction were mainly active carbon species.     

负载型铬基催化材料的制备与应用

负载型铬基催化材料不仅可显著提高铬活性组分的分散度并保留其多价态性,同时兼具多孔载体材料固有的孔结构、强酸性及优异的分子扩散性能,从而表现出良好的催化活性,并作为一类重要的催化剂有效应用于多种催化过程。本文详细阐述了目前负载型铬基催化剂在制备方法及催化应用方面的研究进展,并就合成方法、载体性质、金属前体及助剂等因素对铬物种引入量、分散程度及配位状态的影响以及进而造成对催化剂孔道结构、反应活性及使用寿命的影响进行了详尽地评述。同时指出了通过改变载体的表面酸性、孔结构及其与活性组分铬物种间的相互作用,从而提高铬物种在载体中的分散度和稳定性是今后负载型铬基催化材料研究的重要方向。     

Optimization of the pretreatment procedure in the design of cobalt silica supported Fischer–Tropsch catalysts

The effect of cobalt precursor, catalyst pretreatment and promotion with ruthenium and rhenium on the formation of cobalt metal nanoparticles and catalytic performance of supported Fischer–Tropsch (FT) catalysts was studied using a combination of techniques (DSC–TGA, UV–vis spectroscopy, XPS, XRD, EXAFS–XANES, in situ magnetization measurements, propene chemisorption and catalytic measurements). The cobalt promoted and unpromoted catalysts were prepared by aqueous co-impregnation using cobalt nitrate or acetate, ruthenium nitrosyl nitrate or perrhenic acid. In both unpromoted and Ru and Re-promoted cobalt catalysts after impregnation and drying, cobalt is present mainly in octahedrally coordinated complexes. The repartition of cobalt species between Co₃O₄ and cobalt silicate depends essentially on the exothermicity of precursor decomposition. Cobalt nitrate precursor, with an endothermic decomposition, favors Co₃O₄ crystallites. Lower temperature of cobalt nitrate decomposition and catalyst calcination generally leads to higher dispersion of supported cobalt oxide. Cobalt acetate precursor, with an exothermic decomposition, favors cobalt silicate. By optimizing the conditions of cobalt acetate decomposition, the fraction of cobalt silicate can be decreased favoring a more reducible Co₃O₄ phase. For the catalysts prepared from cobalt nitrate, promotion with ruthenium increases the cobalt dispersion, while maintaining high reducibility. For the catalyst prepared via low temperature decomposition of cobalt acetate, addition of ruthenium increases the fraction of Co₃O₄ crystalline phase and decreases the concentration of barely reducible cobalt silicate. The Fischer–Tropsch reaction rates over unpromoted and promoted cobalt catalysts were found to be primarily a function of the number of cobalt metal sites, which are generated by the reduction of Co₃O₄ crystallites.     

Low temperature oxidation of methane over Pd/SnO2 catalyst

Catalytic activities of supported Pd were investigated for low temperature oxidation of methane. Pd/SnO₂ catalysts demonstrated excellent activity for methane oxidation in spite of their low surface area. The catalytic activity of Pd/SnO₂ was strongly affected by the preparation procedure. Impregnation of Pd on SnO₂ using aqueous solution of Pd(CH₃COO)₂ was most effective in enhancing the catalytic activity. The catalytic activity was also improved when well-crystallized SnO₂ was employed as a support material. TEM observations revealed that catalytic activity is strongly influenced by the dispersion state of Pd. For the active catalysts, strong interaction between Pd and SnO₂ support was observed in the adsorption of oxygen.     

The effects of SO2 on the oxidation of CO and propane on supported Pt and Au catalysts

The catalytic activities of Pt and Au supported on TiO₂ were compared with respect to the oxidation of CO and propane. While the Au catalysts showed higher activities for CO oxidation, the Pt catalysts were more active for propane combustion. A strong de-activation of the CO oxidation activity by SO₂ was observed only over the TiO₂-supported Au catalyst, indicating that SO₂ can block the active sites for CO oxidation over Au catalysts. The results are consistent with a model in which the perimeter sites have a special role in the CO oxidation reaction over Au catalysts.     

过渡金属Ni对Pd/Al_2O_3催化剂甲烷催化燃烧性能的影响

考察过渡金属Ni对Pd/Al_2O_3催化剂甲烷催化燃烧活性的影响以及过渡金属负载量及循环条件对甲烷降解性能的影响,采用扫描电镜、N_2吸附-脱附以及H_2程序升温还原技术对催化剂进行表征。结果表明,过渡金属Ni的添加对催化剂在(375~475)℃下的甲烷催化燃烧活性产生影响。催化剂经多次重复使用后,催化燃烧活性提高。分析原因为经过渡金属Ni改性后,可与载体形成NiAl_2O_4尖晶石,促进活性组分形成较小晶粒,并改善活性组分分散度,提高催化剂催化活性。     

Methane aromatization using Mo-based catalysts prepared by microwave heating

Mo/HZSM-5 and Cu–Mo/HZSM-5 catalysts for the non-oxidative aromatization of methane have been prepared by microwave heating method. The effects of Mo loading, the molar ratio of Cu/Mo and preparation method on the catalytic performance of catalysts were studied. The results were compared with those for the methane aromatization over catalysts prepared by conventional heating. Both two kinds of catalysts have the maximum methane conversion when the Mo loading is 6%. The catalysts prepared by microwave heating exhibited higher selectivity to benzene than that prepared by conventional heating. The addition of metal Cu to Mo/HZSM-5 catalyst prepared by microwave heating enhanced the lifetime of catalyst, and gave rise to a little increase in methane conversion. The molar ratio of Cu/Mo influenced the methane conversion, and the maximum value was attained when Cu/Mo = 0.05, whereas no significant influence on the benzene selectivity was observed with the increase molar ratio of Cu/Mo. N₂ adsorption results showed that the catalysts prepared by microwave heating have the larger surface area and the similar pore volume compared with the catalysts prepared by conventional heating. This fact revealed that the more Mo species located on the outer surface of catalysts prepared by microwave heating is the main reason why they have better catalytic performance. XRD analysis indicated that the Mo species are highly dispersed on HZSM-5 zeolite. The addition of Cu influenced the dispersion. The actual active phase Mo₂C can be identified on the catalyst surface after reaction. TEM analysis revealed the carbonaceous deposition to have the form of carbon nanotube after reaction, with a uniform size range of 10–20 nm. TG analysis indicated that carbonaceous deposition on the catalysts prepared by microwave heating is lower than that by conventional heating, and the metal Cu further prompts the stability of catalyst. Most of the carbonaceous deposition on catalysts prepared by microwave heating is formed at low temperature and it is easy to burn-off. Coke accumulation at high temperature is the main reason of catalyst deactivation. The carbonaceous deposition formed on the catalysts for non-oxidative aromatization of methane is different from those formed on the catalysts for partial oxidation of methane.     

正丁烷脱氢异构制异丁烯的研究进展

正丁烷脱氢异构制异丁烯是提高正丁烷利用率和增产异丁烯的重要途径。对正丁烷脱氢异构制异丁烯的反应热力学进行分析,从热力学角度指出制约反应的关键因素,总结正丁烷脱氢异构制异丁烯反应中各催化体系的研究现状,提出催化剂的研发要点和催化剂研发过程中要解决的关键问题。在传统过渡金属双功能型催化剂中,通过加入助剂等方式提高脱氢活性组分的分散度并降低其聚集度,通过调变载体的酸性和孔道结构等方式提高载体的异构性能,即合理调节脱氢活性位和载体异构性能之间的匹配是传统过渡金属双功能型催化剂研发的关键。在新型催化剂中,探索在缓和条件下制备高比表面积和合适孔道结构的氮化物、碳化物和碳氧化合物的方法是新型催化剂研发的关键。     

Hydrodesulfurization of thiophene on carbon nanofiber supported Co/Ni/Mo catalysts

Co, Mo, NiMo and CoMo catalysts supported on alumina, fishbone and platelet carbon nanofibers (CNFs) have been prepared. The dispersion of the oxide phases was qualitatively studied and compared using X-ray diffraction (XRD) and transmission electron microscopy (TEM). The reducibility of the catalysts was studied by temperature programmed reduction (TPR). Hydrodesulfurization (HDS) of thiophene was used as a model reaction to compare the activity of different catalysts. The activity tests showed that the alumina supported catalysts exhibited higher activity compared to the corresponding CNF supported catalysts, and the NiMo catalysts were more active than the corresponding CoMo catalysts. The thiophene HDS activity was correlated with the dispersion of the molybdenum species and the reducibility of different catalysts. Interestingly, the CNF supported Co catalysts have higher thiophene HDS activity than the CNF supported Co(Ni)Mo catalysts.     

对羟基苯甲酸丁酯的合成研究进展

简要介绍了对羟基苯甲酸丁酯的性能特点及其传统合成方法,着重阐述了目前国内催化合成对羟基苯甲酸丁酯的最新研究进展,其中所涉及的催化剂主要包括无机盐类催化剂、杂多酸盐及其固载化催化剂、固体超强酸催化剂、稀土及其改性固体超强酸催化剂、活性炭固载磺酸类催化剂等五种,在合成对羟基苯甲酸丁酯时,使用这些催化剂可大大改善反应条件,提高产品的收率,明显提高经济效益。     

Potential routes for the nitration of toluene and nitrotoluene with solid acids

New synthesis routes have been investigated for the production of dinitrotoluenes (DNTs) from toluene or an equimolar mixture of 2-nitrotoluene (2-NT) and 4-nitrotoluene (4-NT) and nitric acid using solid acids as heterogeneous catalysts. The main objective was the replacement of liquid sulphuric acid. A secondary goal was the increase of 4-NT and 2,4-DNT in the product mixture, which are more valuable products. Particular consideration was given to the feasibility of future large-scale process implementation. Continuous flow vapour phase reaction, and liquid phase reaction with simultaneous distillation were investigated. DNT formation in the vapour phase reaction was negligible with all solid acids tested. Preshaped silica impregnated with sulphuric acid was the most active catalyst but a continuous loss of sulphuric acid with time-on-stream was observed. Zeolite beta provided a higher 4-NT to 2-NT ratio than ZSM-5, ZSM-12 and mordenite, but deactivated after 5–10 h on-stream. Regeneration of beta was possible by thermal treatment. The para-selectivity of mordenite could be improved by the creation of a mesoporous system. In the reaction with simultaneous distillation, supported liquid acids exhibited true catalytic behaviour for the conversion of NT to DNT, but a loss of the impregnated acid was observed. Zeolite beta was about half as active as supported liquid acids and gave an exceptionally high 2,4-DNT selectivity of up to 94%, compared to 74–79% obtained with all other solid acids.     

硅钨酸稀土盐催化合成丁基多苷

以硅钨酸铈为催化剂。以葡萄糖和正丁醇为原料,采用直接法合成了丁基多苷。详细地研究了醇糖摩尔比、反应温度、催化剂用量和反应时间等因素对葡萄糖转化率的影响,得出最佳反应条件。结果表明：当反应中醇糖比为5：1,油浴温度120℃,反应时间2h,催化剂的量为葡萄糖质量的3％,反应的转化率最高,可达到96．81％。比较了不同硅钨酸稀土盐的催化活性。同时以二氧化硅负载硅钨酸镧和硅钨酸铈作为催化剂．考察活性组分的负载量对葡萄糖转化率的影响。并考察了债载催化剂的萤复利用性能。