Characterization and catalytic performance of CeO_2-Co/SiO_2 catalyst for Fischer-Tropsch synthesis using nitrogen-diluted synthesis gas over a laboratory scale fixed-bed reactor

The surface species of CO hydrogenation on CeO2-Co/SiO2 catalyst were investigated using the techniques of temperature programmed reaction and transient response method. The results indicated that the formation of H2O and CO2 was the competitive reaction for the surface oxygen species, CH4 was produced via the hydrogenation of carbon species step by step, and C2 products were formed by the polymerization of surface-active carbon species （-CH2-）. Hydrogen assisted the dissociation of CO. The hydrogenation of surface carbon species was the rate-limiting step in the hydrogenation of CO over CeO2-Co/SiO2 catalyst. The investigation of total pressure, gas hourly space velocity （GHSV）, and product distribution using nitrogen-rich synthesis gas as feedstock over a laboratory scale fixed-bed reactor indicated that total pressure and GHSV had a significant effect on the catalytic performance of CeO2-Co/SiO2 catalyst. The removal of heat and control of the reaction temperature were extremely critical steps, which required lower GHSV and appropriate CO conversion to avoid the deactivation of the catalyst. The feedstock of nitrogen-rich synthesis gas was favorable to increase the conversion of CO, but there was a shift of product distribution toward the light hydrocarbon. The nitrogen-rich synthesis gas was feasible for F-T synthesis for the utilization of remote natural gas.

Research activities and recent progresses on synthesis gas conversion

Five catalytic processes and their catalysts will be introduced in my talk. Firstly,the demonstration test(3000 ton/a)results using a novel catalyst Co/SiO2 with egg-shell structure and the strategies for this catalyst preparation based on the issues from the mass transfer of produced wax from F-T synthesis will be discussed. Recent progresses on C2-oxygenate synthesis from syngas over a Rh/SiO2 catalyst and a 10 thousands ton/a demonstration test facility in China will be built in 2010 will be reported in the second section. A naphtha and diesel distillate which cut off the heavier end of S-F-A distribution direct synthesis with low methane selectivity from syngas over a Co/AC1 catalyst and a 10000 ton/a demonstration test with a bubble column slurry reactor will be talked about in this speech. A high α-alcohols of C2-C18 direct synthesis with more than 50 wt% selectivity and low methane and methanol selectivities from syngas over a Co2C/AC2 catalyst,a 3000 ton/a demonstration test with a bubble column slurry reactor and the primary fundamental understandings will be detailedly discussed in the forth section. In situ formation of homogeneous active sites on the surface of supported Rh heterogeneous catalysts and their application in hydroformylation of olefins will be introduced in fifth section.

Effect of Several Anions on Fe-Based Catalyst for Fischer-Tropsch Synthesis

The influence of several anions on Fe-based Fischer-Tropsch catalyst, used in the synthesis of light olefins from synthesis gas, was studied. The results indicated that the addition of anions resulted in the reduction of catalytic activity. When the anion content in the catalyst was 500 ppm, the influence of different anions on the catalysis activity was as follows： S^2- 〉Cl^-〉SO4^2-〉NO3. The addition of S^2- improved the selectivity of total hydrocarbons in the products, and Cl^- reduced this selectivity but increased the olefin content in the total hydrocarbons at the same time. When the contents of S^2- and Clin the catalyst were less than 50 ppm, their influence could be ignored. The XRD results indicated that the addition of anions reduced the contents of α-Fe and FeaC, which were the active components in the catalyst.

Production of Synthesis Gases from Ethanol Steam Reforming Process

In this study, the production of synthesis gases has been purposed under between 250oC - 700oC and 1 - 2 bars pressures. The research was conducted over a commercial BASF catalyst and a laboratory prepared catalyst. The catalyst has a content of different substances including basically NiO/Al2O3 and some additionals (Ca, Mg, Cr, Si). The experimental measurements were carried out within a recently developed experimental equipment which can be operated up to 1200o and 1 to 3 bars pressures. The study was conducted over a commercial BASF catalyst and a laboratory prepared catalyst under different ethanol/water ratios, temperatures, and catalyst loads. Under the condition when ethanol/water ratios were decreased from 1/2 to 1/10, it was observed that hydrogen ratios increased in exit gas composition of the reactor. With increments in catalyst loads from 1 to 5 grammes, hydrogen ratios in exit gas composition gradually increased. Reaction of ethanol-steam reforming started nearly at 300oC, and when temperature increments continued further up to 700oC, hydrogen yields in exit gas compositions of the reactor increased significantly to a range of 70% - 80%. In the case of using commercial BASF catalyst, hydrogen ratios in exit gas composition were found slightly higher than laboratory prepared catalyst. According to our observations, life time of laboratory prepared catalyst was found higher than the commercial BASF catalyst. In this study which kinetic measurements were applied, some kinetic parameters of ethanol-steam reaction were calculated. The mean activation energy of ethanol consumptions at 573oK - 973oK was found as 26.87 kJ/mol, approximately. All kinetic measurements were analyzed with a first order reaction rate model. In this study, some diffusion limitations existed, however, overall reaction was chemically controlled.

Gold modified cobalt-based Fischer-Tropsch catalysts for conversion of synthesis gas to liquid fuels

The addition of Au as a promoter/modifier for alumina supported Co catalyst has been studied by combined in-situ high temperature, high pressure Fourier transform infrared （FTIR） and on-line gas chromatography. The combination of these tools permitted the state of the active catalyst surface to be monitored while following the elution of reaction products during the first 5-7 h on stream of the catalyst. The catalysts under study were a 10%Co/ A1203 and a 2.5%Au/10%Co/A1203. Samples were characterised before use using Raman and temperature programmed reduction （TPR）. During the initial stages of reaction, hydrocarbons were built up on the surface of the catalyst as monitored by FTIR and the nature and amount of these species were assessed in terms of CH2/CH3 ratio and the density of these alkyl fragments by employing absorption coefficients for the individual components. The nature and reducibility of the Co particles were modified by the presence of Au while the later also shifted the CO/ H2 balance by acting as an effective water-gas shift catalyst during the early stages of reaction. This characteristic was lost during reaction as a consequence of redistribution of the two metallic phases.

A review of C_1 chemistry synthesis using yttrium-stabilized zirconia catalyst

C1 chemistry based on synthesis gas, methane, and carbon dioxide offers many routes to industrial chemicals. The reactions related to the synthesis of gas can be classified into direct and indirect approach for making such products, such as acetic acid, dimethyl ether, and alcohol. Catalytic syngas processing is currently done at high temperatures and pressures, conditions that could be unfavorable for the life of the catalyst. Another issue of C1 chemistry is related to the methane-initiated process. It has been known that direct methane conversions are still suffering from low yields and selectivity of products resulting in unprofitable ways to produce products, such as higher hydrocarbons, methanol, and so on. However, many experts and researchers are still trying to find the best method to overcome these barriers, for example, by finding the best catalyst to reduce the high-energy barrier of the reactions and conduct only selective catalyst-surface reactions. The appli- cation of Yttria-Stabilized Zirconia （YSZ） and its combination with other metals for catalyzing purposes are increasing. The existence of an interesting site that acts as oxygen store could be the main reason for it. Moreover, formation of intermediate species on the surface of YSZ also contributes significantly in increasing the production of some specific products. Understanding the phenomena happening inside could be necessary. In this article, the use of YSZ for some C1 chemistry reactions was discussed and reviewed.

Effect of CeO_2 and CaO Promoters on Ignition Performance for Partial Oxidation of Methane over Ni/MgO-Al_2O_3 Catalyst

The effect of CeO2 and CaO promoters on the ignition performance over Ni/MgO-Al2O3 catalyst for the partial oxidation of methane （POM） to synthesis gas was investigated. It was found that the POM reaction could not be ignited over lwt%Ni/MgO-Al2O3 catalyst without the promoters in the temperature range from 773 K to 1073 K. CeO2 and CaO promoters enhanced the ignition performance and the POM reactivity of lwt%Ni/MgO-Al2O3 catalyst remarkably. Moreover, the improving effect became greater with the increase of the promoter content under the investigated reactiorrconditions. The modification effects of CeO2 and CaO promoters were closely related to the concentration and reducibility of the surface and bulk oxygen species.

The Dramatic Effect of Metal Precursor on the Catalytic Performance of Co/Sio_2 Catalyst for CO_2 Reforming of CH_4

The cobalt precursor affects the catalytic performance of Co/SiO_2 catalyst remarkably. The catalyst prepared from cobalt acetate exhibits excellent activity, stability and resistance to carbon deposition.

A Novel Catalyst for CO_(2) Reforming of CH_4

A novel Ni-Co/SiO2 catalyst which exhibits high activity and excellent anti-carbon deposition property for CO2 reforming of CH4 to synthesis gas is developed.

Improvement of catalytic stability for CO_2 reforming of methane by copper promoted Ni-based catalyst derived from layered-double hydroxides

Copper-promoted nickel-based metal nanoparticles (NPs) with high dispersion and good thermal stability were derived from layered-double hydroxides (LDHs) precursors that were facilely developed by a co-precipitation strategy. The copper-promoted Ni-based metal NPs catalysts were investigated for methane reforming with carbon dioxide to hydrogen and syngas. A series of characterization techniques including XRD, N2adsorption and desorption, H2-TPR, XPS, CO2-TPD, TEM, TGA and in situ CH4-TPSR were utilized to determine the structure-function relationship for the obtained catalysts. The copper addition accelerated the catalyst reducibility as well as the methane activation, and made the Ni species form smaller NPs during both preparation and reaction by restricting the aggregation. However, with higher copper loading, the derived catalysts were less active during methane reforming with CO2to syngas. It was confirmed that the catalyst with 1 wt% Cu additive gave the higher catalytic activity and remained stable during long time reaction with excellent resistance to coking and to sintering. Furthermore, the mean size of metal NPs changed minimally from 6.6 to 7.9 nm even after 80 h of time on stream at temperature as high as 700 °C for this optimized catalyst. Therefore, this high dispersed anti-coking copper-promoted nickel catalyst derived from LDHs precursor could be prospective catalyst candidate for the efficient heterogeneous catalysis of sustainable CO2conversion. © 2016 Science Press

Industrial Feasiblity of Direct Methane Conversion to Hydrocarbons over Fe-Based Fischer Tropsch Catalyst

Recently, as a direct consequence of the dwindling world oil reserves and the growing awareness of the environmental problems associated with the use of coal as energy source, there is growing interest in cheaper, abundant and cleaner burning methane. The Gas-to-Liquid technology offers perhaps the most attractive routes for the exploitation of the world huge and growing natural gas resources. Using this process the erstwhile stranded gas is converted to premium grade liquid fuels and chemicals that are easily transported. However, a widespread application of the GTL process is being hampered by economical and technical challenges. The high cost of synthesis gas, for instance, weighs heavily on the economics and competitiveness of the process limiting its wider application. This work presented a modified Gas-to-Liquid process that eliminates the costly synthesis gas production step. The proposed process utilized an alternative pathway for methane activation via the production of chloromethane derivatives which are then converted to hydrocarbons. It established that hydrocarbons mainly olefins can be economically produced from di- and tri-chloro- methanes over a typical iron-based Fischer Tropsch catalysts in a moving bed reactor at industrially relevant conditions. Some of the attractions of the proposed process include a) the elimination of the costly air separation plant requirement b) high process selectivity and c) significant reduction of carbon dioxide emissions thereby saving on feedstock loss and the costly CO2 removal and isolation processes.

In situ time-resolved FTIR investigation on the reaction mechanism of partial oxidation of methane to syngas over supported Rh and Ru catalysts

In situ time-resolved FTIR spectroscopy was used to study the reaction mechanism of partial oxidation of methane (POM) to synthesis gas and the reaction of CH4/O2/He (2/1/45, molar ratio) gas mixture with adsorbed CO species over Rh/SiO2, Ru/γ-Al2O3 and Ru/SiO2 catalysts at 500-600℃. It was found that CO is the primary product of POM reaction over reduced and working state Rh/SiO2 catalysts. Direct oxidation of CH4 is the main pathway of synthesis gas formation over Rh/SiO2 catalyst. CO2 is the primary product of POM over Ru/γ-Al2O3 and Ru/SiO2 catalysts. The dominant reaction pathway for synthesis gas formation over Ru/γ-Al2O3 catalyst is via the reforming reactions of CH4 with CO2 and H2O. For the POM reaction over Rh/SiO2 and Ru/γ-Al2O3 catalysts, consecutive oxidation of surface CO species is an important pathway of CO2 formation.

我国苯乙烯合成技术研究进展

苯乙烯是一种重要的有机化工产品,广泛应用于合成树脂和合成橡胶等领域。文章介绍了我国CO_(2)氧化乙苯脱氢、苯乙炔选择性加氢、甲苯和甲醇侧链烷基化等合成苯乙烯技术的研究进展,并提出了今后的发展建议。

Advances in the Partial Oxidation of Methane to Sy thesis Gas

The conversion and utilization of natural gas is of significant meaning to the national economy, even to the everyday life of people. However, it has not become a popular industrial process as expected due to the technical obstacles. In the past decades, much investigation into the conversion of methane, predominant component of natural gas, has been carried out. Among the possible routes, of methane conversion, the partial oxidation of methane to synthesis gas is considered as an effective and economically feasible one. In this article, a brief review of recent studies on the mechanism of the partial oxidation of methane to synthesis gas together with catalyst development is wherein presented.

Enhanced aromatic selectivity by the sheet-like ZSM-5 in syngas conversion

Aromatics are important basic chemicals. However, direct conversion of syngas via the conventional Fischer-Tropsch synthesis produces little aromatics. We presented herein that a bifunctional composite of ZSM-5 in combination with Zn Cr Oxcatalyzes syngas conversion to aromatics. Particularly, ZSM-5 crystals with a sheet-like morphology can enhance significantly the aromatization activity. The lower length ratio of the b/a axes of the crystals, the more aromatics form but without influencing the selectivity of small molecules such as CH4 and C2–C4. Since the acid properties and the Al chemical environment were not altered while the morphology changed, the enhanced aromatic selectivity is likely attributed to the favored diffusion of aromatics in these sheet-like crystals.

Process conditions for preparing methanol from cornstalk gas

The low-heat-value cornstalk gas produced in the down-flow fixed bed gasifier was tentatively used for methanol synthesis. The cornstalk gas was purified and the technical procedures such as deoxygenation, desulfurization, catalytic cracking of tar, purification and hydrogenation were studied. The catalytic experiments of methanol synthesis with cornstalk syngas were carried out in a tubular-flow integral and isothermal reactor. The effect of reaction temperature, pressure, catalysttypes, catalyst particle size, syngas flow at entering end and composition of syngas was investigated. The optimum process conditions and yield of methanol from cornstalk syngas were obtained. The experimental results indicated that the proper catalyst of the synthetic reaction was C301 and the optimum catalyst size （φ） was 0.833 mm×0.351 mm. The optimum operating temperature and pressure were found to be 235℃ and 5 Mpa, respectively. The suitable syngas flow 0.9-1.10 mol/h at entering end was selected and the best composition of syngas were CO 10.49%, CO2 8.8%, N2 37.32%, CnHm 0.95% and H2 40.49%. The best methanol yield is 0.418 g/g cornstalk. The study provided the technical support for the industrial test of methanol production from biomass （cornstalk）gas.

常温常压电化学合成氨催化剂研究进展

氨是化肥工业和基本有机化工的主要原料。目前,工业上普遍采用Haber-Bosch法合成氨,该工艺需要高温高压的反应条件,而且存在能耗高、转化率低且释放大量温室气体等问题。近年来,伴随着人们对能源和环境问题的日益重视,具有能耗低、反应条件温和、绿色环保等优势的常温常压电化学合成氨成为研究热点。催化剂是电化学合成氨的关键,本文介绍了近年来各类常温常压电化学合成氨催化剂的研究与应用进展,并展望了未来发展方向。

MOFs材料在CO_(2)加氢制甲醇催化剂中的应用

作为最主要的温室气体,CO_(2)的大量排放引发了全球变暖等一系列环境问题。利用CO_(2)加氢合成甲醇是实现CO_(2)循环利用、解决环境问题的切实可行的途径。开发高效、高选择性的催化剂是实现CO_(2)加氢制甲醇工业化应用的关键。近年来,金属有机骨架(MOFs)材料由于其结构多样性、设计灵活性的特点在催化领域引起了广泛关注,MOFs材料应用于CO_(2)加氢制甲醇催化剂的合成,可以有效解决目前CO_(2)加氢制甲醇催化剂存在的反应选择性低、CO_(2)转化率低、合成速率低等一系列问题,提高催化性能。综述了CO_(2)加氢制甲醇MOFs材料催化剂的研究进展,论述了MOFs材料应用于CO_(2)加氢制甲醇催化剂的优势及合成方法,评价了MOFs材料对不同的金属基催化剂的改善作用及存在的不足,并对其应用的挑战和前景进行了讨论。

银催化的环化反应合成异喹啉的研究进展

含有异喹啉骨架的化合物是一类很重要的含氮杂环化合物,广泛存在于具有生物活性的天然产物、有机材料以及药物分子中。传统的合成异喹啉的方法需要苛刻的反应条件,因此,使用温和及简单的方法构建这一骨架的化合物具有重要的现实意义。银类化合物具有路易斯酸特性,能够催化活化三键。利用这一特点并使用含氮的亲核试剂进行分子内亲核加成活化的三键是合成异喹啉衍生物的重要方法。本文主要综述了以2-炔基苄亚胺、2-炔基苄基叠氮、2-炔基苯甲醛肟、2-炔基苯甲醛腙及其(2-(乙炔基)芳基)-1,2,3-三唑为反应物,在银催化条件下构建异喹啉环的研究进展,并对部分反应的机理进行了讨论。