超临界流体处理活性炭时Ni/C催化剂催化加氢性能研究

分别以高温煅烧、超临界水、超临界甲醇、超临界H2O2溶液及超临界KOH溶液处理活性炭,采用浸渍-沉淀法制备镍基催化剂。考察了不同处理方法处理载体所制催化剂催化对硝基苯酚液相加氢的影响。结果表明,通过不同的超临界流体处理能有效地降低活性炭表面酸性基团含量,能不同程度提高活性炭的比表面积和孔容积,提高镍在其表面的分散程度,提高催化剂的活性。在相同的反应条件下,超临界KOH溶液处理的活性炭作载体所制得的催化剂催化效果最佳。     

超临界流体技术制备Ru/C催化剂的研究

以活性炭为载体、氯化钌为活性前驱体,采用超临界CO2流体沉积技术制备了Ru/C催化剂,用葡萄糖加氢生产山梨醇反应考察催化剂的催化活性.用正交实验考察了温度、CO2的量和还原剂KBH4的量等因素对制备Ru/C催化剂催化活性的影响规律;用红外光谱(IR)和扫描电镜(SEM)对Ru/C催化剂样品进行了结构表征.结果表明:制备...     

乙二醇水混合溶剂改性活性炭负载Pd催化剂性能

本文研究了乙二醇水混合溶剂预处理温度对活性炭物理结构、化学性质及负载Pd催化剂性能的影响。结果表明:经过高温醇水蒸气预处理后,活性炭比表面积,孔容、孔径基本保持不变,当处理温度超过140℃时,活性炭表面的含氧基团羧基、酚羟基更加丰富,促进了钯离子的吸附及金属Pd在活性炭表面的分散。在N-苄基苯胺氢解反应中表现出更高的反应活性。     

活性炭及其改性对钌基氨合成催化剂性能的影响

介绍了活性炭的物理、化学性能及其生产方法,以及活性炭作钌基催化剂载体的特点和活性炭改性处理方法对活性炭表面性质及其负载的钌基催化剂性能的影响。     

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。     

钌基催化剂用于直接法合成气制低碳烯烃反应

以γ-Al₂O₃为载体,通过等体积浸渍法制备钌基催化剂,用其进行催化CO加氢,研究制低碳烯烃反应中钌基催化剂的催化性能,考察催化剂的焙烧温度、工艺条件及碱金属助剂Na对钌基催化剂CO加氢反应的影响。结果发现,焙烧温度400 ℃制备的钌基催化剂具有最大的比表面积,在反应温度220 ℃、反应压力1.0 MPa和空速1 500 mL·(h·g)^-1条件下,可以保证较高的CO转化率及低碳烯烃选择性。碱金属助剂Na提高了催化剂催化活性,Na质量分数为4%6%时,钌基催化剂表现出最佳的CO转化率及低碳烯烃选择性。     

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。     

超声处理对活性炭表面形态及负载催化剂活性的影响

采用超声预处理活性炭,并用N_2物理吸附、X射线能谱仪(EDS)、透射电镜(TEM)、和场发射扫描电镜(FE-SEM)等表征手段,研究了超声预处理条件对活性炭表面结构、化学成分及表面形貌以及所负载钌基氨合成催化剂性能的影响。研究结果表明,超声预处理活性炭,可有效降低活性炭表面灰分和不稳定含氧基团的含量,从而提高所负载催化剂的活性。在实验范围内,当超声频率为39.0 kHz,功率为100w时,在10 000 h~(-1),10.0 MPa和400℃的反应条件下,钌基催化剂的反应速率达到了97.6 mmol/(g·h)。     

载体预处理对Pd/C催化剂催化性能的影响

研究了活性炭硝酸表面改性对以其为载体制备的负载钯催化剂性能的影响。利用表面官能团滴定、N₂物理吸附和扫描电镜对催化剂进行表征，以邻硝基氯苯催化加氢制备2，2'-二氯氢化偶氮苯反应为模型反应对催化剂的性能进行评价。结果表明，经过不同浓度的HNO₃处理，活性炭孔结构性能变化不大，但是活性炭表面酸性含氧基团的浓度有了较大程度的增长，为Pd金属粒子的沉积提供了大量的吸附位，提高了Pd金属的分散度，从而制得高活性的Pd/C催化剂。通过30%HNO₃ 60 ℃水浴中回流4 h处理的活性炭可以达到最佳效果，所制得催化剂的活性是以未经硝酸处理过的活性炭载体制备的催化剂活性的2.3倍。     

HNO3改性活性炭对Cr(Ⅵ)的吸附性能及机理

活性炭的吸附性能与其表面化学密切相关,本研究为讨论活性炭表面氧化改性对其Cr(Ⅵ)吸附特性的影响,分析了Cr(Ⅵ)吸附过程与活性炭表面化学性质的关系,阐释吸附机理。结果表明,与未改性活性炭相比,硝酸氧化改性后活性炭对溶液中Cr(Ⅵ)的吸附性能提高,且改性后活性炭的比表面积和孔容积降低,表面的羧基、内酯基和酚羟基等酸性含氧官能团的数量增多。改性活性炭对Cr(Ⅵ)的吸附过程可用Langmuir、Freundlich、D-R和Temkin4种吸附模型模拟,吸附动力学数据与拟二级动力学模型吻合。采用X射线光电子能谱(XPS)表征了改性前后活性炭的表面化学性质。Cr(Ⅵ)在活性炭上的吸附机理主要为静电吸引、还原和配位络合等,与Cr(Ⅵ)发生络合作用的是活性炭表面含氧官能团。     

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。     

Influence of oxidation on heat-treated activated carbon support properties and metallic dispersion of Ru/C catalyst

Heat-treated activated carbon has been oxidized to improve the properties related to the use as a support for the preparation of 5wt% Ru/C catalysts by impregnation. The pore structure, surface oxygen groups of the heat-treated activated carbon before and after oxidation in the gas and liquid phase, as well as catalytic activities and dispersion of Ru in the catalysts were investigated systematically. The pore structures of the samples were characterized by N₂ physisorption. Temperature-programmed desorption (TPD) was conducted to determine the chemical properties of the samples. Ru dispersion was measured by CO pulse chemisorption. The effects of oxidation treatments on carbon surface chemistry and pore structure which are closely related to Ru dispersion and catalytic activity, was examined. Furthermore, the modified heat-treated activated carbon support obtained by gas phase oxidation in CO₂ and liquid phase oxidation in nitric acid was more suitable to prepare Ru-based catalysts for ammonia synthesis than that without treatment.     

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.     

活性炭表面性质对其吸附及氧化氢醌的影响

研究了活性炭表面性质对活性炭吸附及氧化氢醌的影响。考察了3种材质活性炭在不同初始pH下吸附和氧化氢醌的性能以及氢醌吸附率、表观转化率与活性炭材质及用量的关系。实验结果表明：活性炭可以吸附及氧化氢醌,木屑材质活性炭对氢醌的吸附及转化效果好于其他两种,在未调节初始pH,反应时间3 h,反应温度25℃,木屑质活性炭用量为0.5 g·L^-1时,对氢醌的吸附率可达95.5%;木屑质活性炭用量为0.1 g·L^-1,其对氢醌的表观转化率为32.1%。木屑质活性炭微孔面积更大,表面的酚羟基、羧基和羰基官能团更丰富,故其吸附及转化氢醌的效果更好。在此基础上,提出了活性炭吸附及氧化氢醌的机理,为活性炭作为吸附剂或催化剂载体处理废水中酚类有机污染物提供理论依据。     

Catalytic oxidation of aqueous methyl and dimethylamines by activated carbon

The catalytic wet air oxidation (CWAO) of methyl and dimethylamines was studied. A commercial peach stones activated carbon and its oxidized and reduced forms were used as catalysts. The observed catalytic behavior is related to the presence of oxygenated surface functional groups on the activated carbons. The N-compounds were selectively oxidized to nitrogen, water and carbon dioxide using these activated carbon catalysts. It is proposed that the quinonic surface groups are responsible for the selective catalytic oxidation of these amines. Carboxylic, lactonic and anhydride groups strongly adsorb the amine compounds producing inhibition of the catalytic activity of the activated carbon in the CWAO process.     

Hierarchical pore structure of activated carbon fabricated by CO2/microwave for volatile organic compounds adsorption

An activated carbon pore-expanding technique was achieved through innovative reactivation by CO_2/microwave.The original and modified activated carbons were characterized by nitrogen adsorption–desorption,scanning electron microscopy,transmission electron microcopy,and Fourier transform infrared spectroscopy.The mesopore volume increased from 0.122 cm~3·g~(-1) to 0.270 cm~3·g~(-1),and a hierarchical pore structure was formed.A gradual decrease in the phenolic hydroxyl and carboxyl groups on the surface of activated carbon enhanced the surface inertia of granular activated carbon(GAC).The toluene desorption rate of the modified sample increased by 8.81% compared with that of the original GAC.Adsorption isotherm fittings revealed that the Langmuir model was applicable for the original and modified activated carbons.The isosteric adsorption heat of toluene on the activated carbon decreased by approximately 50%,which endowed the modified sample with excellent stability in application.The modified samples showed an enhanced desorption performance of toluene,thereby opening a way to extend the cycle life and improve the economic performance of carbon adsorbent in practical engineering applications.     

Elastomer–carbon black interaction: Influence of elastomer chemical structure and carbon black surface chemistry on bound rubber formation

The contribution of elastomer polarity and reactivity to bound rubber formation has been investigated. In this study, a number of elastomers of different chemical nature have been tested. The surface of the carbon black (N110) has also been modified by nitric acid oxidation in order to increase the concentration of surface functional groups. The experimental results have shown that the bound rubber formation is barely related to the polarity of the polymers. It is the reactive sites in both the elastomer and carbon black which are mainly responsible for bound rubber formation. It therefore appears that the elastomer/carbon black interaction leading to the formation of bound rubber is essentially a chemical process involving primary bond formation between elastomer and carbon black. The oxidized carbon black exhibits a higher surface activity which may be due to an increased concentration of oxygen-containing reactive surface sites, namely, phenolic hydroxyl, carboxyl, lactone, and quinone groups. © 1995 John Wiley & Sons, Inc.     

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.     

Influences of surface functional groups on catalytic activity over activated carbon catalysts for sulfur dioxide removal from flue gases

The catalytic oxidation of sulfur dioxide in flue gases over activated carbon catalysts was studied. Catalysts made from different materials or by different methods were markedly different. The catalysts were characterized by BET isotherms and X-ray power diffraction. The acidic and basic sites and/or strength on the catalysts were determined by temperature-programmed desorption, while surface functional groups were determined by X-ray photoelectron spectroscopy. The catalytic activity depended on oxygen-containing surface functional groups with Brønsted basicity properties. These groups on a furfural residue activated carbon could be increased by a suitable treatment to enhance the catalytic activity but other catalysts in this study showed no activity enhancement with a similar treatment.     

Preparation and characterization of carbon adsorbents from furfural

Carbon adsorbents with different properties were obtained from furfural with variations in the activation reagents and conditions of treatment. They possess insignificant ash and sulfur contents. Pore volume, pore size distribution and the chemical character of the surface of the obtained carbon adsorbent depend on the activation reagent and temperature of treatment. Various oxygen-containing groups of acidic character (carboxyl groups, carboxyl groups in lactone-like binding, phenolic hydroxyl and carbonyl groups) and different chemical properties are present on the surface of carbon oxidized with air. The sample activated with water vapour contains predominantly oxygen-containing groups with basic character.