Activated carbon as catalyst in wet oxidation of phenol: Effect of the oxidation reaction on the catalyst properties and stability

Catalytic wet oxidation (CWO) of phenol has been carried out in a continuous three-phase reactor by using a commercial activated carbon (AC) as catalyst, feeding oxygen as gas phase and an aqueous solution 1000 ppm in phenol to the reactor. A stable catalyst under operation conditions is one of the main difficulties to pass up in the catalytic wet oxidation process, so the stability of the activated carbon with the time on stream (TOS) was investigated. To do this the phenol conversion change was analyzed with TOS and results were contrasted to the change of the physicochemical properties of the AC with the TOS. Gas adsorption/desorption, TPD, XPS and SEM measurements were applied to the AC taken from the reactor after several TOS values. A significant reduction of the micro-pore volume and BET surface area of the catalyst was observed with TOS. However, as reaction proceeded the external surface area and the total amount of oxygen surface group increased. Moreover, regeneration of the initial catalyst properties was done by washing with water saturated in oxygen, at the reaction conditions or by heating in N₂ atmosphere at 450, 700 and 900 °C. The total micro-pore volume and internal surface area of the catalyst were not recovered by the regeneration process, probably due to blockage of the narrow micropores by pyrolytic carbon produced during the first step of the wet oxidation process.     

Pyrolysed carbon supported cobalt porphyrin: a potent catalyst for oxidation of hydrogen sulfide

Pyrolysed carbon supported cobalt porphyrin, an electrocatalyst that is frequently used for oxygen reduction in fuel cells, is evaluated for catalytic oxidation of hydrogen sulfide by dissolved dioxygen. The catalyst performs best after heat treatment at 880 °C_, at pH 8. Analysis of the reaction products reveals that sulfur is the dominant product throughout the investigated pH range 5–10. The catalyst performs much better than powdered activated carbon, granular activated carbon and different other forms of unmodified carbon catalysts. This is as far as we know the first time that heat treated cobalt porphyrins are evaluated for non-electrocatalytic applications.     

利用硫化氢的部分氧化生产氢、硫磺、乙烯和丙烯

阐述用硫化氢生产氢、乙烯、丙烯等新技术的基本原理，由于其中涉及元素硫的生产，故可将其作为硫回收总体方案中的一部分。这些工艺的主要优点是，生产每种终端产品时不必输入外部能量，因此燃料消耗大大低于目前采用的氢和烯烃生产工艺。此外．乙烯和丙烯的产率较高，选择性较好。这些技术的另一个重要方面是，在所谓的石油时代以后，由于可用生物质作为有机原料，并用硫磺作为循环方案的最初氧化剂，故它们是可持续的。     

Nanofibrous carbon with herringbone structure as an effective catalyst of the H2S selective oxidation

Granular nanofibrous carbons (NFCs) with herringbone structure were synthesised by the decomposition of natural gas over Ni/Al₂O₃ catalysts, and their performance in the selective oxidation of hydrogen sulphide was studied. Samples obtained over pure Ni catalysts are the strongest mechanically and easiest to produce. However, they show low selectivity for sulphur and are unstable during operation. Boiling in nitric acid followed by annealing led to improvements in catalytic stability and a significant increase in the selectivity for sulphur in the direct oxidation of hydrogen sulphide. The addition of large amounts of water vapour to the reaction mixture dramatically improved the selectivity and stability of the NFCs.     

Microbial treatment of sour gases for the removal and oxidation of hydrogen sulphide

It has been demonstrated that the bacterium Thiobacillus denitrificans may be readily cultured aerobically and anaerobically in batch and continuous cultures on hydrogen sulphide (H₂S) gas under sulphide-limiting conditions. Under these conditions sulphide concentrations in the culture medium were less than 1 μM resulting in very low concentrations of H₂S in the reactor outlet gas. The stoichiometries of both the aerobic and anaerobic reactions were determined and stable reactor operation demonstrated for up to five months. Maximum loading of the biomass was determined to be 5.4–7.6 mmoles H₂S/h-g biomass under anaerobic conditions and 15.1–20.9 mmoles H₂S/h-g biomass under aerobic conditions. Indicators of reactor upset were determined and recovery from upset demonstrated. Heterotrophic contamination was shown to have negligible effect on reactor performance with respect to hydrogen sulphide oxidation. In fact, growth of T. denitrificans in the presence of floc-forming heterotrophs produced a hydrogen sulphide active floc with excellent settling characteristics. A case study of the application of this technology to the removal and oxidation of H₂S from biogas is presented.     

活性炭材料的孔结构调控及表面修饰

活性炭材料是一种性能优良的吸附剂,在环境治理方面具有重要的意义。活性炭材料的孔隙结构及表面性质决定了活性炭的性能,通过孔隙结构的调控和表面修饰可以提高其吸附性能。概述了活性炭的各种孔结构调控和表面修饰处理的方法,展望了其发展趋势。     

The role of nitrogen in a carbon support on the increased activity and stability of a Pt catalyst in electrochemical hydrogen oxidation

Nitrogen-containing carbon materials were prepared by acetonitrile pyrolysis on carbon black and used as a support for a Pt catalyst. The Pt particles on N-containing carbon exhibited increased activity and stability in electrochemical hydrogen oxidation relative to Pt on pristine carbon black. The N-doped carbon had a graphitic structure and contained pyridinic and quaternary nitrogen species. The Pt nanoparticles were better-dispersed because of increased hydrophilicity induced by the nitrogen species. The Pt/N-containing carbon showed higher stability in a potential cycling test than Pt/C, because of an increased metal-support interaction. Using XPS and EELS mapping, we demonstrated that the metal-support interaction became stronger and more specific by adding nitrogen into carbon.     

New effective catalysts based on mesoporous nanofibrous carbon for selective oxidation of hydrogen sulfide

The systems based on granular mesoporous nanofibrous carbonaceous (NFC) materials synthesized by decomposition of hydrocarbons over nickel-containing catalysts are promising catalysts for selective oxidation of hydrogen sulfide. Sample series of nanofibrous carbon with three main types of their fiber structures and different contents of metal catalysts inherited from the catalysts for their synthesis were studied in this reaction. The correlation between NFC structure and its activity and selectivity in hydrogen sulfide oxidation was determined. The metal inherited from the initial catalysts for the synthesis of NFC influences the activity and selectivity of the resulting carbon catalysts. A particular influence is observed in the case of the catalyst withdrawn from the synthesis reactor at the stage of stationary operation of the metal catalyst (low specific carbon yields per unit weight of the catalyst). The presence of the metal phase results in an increase in the carbon catalyst activity and in a decrease in the selectivity to sulfur. NFC samples with the highest activity and selectivity are nanotubes and those with graphite planes perpendicular to the axis of the fibers. Carbon nanotubes have high selectivity, while samples obtained on copper–nickel catalysts also possess high activity. The promising NFC catalysts provide high conversion and selectivity (almost independent of the molar oxygen/hydrogen sulfide ratio) when a large excess of oxygen is contained in the reaction mixture.     

活性炭的改性条件及其对硫化氢吸附性能的影响

以工业活性炭为载体制备改性活性炭,对比研究了未改性活性炭,NaOH、Na2CO3、Fe(NO3)3、Cu(Ac)2改性活性炭及挂膜硫氧化细菌后活性炭在相同条件下对硫化氢穿透时间及吸附容量的影响。结果表明：在相同控制条件下,NaOH改性活性炭明显优于其它改性剂;不同梯度改性剂条件下,20% NaOH改性活性炭对硫化氢的吸附效果最好,吸附穿透容量为78.25 mg/g,穿透时间可以达到2000 min以上;不同改性剂挂膜硫氧化细菌后对硫化氢均有一定的处理效果,其中对已达到饱和吸附的NaOH改性活性炭挂膜后的再生效果可以达到100%以上,说明挂膜硫氧化细菌活性炭对硫化氢的处理具有很好的效果。     

Simulation of reverse flow operation for manipulation of catalyst surface coverage in the selective oxidation of ammonia

A mathematical model has been developed for the simulation of the ammonia oxidation in a reverse flow reactor. Computer simulations were carried out with a kinetic scheme, based upon elementary reaction steps. Aim was to explore the potential of a reverse flow reactor for selective oxidation of NH₃ to produce either N₂, NO, or N₂O via a dedicated operation procedure. Therefore, the conversion of NH₃ and the selectivity toward N₂, NO, or N₂O, were compared for a reverse flow operation and a steady state, once-through operation.A new operation concept of reverse flow operation in combination with a periodically lower feed concentration is proposed. The novel reactor concept shows a better performance compared to normal reverse flow operation and to steady state, once-through operation. The results indicate that reverse flow operation can be applied for manipulation of conversion and selectivity. A periodically lower feed concentration may increase the conversion, even up to levels that exceed the steady state value.     

Activated carbon monoliths for methane storage: influence of binder

In the present work, the agglomeration of a high adsorption capacity powdered activated carbon suitable for methane storage has been studied. Activated carbon monoliths have been prepared using the starting activated carbon and six different binders. Porous texture characterization of all the monoliths has been carried out by physical adsorption and helium density. Experimental methane adsorption capacity and delivery values have been obtained for all the samples. The results show that the adsorption capacities of the activated carbon monoliths are reduced with respect to the starting activated carbon. In addition to the adsorption capacity and delivery, the monolith density is also a crucial parameter for methane storage applications. This parameter has been obtained for all the samples. Moreover, the evaluation of the mechanical properties of the monoliths has been carried out with compression tests. According to our results, among all the binders studied, the one which produces monoliths with the best equilibrium between adsorption capacity and piece density has a methane delivery of 126 V/V. The important effect of the percentage of this binder in piece density and mechanical properties has been shown. Finally, a preliminary kinetic study of methane adsorption up to 4 MPa for the monoliths has shown that activated carbon monoliths do not present diffusional problems for adsorption of methane.     

Inhibition effect of carbon dioxide on the oxidation of hydrogen over a platinum foil catalyst

This paper investigates the catalytic ignition of the H₂/O₂/CO₂ mixture on platinum in a stagnation flow at atmospheric pressure experimentally and numerically. We measure the ignition temperatures of the gas mixtures flowing towards resistively heated platinum with various composition ratios and various diluent gases of N₂, Ar and CO₂. Compared with N₂ or Ar, the CO₂ dilution shows higher ignition temperature by about 50 K, even at the same composition ratio. The ignition temperature increase is proportional to the dilution ratio. Through the numerical simulation, it is illustrated that higher ignition temperature is caused by the adsorption of CO₂ and following dissociation on platinum surface, which was to date considered negligible in catalytic combustion.     

Cu-silicalite-1 catalyst for the wet hydrogen peroxide oxidation of phenol

The aim of the present work is to study the heterogeneous wet hydrogen peroxide catalytic oxidation (WHPCO) of phenol using copper bearing Silicalite-1 type zeolite, prepared by direct hydrothermal synthesis. The catalysts used for this study were three: one (Na)Cu-Silicalite-1 and two (H)Cu-Silicalite-1 prepared by different ion exchange methods. The results on catalytic activity for phenol abatement and hydrogen peroxide consumption of these materials are presented. The copper leaching during the reaction was evaluated for all samples. A comparison with the catalytic activity and stability of a Cu-Silicalite-1 material prepared by ionic exchange method is presented.     

Improved gas sensing of electrospun carbon fibers based on pore structure, conductivity and surface modification

A polyacrylonitrile and carbon black complex was fabricated as a gas sensor using an electrospinning method. The electrospun fibers were thermally treated to obtain carbon fibers, which were then chemically activated to improve the active sites for gas adsorption. The surface of the activated sample was modified by a fluorination treatment. The electrical conductivity was improved by the inclusion of carbon black additives. The activation process improved the porous structure, increasing the specific surface area around 100 times. The gas sensing ability was improved by the developed porous structure and induced functional groups. This treatment improves each of the three steps in the gas sensing mechanism. First, the induced functional groups attracted the target gas to the surface of the gas sensor through induced functional groups. Second, the pore structure significantly increased the amount of adsorbed gas. Third, the electrically conductive carbon black additives resulted in an efficient transfer of the resistive response from the surface of the gas sensor to the electrode. In total, the sensor sensitivity for NO and CO gases was improved about five times based on the effects of chemical activation, carbon black additives, and fluorination treatments.     

Au/MnO2–TiO2 catalyst for preferential oxidation of carbon monoxide in hydrogen stream

The catalytic activity of nanosize gold catalysts supported on MnO₂–TiO₂ and prepared by deposition–precipitation method has been investigated for preferential oxidation of carbon monoxide in H₂ stream. The catalysts were characterized by inductively coupled plasma-atomic emission spectroscopy, X-ray diffraction, nitrogen sorption, transmission electron microscopy, and X-ray photoelectron spectroscopy. The influence of pH in the preparation process and the amount of MnO₂ loading on the catalytic properties of the Au/MnO₂–TiO₂ catalysts were also studied. Fine dispersion of gold nanoparticles on all the supports was obtained. Especially, Au/MnO₂–TiO₂ with MnO₂/TiO₂ mol ratio of 2:98, showed a mean Au particle size of 2.37 nm. The nanosized support constrained the size of gold. The addition of MnO₂ on Au/TiO₂ catalyst improved the selectivity of CO oxidation without sacrificing CO conversion in hydrogen stream between 50 and 100 °C. This could be attributed to the interactions of gold metal with MnO₂–TiO₂ support and the optimum combination of metallic and electron-deficient gold on the catalyst surface.     

物理吸附仪测定活性炭载体比表面积及孔结构的方法

介绍了利用物理吸附仪测定活性炭的基本原理、模型及测定方法。通过改变相对压力点（P／Po）使活性炭孔结构的测定更加准确。     

Complex metal oxide catalysts for selective oxidation of propane and derivatives: II. The relationship among catalyst preparation, structure and catalytic properties

The effects of the preparation methods on the structure and catalytic performance of the MVTeNb (M=Mo or W) complex metal oxides (CMO) in selective oxidation of propane to acrylic acid (AA) were investigated. Preparation methods can play as significant roles as the chemical composition in determining the structures and catalytic properties of a CMO catalyst. Undesirable preparation methods or conditions can lead to the formation of ineffective crystal phases in the resulting catalysts, leading to poor catalytic activity or selectivity. An effective MoVTeNb oxide catalyst for propane selective oxidation to acrylic acid could be obtained with a combination of a proper metal ratio and proper preparation procedures. Certain drying methods, such as freeze dry and heat evaporation, are undesirable because phase segregation tends to occur during such processes, which negatively affect the catalytic performance. The preferred drying method is the rotavap method, which favors the formation of an effective crystal phase and suppresses the formation of impurity phases. The preferred calcination atmosphere is an inert atmosphere while a calcination atmosphere containing oxygen leads to the formation of significant amounts of MO₃ in MVTeNb oxides (M=Mo or W), which is known to be inactive in propane oxidation. It is proposed that an effective MoVTeNb oxide catalyst for propane selective oxidation to acrylic acid should contain at least two major crystal Phases A and B. Based on studies of oxides of pure Phase A and those exclusively enriched with Phase B, X-ray diffraction (XRD) characteristics of the two major crystal phases (A and B) have been identified and their catalytic functions studied. It is proposed that Phase A is active in propane activation but relatively unselective for the acrylic acid formation, while Phase B is reasonably active for propane activation and fairly selective for acrylic acid formation. It has been shown that using MoVTeNb oxide catalyst with a proper ratio of Phases A and B and synergy between them, very high propane conversion (73%) and acrylic acid selectivity (58%) can be achieved at the same time.