Dehydrogenation of Ethylbenzene in the Presence of CO2 over V Catalysts Supported on Nano-sized Alumina

Carbon-covered alumina (CCA) were synthesized from mesoporous alumina and a series of carbon sources (including sucrose, furfuryl alcohol, and benzene). They had structural properties of alumina and surface characteristics of carbon. When they were used as supports for molybdenum carbide, nitride, and phosphide catalysts, significantly higher activities were obtained in hydrazine decomposition as compared to those supported on the conventional alumina. The difference in the interactions of catalytic active sites with the CCA and with the alumina supports was preliminarily deemed to be the main cause of the better performance of CCA supported catalysts. Carbon contents on alumina and carbon sources were found to be important for CCA to be a good support. Carbon deposited on alumina in a near monolayer form showed the best activities. In contrast with sucrose and furfuryl alcohol, benzene as the carbon source readily yielded CCA supports with a hydrophobic surface, which resulted in relatively low dispersions of metal and, in turn, decreased activity of the supported catalysts.     

Nontraditional method for the preparation of carbon sorbents from composites based on phenol-formaldehyde resins

A technology for the preparation of high-strength carbon sorbents based on phenol-formaldehyde resins with the use of microwave energy at the stages of the carbonization of starting raw materials, the activation of carbonization products, and the regeneration of spent sorbents was developed. These sorbents were effective in a pulp countercurrent process for the recovery of noble metals. The physicomechanical, structural, and adsorption characteristics of the resulting sorbents were tested.     

Carbon sorbents from waste crumb tires

The applicability of wastes from the chemical utilization of automobile tires as a raw material for the manufacture of carbon sorbents was studied. The thermogravimetric analysis of the thermal degradation of this raw material was performed; the proximate and ultimate analyses were carried out, and a process for the manufacture of crushed and granulated sorbents was developed. The formation of the structural and adsorptive properties of carbon sorbents based on waste crumb tires was studied. It was found that the sorbents were characterized by low and high sorption capacities for substances from aqueous solutions and saturated vapors, respectively. This phenomenon can be explained by the pore structure peculiarities of sorbents from waste crumb tires, which contained supermesopores that turned into capillaries; they are responsible for an entirely different mechanism of absorption: the capillary condensation of vapors.     

负载型煤气脱硫剂用载体的研究现状

煤气净化用脱硫剂的载体在脱硫剂硫化再生过程中具有重要的作用,好的载体不仅可以均匀分散活性组分、增大表面积,而且能够提高其耐热性和机械强度。在分析γ-Al2O3,活性炭和TiO2 3种常用载体在脱硫剂应用中存在的优势和不足的基础上,进行了载体改性的探讨,指出经过改性的载体以及复合型载体在脱硫领域将具有更为广泛的应用前景。     

Progress in carbon dioxide capture and separation research for gasification-based power generation point sources

The purpose of the present work is to investigate novel approaches, materials, and molecules for the abatement of carbon dioxide (CO₂) at the pre-combustion stage of gasification-based power generation point sources. The capture/separation step for CO₂ from large point sources is a critical one with respect to the technical feasibility and cost of the overall carbon sequestration scenario. For large point sources, such as those found in power generation, the carbon dioxide capture techniques being investigated by the Office of Research and Development of the National Energy Technology Laboratory possess the potential for improved efficiency and reduced costs as compared to more conventional technologies. The investigated techniques can have wide applications, but the present research is focused on the capture/separation of carbon dioxide from fuel gas (pre-combustion gas) from processes such as the Integrated Gasification Combined Cycle (IGCC) process. For such applications, novel concepts are being developed in wet scrubbing with physical sorption, chemical sorption with solid sorbents, and separation by membranes. In one concept, a wet scrubbing technique is being investigated that uses a physical solvent process to remove CO₂ from fuel gas of an IGCC system at elevated temperature and pressure. The need to define an “ideal” solvent has led to the study of the solubility and mass transfer properties of various solvents. Pertaining to another separation technology, fabrication techniques and mechanistic studies for membranes separating CO₂ from the fuel gas produced by coal gasification are also being performed. Membranes that consist of CO₂-philic ionic liquids encapsulated into a polymeric substrate have been investigated for permeability and selectivity. Finally, processes based on dry, regenerable sorbents are additional techniques for CO₂ capture from fuel gas. An overview of these novel techniques is presented along with a research progress status of technologies related to membranes and physical solvents.     

活性炭载体预处理对Ru/C氨合成催化剂活性的影响

将活性炭在惰性气体保护下进行高温热处理,随后在 O2/N2体积比为10%条件下进行氧化处理。采用元素分析、物理吸附和XRD方法,考察了不同处理后炭载体的化学组分、表面织构和物相变化。以不同预处理的活性炭为载体,制备了钡助催钌催化剂,在425 ℃,10.0MPa和10 000 h^－1条件下进行氨合成活性测试。结果表明,1 800 ℃热处理导致活性炭部分石墨化,能有效消除非炭成分,同时炭载体的比孔容下降了90%。随后的氧化处理能使炭载体比表面得到有效的恢复,以扩孔处理的炭为载体制备的钌催化剂能够使活性金属在载体中均匀分散,制备出高活性的氨合成钌催化剂。     

Selective catalytic reduction of nitric oxide with ammonia on Mn‐promoted carbonized used silica–alumina sorbents

Deactivated (waste) silica–alumina sorbents were carbonized and used as supports. The introduction of manganese led to active and selective SCR catalysts at low temperatures. Two methods of Mn promoting were compared: wet impregnation and adsorption. They influenced the distribution of Mn and N₂O production. The catalysts behaved similarly to Mn‐promoted active carbon. This revised version was published online in July 2006 with corrections to the Cover Date.     

Understanding the performance of membrane for direct air capture of CO2

Direct air capture (DAC) of CO₂ is becoming increasingly important for reducing greenhouse gas concentrations in the atmosphere. However, the cost and energy requirements associated with DAC make it less economically feasible than carbon capture from flue gases. While various methods like solid sorbents and gas–liquid absorption have been explored for DAC, membrane processes have only recently been investigated. The objective of this study is to examine the separation performance of a membrane unit for capturing CO₂ from ambient air. The performance of a membrane depends on several factors, including the composition of the feed gas, pressure ratio, material selectivity, and membrane area. The single-stage separation process with the co-current flow and constant permeability flux model is evaluated using a commercial module integrated with a process simulator to separate a binary mixture of carbon dioxide and nitrogen to assess the sensitivity of selectivity on purity and recovery of CO₂ in permeate, and power requirement. Additionally, three levels of CO₂ reduction from the feed stream to the retentate stream (25%, 50%, and 75%) are studied. A trade-off between purity and recovery factor is observed, and achieving high purity in permeate requires high concentration in the retentate.     

干法脱硫过程中活性炭基脱硫剂的放硫

活性炭基干法脱硫过程中的放硫关系到活性炭基脱硫的应用领域,研究避免和降低活性炭基脱硫过程中的放硫非常必要.根据脱硫过程中进口与出口硫化物形态的异同,总结了活性炭基脱硫过程中放硫的现象,重点介绍了脱硫过程中二氧化硫和羰基硫生成的放硫现象.从脱硫过程中气体组成出发,给出了活性炭基脱硫机理和放硫机理.综述了活性炭基脱硫剂本体...     

Effect of thermal and oxidative treatments of activated carbon on its surface structure and suitability as a support for barium-promoted ruthenium in ammonia synthesis catalysts

The effect of heat-treating a typical activated carbon at 1600-2500 °C on its structural and textural properties was investigated by gas sorption and X-ray diffraction. Particular attention was paid to the recovery of the surface area and porosity of thermally treated carbons by means of oxidation treatments. It was found that the thermal modification of activated carbon could eliminate carbon impurities, bring about different degrees of graphitization, and improve the resistance of the carbon support to undergo methanation under ammonia synthesis conditions, but the surface area and porosity decreased dramatically. Oxidative treatment partially recovered the surface area and porosity. The higher the thermal treatment temperature, the greater the stability of the carbon support, and the more difficult the recovery of the surface area and porosity becomes. A series of unpromoted ruthenium/carbon catalysts showed that the highly developed texture of the carbon support resulted in a significant increase in Ru dispersion. The ammonia synthesis activity of a Ba-promoted Ru catalyst was greatly improved by using activated carbon C1900ox as a support, which was heated at 1900 °C in an inert atmosphere and then subjected to oxidation treatment.     

碳限域铁基费托合成催化剂研究进展

利用费托合成工艺,将煤、生物质等原料气化产生的合成气转化为液体燃料或化学品,符合我国能源特点和战略需求,而高性能铁基费托合成催化剂的开发能够推动该工艺进步,载体的结构和电子环境会显著影响催化剂的性质。碳材料是铁基费托合成催化剂备受关注的一类载体。本文回顾了不同种类的碳限域载体（包括碳纳米管、介孔碳、有机物衍生、石墨烯等）在费托合成中的最新进展,并重点从几何效应和电子效应两方面阐述了碳材料对铁基费托合成催化剂的限域作用,如对气体扩散和局部浓度、铁物种还原和碳化、碳化铁的相态和晶粒尺寸的稳定性等方面的影响。今后的研究重点是解决催化剂可控制备及碳材料本身在工业操作条件下的稳定性问题,并进一步探明碳包覆结构对碳化铁物相形成和反应机理的影响机制。     

纳米结构多孔固体在二氧化碳吸附分离中的应用

二氧化碳（CO2）的双重角色（温室气体及一碳化工原料）使其吸附分离研究具有重要学术及社会经济意义。本文以多孔吸附材料为主线,系统评述了多孔炭、分子筛、有机金属骨架类材料及多孔聚合物等的CO2吸附分离最新研究进展。这些吸附材料的特点：多孔炭的微观及宏观形貌可控,孔结构可调,稳定性好;分子筛的具有丰富的微孔,孔径分布集中;有机金属骨架及多孔聚合物的种类多样,代表一类新兴的CO2吸附材料。分析了多孔固体应用于CO2吸附分离所涉及的关键科学问题,即高效吸附材料立体设计及影响选择性和吸附量等重要参数。提出澄清微孔/介孔/大孔比例以及表面基团种类和数量对CO2吸附贡献的定量关系的必要性,对材料的定向合成与优化有重要指导意义。     

固体碱负载Ru催化山梨醇氢解制备低碳二元醇

采用羟基磷灰石和镁铝水滑石两种固体碱为载体制备了Ru催化剂,通过N₂物理吸附、扫描电子显微镜、高分辨透射显微镜、X 射线衍射分析表征了形貌和物理化学性能,并与纳米碳纤维负载的Ru催化剂（Ru/CNFs）在无碱促进剂及有碱促进剂存在下催化山梨醇氢解制备二元醇的活性进行了比较。结果表明,固体碱负载的Ru催化剂,在无碱促进剂的条件下在山梨醇氢解中均表现出与Ru/CNFs相当的催化活性。其中镁铝水滑石负载的Ru催化剂在优化的制备条件下,其催化活性优于加入碱促进剂的Ru/CNFs催化体系,乙二醇和丙二醇等目标产物选择性更高,副产物减少,同时还免除了碱助剂的后续分离和回收,具有良好的应用前景。     

聚醚砜酮基炭膜的制备及其气体分离性能

采用浸渍涂膜法,以商用聚醚砜酮(PPESK)为前驱体制备了管式复合炭膜,考察了涂膜次数、改性剂及其加入量对所制备炭膜的气体分离性能的影响.结果表明,随着涂膜次数增多,气体分子的渗透速率逐渐减小而选择性呈增大趋势;加入改性剂后的复合炭膜渗透速率和分离系数均有不同程度的提高,表明改性剂不仅改善了涂膜液与支撑体之间的复合效果、减少涂膜次数,同时也促进了气体渗透速率的提高.利用扫描电镜对复合炭膜的微观形貌进行观测,可以看出,复合炭膜由支撑体和分离膜层2部分组成.膜表面很致密均匀,无明显缺陷,分离层薄而均一,厚度在5μm左右,且与支撑体结合紧密.     

Increasing the activity of Fe/N/C catalysts in PEM fuel cell cathodes using carbon blacks with a high-disordered carbon content

Fe/N/C catalysts for the reduction of oxygen in PEM fuel cells were prepared by pyrolyzing three series of iron acetate-impregnated developmental carbon blacks at 950 °C. The carbon supports used were derived from the N234, N330, and N650 commercial furnace grades. In this study, we tried to increase the performance of Fe/N/C-based cathode of PEM fuel cells by using the following two approaches: (1) increasing the number of catalytic sites on the carbon black either by optimizing the structural parameters of the pristine carbon supports or by increasing the initial metal content above 0.2 wt% Fe on the carbon support; (2) increasing the catalyst loading in the cathodic layer of a PEM fuel cell. For (1), we show, on the one hand, that optimizing the structural parameters of the pristine carbon support, in order to increase the number of catalytic sites, has its limits and that these limits have been reached for the present synthesis method of Fe/N/C catalysts. On the other hand, increasing the initial metal content above 0.2 wt% Fe leads to a decrease in catalytic activity. For (2), it is shown that increasing the catalyst loading per cm² of cathode well improves the performance of a cathode based on Fe/N/C catalysts in the kinetic region of the polarization curve. At lower potentials, a large improvement in the performance of these non-precious metal cathodes would occur if the mass transport properties in these electrodes were significantly increased.     

Reactivity of Metal Oxide Sorbents for Removal of Sulfur Compounds from Coal Gases at High Temperature and Pressure

Abstract

Hot-gas desulfurization for the integrated gasification combined cycle (IGCC) process has been investigated to effectively remove hydrogen sulfide with various metal oxide sorbents at high temperatures and pressures. Metal oxide sorbents such as zinc titanate oxide, zinc ferrite oxide, copper oxide, manganese oxide, and calcium oxide were found to be promising sorbents in comparison with other removal methods such as membrane separation and reactive membrane separation. The removal reaction of H₂S from coal gas mixtures with zinc titanate oxide sorbents was conducted in a batch reactor. The main objectives of this research are to formulate promising metal oxide sorbents for removal of hydrogen sulfide from coal gas mixtures, to compare reactivity of a formulated sorbent with a sorbent supplied by the Research Triangle Institute at high temperatures and pressures, and to determine effects of concentrations of moisture contained in coal gas mixtures, and to determine effects of concentrations of moisture contained in coal gas mixtures on equilibrium absorption of H₂S into metal oxide sorbents. Promising durable metal oxide sorbents with high-sulfur-absorbing capacity were formulated by mixing active metal oxide powders with inert metal oxide powders and calcining these powder mixtures.     

负载型碳酸钾催化剂上二氧化碳与1,2-丙二醇合成碳酸丙烯酯反应研究

在负载型碳酸钾催化剂上对二氧化碳与1,2-丙二醇(PG)合成碳酸丙烯酯(PC)反应进行了研究.结果表明,负载型碳酸钾催化剂的最佳制备条件为:活性炭为载体,碳酸钾负载量为15%(wt),焙烧温度423.15 K.在反应温度443.15 K、催化剂用量为2.0%(wt)、溶剂(乙腈)/PG/二氧化碳(摩尔比)为19.2:3:4、二氧化碳初始压力为2.0 MPa、反应时间12 h的条件下,PG的转化率为12.9%,PC的收率为9.6%,选择性为74.4%.对活性炭负载碳酸钾催化剂进行了XRD分析,发现存在K2CO3和K2O两种晶相.BET分析结果表明,载体的比表面积对负载型碳酸钾催化剂的催化活性有较大影响.与均相碳酸钾催化剂相比,负载型碳酸钾催化剂上PC的选择性提高了40.3%.     

Effects of reduction of metal oxide sorbents on reactivity and physical properties during hot gas desulphurization in IGCC

In this study, the changes of physical properties and reactivity of the metal oxide sorbents were investigated under the reducing conditions of coal gas. Metal oxide sorbents are converted into metal sulphides as a result of reaction with H₂S in synthesis gas. This could cause the reduced reactivity of sorbents if the metal oxides were converted into metallic elements due to the reduction by either hydrogen or carbon monoxide. In this experiment, the changes of physical properties and reactivity of the metal oxides were investigated over the temperature range 480-700 °C. It is confirmed that the reactivity of sulphidation and the reduction of metal oxide increased with increasing temperature. Even though the sulphur capacity of the sorbents in the early stage was high, it reduced rapidly due to the progressive reduction of metal oxides as the sulphidation/regeneration process was repeated. The reduction of metal oxide and the extent of reduction were verified by measuring the amount of oxygen consumed and the amount of SO₂ produced during the regeneration of sulphidated sorbents with the aids of a gas analyser. It was concluded that the reactivity of the metal oxide sorbents was influenced by reduction with coal gas at high temperature.     

Carbon nanofibers supported Pt-Ru electrocatalysts for direct methanol fuel cells

Oxidized and reduced carbon nanofibers (OCNF and RCNF) were used as supports to prepare highly dispersed PtRu catalysts for the direct methanol fuel cells (DMFC). The structural and surface features and electrocatalytic properties of bimetallic PtRu/OCNF and PtRu/RCNF were extensively investigated. FT-IR spectra show that carboxyl groups exist on the surface of the OCNF, which greatly influence the morphology and crystallinity of the electrocatalysts. Transmission electron microscopy and X-ray diffraction consistently show that PtRu/RCNF has a smaller particle size and more uniform distribution than PtRu/OCNF. However, both catalysts have very similar methanol oxidation peak current densities that are significantly lower than commercial catalyst based on current-voltage (CV) results. These two catalysts also give very similar single cell performance except for some difference in the resistance polarization region. The OCNF supported catalysts give better performance than commercial catalysts when current density is higher than 50 mA cm⁻² in spite of low methanol oxidation peak current density. These results can be ascribed to the specific surface and structural properties of carbon nanofibers.     

微波与碳基催化剂协同促进果糖制5-羟甲基糠醛

生物质转化为高附加值的化学品是替代石化产品的有效途径,微波与催化剂的协同作用有助于提升糖类的转化效率。碳材料具有良好的化学稳定性和介电性,是微波反应过程中理想的催化剂载体和吸波剂。为了探究碳基催化剂对微波场的响应能力,本文以4种碳材料为载体应用于果糖转化过程,包括碳纳米管（CNT）、碳纳米纤维（CNF）、炭黑（CB）和活性炭（AC）。以果糖转化率和5-羟甲基糠醛（5-HMF）收率为评价指标,对比不同催化剂在常规和微波加热条件下的催化性能,探究微波与不同载体的耦合作用对反应的强化效果。在微波场中测量不同碳材料悬浮液的温度曲线,评价碳基催化剂在微波场中的加热能力。通过表征样品结构和介电参数,解释载体与微波间耦合作用差异的原因。结果表明,碳基催化剂的微波诱导热效应可以有效提升反应转化率和收率,拥有高损耗角正切值和电导率的催化剂把微波能转化为热量的能力较强,更有助于将微波能量传递至反应表面。高比表面积、高长径比、低密度和高石墨化度的碳基催化剂也有利于产生微波热效应。另外,由于显著的微波热效应,碳纳米管基催化剂CNT-SA在4类催化剂中催化性能最优,以110℃微波辐射10min,5-HMF收率可达96.30%,且催化剂具有良好的循环使用性能。