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.     

Comparative study of support effects in ruthenium catalysts applied for wet air oxidation of aromatic compounds

Catalytic wet air oxidation (CWAO) reactions of aniline and phenol were conducted over supported ruthenium catalysts. Three support materials were employed: ZrO₂ and graphite, which exhibit medium adsorption capacities for pollutants and present mesopores in their texture, and an activated carbon. This latter has higher adsorption capacity for pollutants because of the large capability of the micropores for contaminant retention from water. The Ru catalysts supported on the activated carbon material showed the higher values of conversion in the oxidation of aniline and of conversion and mineralization in the reaction of phenol. Under our experimental conditions the role of micropores present on the support material seems to be relevant for improving catalytic performances. The incorporation of Ru nanoparticles from different precursors has been also evaluated. Even if the final Ru particle size is a key parameter for the catalytic mineralization, a cooperative effect with the activated carbon support has been established.     

Hydrodechlorination of 1,2,4-trichlorbenzene over supported ruthenium catalysts on various supports

Hydrodechlorination of 1,2,4-trichlorbenzene was carried out over ruthenium catalysts supported on γ-Al₂O₃, CeO₂, ZrO₂, SiO₂, SBA-15 and activated carbon. In the hydrodechlorination of 1,2,4-trichlorobenzene, higher catalytic activities and longer catalyst life was achieved for Ru catalysts supported on carbon compared to Ru catalysts supported on other supports. The higher catalytic activity exhibited by carbon supported ruthenium catalysts was attributed due to high dispersion of Ru, metal area and smaller crystallite size owing to strong chemisorption of 1,2,4-trichlorobenzene leading to complete hydrodechlorination.     

Catalytic behavior of vanadium substituted mesoporous molecular sieves

A series of V-MCM-41 samples with different pore sizes has been systematically investigated with both gas and liquid phase reactions. Methanol oxidation has been performed in the gas phase on these catalysts. Turnover frequencies are normalized by oxygen uptake measured under reaction conditions. A strong effect of pore size on the catalytic activity was observed in the form of a “volcano curve” and may be correlated with a variation in the local bond angle of Si–O–V. Considering this effect, the catalytic activity may be ‘tuned' to maximum by varying the pore size. As expected, the same effect was observed in the liquid phase oxidation of cyclohexene. In order to interpret the pore size effect, the reaction rates of both the gas phase and liquid phase oxidation were then correlated with the variation of edge energies of V K-edge XANES on these MCM-41 catalysts. Additional reactions were performed in the liquid phase to compare the activity of V-MCM-41 with that of crystalline vanadium and titanium silicalite zeolites. The possible causes of the difference in the catalytic behaviors of these materials is also discussed.     

Catalytic destruction of methyl tertiary butyl ether (MTBE) using oxidized carbon

Decomposition of methyl tert-butyl ether (MTBE) in the gas phase was studied using carbon catalysts with chemically modified surface. Carbon samples with different surface chemical properties were obtained from commercial activated carbon D43/1 (CarboTech, Essen, Germany) by oxidation in liquid phase with various oxidants as well as in air. The catalytic tests were performed in a flow reactor at a temperature range of 353–473 K. Isobutene and methanol are the only products of the MTBE decomposition. The generation of surface acidic oxides considerably enhances the catalytic activity of the carbons. However, the activity is controlled not only by the number and strength of acidic groups, but also by their accessibility. The most active carbon is that oxidized with air at 673 K, which contains pores wider than the pores of other oxidized carbons.     

Further insights into the Ru nanoparticles-carbon interactions and their role in the catalytic properties

Temperature-programmed reduction (TPR) and CO adsorption microcalorimetry along with the catalytic behaviour in the n-butane/H₂ test reaction were performed in order to determine the specific interactions of Ru nanoparticles supported on different carbon materials. Aspects such as the porous structure and surface chemistry (presence and elimination of surface oxygen functional groups) of the carbon material, or the effect of the metal precursor (e.g. presence of residual chlorine) on the final metal dispersion and on the surface structure of the Ru nanoparticles have been studied.The results obtained confirm that surface oxidation of the support along with the nature of the Ru precursor affects the distribution of the metal precursor over the support (and, consequently, the final ruthenium dispersion) and also the surface site distribution. Besides, elimination of the surface oxygen functional groups of the carbon material, during the reduction treatments of the fresh catalyst samples, leads to surface reconstructions on the Ru nanoparticles that seem to expose different crystallographic planes. The presence of residual chlorine leads to electron deficient Ru sites, and this modifies the CO chemisorption heats and affects the catalytic properties in the n-butane/hydrogen test.     

钌炭催化剂的制备及其在芳环加氢反应中的应用

芳环加氢反应是最重要的合成反应之一,钌炭催化剂在芳环加氢反应中具有优异的催化性能。综述钌炭催化剂的制备方法和载体性质对钌炭催化剂的影响以及钌炭催化剂在苯、苯甲酸和对苯二甲酸二甲酯等芳环加氢反应中的应用进展。负载型钌炭催化剂的制备方法主要有浸渍法、沉淀法和升华法,超声辅助浸渍法可将大部分钌纳米粒子引入到炭载体的孔道内部,得到限域型负载钌炭催化剂。而镶嵌式钌炭催化剂主要是指通过原位炭化的方法将钌粒子部分镶嵌在炭的孔壁上,一步得到钌炭催化剂,其制备方法主要有软模板剂法和硬模板剂法。除制备方法外,炭的骨架结构、表面性质及氮掺杂对钌炭催化剂的性能影响也较大。镶嵌式钌炭催化剂具有钌纳米粒子和炭载体之间的相互作用强、催化剂抗流失及烧结性能好,在芳环加氢反应中表现出卓越的催化性能和稳定性。随着新制备技术的出现,新型镶嵌式钌炭催化剂将可能实现产业化。     

Hydrogenation of succinic acid to γ-butyrolactone (GBL) over ruthenium catalyst supported on surfactant-templated mesoporous carbon

Mesoporous carbon support (denoted as STC) was prepared by a surfactant-templating method for use as a support for ruthenium catalyst. For comparison, porous carbon (denoted as TC), spherical carbon (denoted as SC), and microporous carbon (denoted as DC) supports were also prepared by a templating method, hydrothermal method, and direct carbonization method, respectively. Ruthenium catalysts supported on carbon supports (Ru/C) were then prepared by an incipient wetness impregnation method. The Ru/C (Ru/DC, Ru/SC, Ru/TC, and Ru/STC) catalysts were characterized by FE-SEM, N₂ adsorption–desorption isotherm, BET, XRD, and HR-TEM analyses. Liquid-phase hydrogenation of succinic acid to γ-butyrolactone (GBL) was carried out over Ru/C catalysts in a batch reactor. In the hydrogenation of succinic acid, Ru/STC catalyst showed the highest conversion of succinic acid and the highest yield for GBL. The superior catalytic performance of Ru/STC catalyst compared to the other catalysts (Ru/TC, Ru/SC, and Ru/DC) was due to fine dispersion of ruthenium (ruthenium surface area). Thus, ruthenium surface area played a key role in determining the catalytic performance in the liquid-phase hydrogenation of succinic acid to GBL over Ru/C catalysts.     

Ordered mesoporous carbons supported wacker‐type catalyst for catalytic oxidative carbonylation

Ordered mesoporous carbons (OMCs) were used as supports to prepare Wacker‐type catalysts for diethyl carbonate (DEC) synthesis by oxidative carbonylation of ethanol in a gas‐phase reaction. The effect of support structure on the dispersion of the active species and catalytic properties were investigated. Nitrogen sorption, X‐ray diffraction (XRD) and transmission electron microscopy (TEM) results revealed that the active components have encapsulated in pore channels of OMCs. Characterizations of the catalysts, such as TEM, scanning electron microscope (SEM) and XRD, indicated that active components supported on OMCs have better dispersion compared to activated carbon (AC). The ethanol conversion of the catalysts was improved by ～65% using OMCs as the catalyst support than AC. The stability of the catalytic activity can also be enhanced through surface modification of OMCs. Surface oxygen‐containing groups (OCGs) on OMCs before and after surface modification were characterized by transmission IR spectra and the Beohm titration. The relationship between surface OCGs and anchor ability of OMCs was studied. © 2013 American Institute of Chemical Engineers AIChE J, 59: 3797–3805, 2013     

活性炭表面改性对钌基氨合成催化剂的影响

研究了活性炭经HNO₃进行表面改性后对Ru/AC催化剂的影响。利用表面官能团滴定、N₂物理吸附和CO化学吸附方法对催化剂进行表征,并对催化剂进行氨合成活性评价。结果表明,活性炭经适量的HNO₃改性处理后,中孔有所增加,更主要的是增加了表面羧基,使活性炭的亲水性得到提高,从而提高了以水溶液浸渍法制备的Ru/AC催化剂的活性以及Ru的分散度;但过量HNO₃的改性处理会使活性炭表面不稳定基团增加,这些不稳定基团会降低Ru/AC催化剂的活性以及Ru的分散度。用5 mol·L^-1的HNO₃进行改性处理可以达到最优的效果。     

Sibunit-based catalytic materials for the deep oxidation of organic ecotoxicants in aqueous solutions. III: Wet air oxidation of phenol over oxidized carbon and Rr/C catalysts

This article presents the first systematic study concerning the effect of the oxidative treatment conditions on the surface chemical composition and the catalytic properties in the deep wet oxidation of organic ecotoxicants of a Sibunit type carbon material (S4) which was earlier identified as promising for the oxidative treatment of industrial wastewaters. The influence of the surface chemistry of the carbon materials oxidized under different conditions on the catalytic performances in the wet air oxidation of phenol of the bare carbon materials as well as the ruthenium-containing catalysts (3 wt % Ru) supported on the oxidized carbon samples was studied. The catalytic activity of the bare carbon samples appeared to be moderate and either (i) increased with the total number of carbonyl and phenolic surface groups or (ii) decreased with the total concentration of surface carboxylic and lactonic species. However, the catalytic performances of the Ru-containing catalysts were significantly higher. Based on our results, an optimum pretreatment of the carbon support could be identified to obtain the most stable and active Sibunit-supported ruthenium catalysts in the wet air oxidation of phenols.     

Acid properties of phosphoric acid activated carbons and their catalytic behavior in ethyl-tert-butyl ether synthesis

Carbon catalysts were prepared by phosphoric acid activation of styrene-divinylbenzene copolymer followed by liquid phase oxidation with nitric acid. Their surface properties were modified by heat treatment at 300-600 °C in an argon atmosphere, and their acid properties were characterized by quasi-equilibrium temperature desorption of ammonia and by acid-base titration. The pore structure was characterized by nitrogen adsorption at −196 °C. Their catalytic activity in the synthesis of ethyl-tert-butyl ether (ETBE) from isobutene and ethanol was investigated. It has been shown that the carbon catalysts are active and selective in ETBE synthesis. The main factor determining the catalytic activity of carbon catalysts is the total number of acid surface sites. A linear correlation between total amount of surface sites and catalytic activity was found.     

Production of Hydrogen by Partial Oxidation of Methanol over Carbon-Supported Copper Catalysts

Copper-zinc catalysts deposited by impregnation on different oxidised carbon supports (activated carbon, black carbon and carbon fibres) were tested in the partial oxidation of methanol (POM) (CH₃OH + 1/2 O₂ 2 H₂ + CO₂). Characterisation of the samples by N₂ adsorption, X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) revealed differences in the dispersion, location and relative distribution of the active phase on the surface of the carbonaceous supports. These properties have important implications in the catalytic behaviour of the samples in the POM reaction. The location of active phases on the microporous structure implies lower initial activities and better thermal stability. These results may be due to limitations in the access of the reagents to the active phase and the prevention of copper-sintering effects.     

Noble metals supported on carbon black composites as catalysts for the wet-air oxidation of phenol

Pt, Pd and Ru catalysts supported on carbon black composites (CBC) were characterized in the wet air oxidation of phenol solution using a fixed-bed reactor working in a trickle-flow regime under relatively mild conditions: temperature, 393-433 K; pressure, 50-80 bar; liquid hourly space velocity (LHSV), 0.5-6 h⁻¹. The activity of the catalysts decreases in the following order: Pt/CBC>Pd/CBC≈Ru/CBC?CBC. The physicochemical properties of the CBC are affected by its reaction with oxygen during the oxidation process. Combustion of the CBC material in the aqueous phase proceeds at a lower temperature than that in the gas phase; its surface properties change according the same rules as during low temperature oxidation by gaseous air.     

Effect of the support on the selective hydrogenation of benzeneover ruthenium catalysts. 1. Al2O3 and SiO2

The effect of the support on the liquid phase selective hydrogenation of benzene to cyclohexene over Ru catalysts was studied. Catalysts were prepared using RuCl₃ as precursor and characterized by hydrogen chemisorption, XPS and TPR. The reaction was carried out at 373 K and 2 MPa using a stirred tank reactor. It was found that the catalytic activity is not influenced by the Ru dispersion. More electron-deficient Ru species are present on Al₂O₃ than on SiO₂. The electronic state of Ru affects the selectivity to cyclohexene.     

Characteristics of adsorbed CO and CH3OH oxidation reactions for complex Pt/Ru catalyst systems

Pt/Ru powder catalysts of the same nominal Pt to Ru composition were prepared using a range of methods resulting in different catalyst properties. Two PtRu alloy catalysts were prepared, one of which has essentially the same surface and bulk Pt to Ru composition, while the second catalyst is surface enriched with Ru. Two powders consisting of non-alloyed Pt phases and surfaces enriched with Ru were also prepared. The oxidation state of the surface Ru of the latter two catalysts is mainly metallic Ru or Ru-oxides. The catalyst consisting of Ru-oxides was formed at 500 °C. Part of this catalyst was then reduced in a H₂ atmosphere under “mild” conditions, thus catalyst properties such as particle size are not changed, as they are locked in during previous high temperature treatment. The oxidation kinetics of adsorbed CO (CO_ads) and solution CH₃OH were studied and compared to the Ru ad-metal state and Pt to Ru site distribution of the as-prepared catalysts. The kinetics of the CO_ads oxidation reaction were observed to be slower for the catalyst containing Ru-oxides as opposed to mainly Ru metal. The CH₃OH oxidation activities measured per Pt surface area, i.e., the catalytic activities are better (by ca. seven times) for the alloy catalysts than the non-alloyed Pt/Ru catalysts. The latter two catalysts showed essentially the same catalytic CH₃OH oxidation activities, i.e., independent of the Ru ad-metal oxidation state of the as-prepared catalysts. Furthermore, it is shown that CO_ads oxidation experiments can be used to extract characteristics that allow the comparison of catalytic activities for the CO_ads oxidation reaction and Pt to Ru site distribution for complex catalyst systems.     

活性炭载体对钌催化剂制备及其活性的影响

选择 5 种活性炭作为载体制备负载型钌催化剂，采用元素分析、物理吸附和化学吸附等表征手段，考察活性炭载体的化学组成和表面结构对钌催化剂金属分散状况的影响。以不同活性炭为载体制备了一系列钡助催钌催化剂，并在450 ℃、10.0 MPa条件下进行氨合成活性评价。研究结果表明，活性炭载体的原材料及其制备工艺决定了载体的化学组成和表面结构，以具有高纯度、较大比表面积、较大比孔容和适当孔结构分布的活性炭为载体制备的钌催化剂具有较高的氨合成催化活性。     

Effect of activated carbon on the dispersion of Ru and K over supported Ru-based catalyst for ammonia synthesis

A series of Ru-based activated carbon supported catalysts for ammonia synthesis were prepared by impregnation. The effects of activated carbon and their oxygen surface groups on the dispersion of Ru and promoter K were investigated. The different treatment ways of activated carbons are also used in order to study the effect of these groups. TPD-MS, CO and CO₂ pulse chemisorption were carried out to obtain better insight into the relation between the surface groups and the dispersion of Ru and K. The results showed that the surface groups could improve the hydrophilicity and the dispersion of Ru and K. Therefore, improve the ammonia synthesis activity of the catalyst.     

Activated Carbon Modified with Different Chemical Agents as a Catalyst in the Dehydration and Dehydrogenation of Isopropanol

Activated carbons modified with different chemical agents such as HNO₃, H₂SO₄, peroxyacetic acid (PAA), air, NH₃ and Cl₂ have been tested as catalysts in decomposition (dehydration and dehydrogenation) of isopropanol. The majority of the samples obtained have been characterised by well-developed microporous surface with a small contribution of mesopores (8–18%). The influence of the surface area of the samples on their catalytic performance has been insignificant. The carbon oxidation with oxidants in the liquid or gas phase leads to an increased catalytic activity and the dominant process is dehydration of the alcohol studied. Carbon modification by contact with gas ammonia or chlorine results in a decrease in the catalytic activity and a significant increase in the contribution of dehydrogenation of isopropanol. It has been shown that such behaviour of the catalysts has been a consequence of changes in the acid-base character of the carbons induced by their modification.     

活性炭负载钌基氨合成催化剂的制备

利用浸渍法制备了活性炭负载钌基氨合成催化剂,讨论了影响钌分散度与氨合成催化活性的若干因素. 研究发现,若活性炭载体具有较大的比表面和较好的孔结构将有利于活性组分的分散. 同时,在浸渍之前,样品需在100～200 ℃干燥6～8 h. 催化剂各组分浸渍后对载体的表面结构影响不同,实验发现,Ba的添加可能为Ru的分散提供了合适的表面,而K主要填充于载体中孔并和Ru充分接触,并为Ru提供电子.同时要控制母体钌水溶液的pH值,并选用合适的浸渍顺序,方能达到较好的效果.