The pyrolysis of propane. II. Effect of hydrogen sulphide

Hydrogen sulphide has been found to have a significant effect on the rate of carbon formation during the pyrolysis of propane. Studies have been carried out to measure carbon formation on pre-sulphided foils of nickel, copper, iron and stainless steel, and to measure carbon formation on the metals from a mixture of propane and hydrogen sulphide. No changes could be detected in the gaseous or liquid products of pyrolysis in the presence of sulphides, but carbon formation was either inhibited or accelerated. The formation of stable metal sulphides inhibited carbon formation. The formation and subsequent decomposition of metal sulphides accelerated carbon formation.     

Dechlorination of Chlorinated Aliphatic Compounds by Micro-scale Al-Zn-Mg/Fe Powders as Advanced Zero-valent Iron

Micro-scale Al-Zn-Mg/Fe composite powders (MAF) with high reactivity and good storage properties were prepared by reducing iron onto the surface of Al-Zn-Mg alloy powders. Experimental results show that MAF as advanced zero-valent iron are highly effective for degradation of chlorinated organic compounds. The efficiency of degradation for carbon tetrachloride and perchloroethylene is higher than 99% within a period of 2 h. The efficiency of degradation for trichloroethylene by MAF after storing for one month is equivalent to that by freshly prepared nano-size zero-valent iron particles.     

Al-Zn-Mg／Fe复合粉体降解水体中氯代有机物污染的研究

Micro-scale Al-Zn-Mg/Fe composite powders (MAF) with high reactivity and good storage properties were prepared by reducing iron onto the surface of AI-Zn-Mg alloy powders. Experimental results show that MAF as advanced zero-valent iron are highly effective for degradation of chlorinated organic compounds. The efficiency of degradation for carbon tetrachloride and perchloroethylene is higher than 99% within a period of 2 h. The efficiency of degradation for trichloroethylene by MAF after storing for one month is equivalent to that by freshly prepared nano-size zero-valent iron particles.     

Hydrogen adsorption in nitrogen enriched ordered mesoporous carbons doped with nickel nanoparticles

Ordered mesoporous carbons were enriched with nitrogen, then loaded with nickel nanoparticles and the effects on hydrogen storage were investigated. Firstly, a comparative characterization was carried out using transmission electronic microscopy, X-ray diffraction, nitrogen adsorption isotherm and thermogravimetric analysis. It was shown that the nickel was interacting with the nitrogen functional groups on the surface of the carbon support and even led to the formation of particles of different sizes. Secondly, hydrogen storage was studied. Hydrogen adsorption by volumetric method at 77, 298 and 373 K and high pressures (3 MPa) exhibited two distinct behaviors. At 77 K, the textural properties are critical and the adsorption capacities decreased with the nickel loading. On the contrary, at ambient and higher temperatures, the contribution of nickel nanoparticles was positive and marked by increased amounts of hydrogen reversibly adsorbed. Furthermore, the electrosorption of hydrogen was examined. It consists of the electrolysis of water that causes the formation and the diffusion of hydrogen on the adsorbent surface. In that particular application, the combination of nickel doping and nitrogen enrichment was detrimental to the adsorption capacities. However, nickel doped on pure carbons enhanced the amount of hydrogen electrosorbed.     

不同浸渍方法制备生物质活性炭及其活化机理的研究

利用生物质废料——棕榈壳,采用不同的浸渍方法制备高效活性炭。详细探讨了活化温度和浸渍剂(氢氧化钠)浓度对活性炭性能的影响。采用固定床吸附二氧化硫气体,评价了制备样品的吸附能力。还开展了解吸过程的研究,证明了二氧化硫与活性炭表面之间发生的化学吸附或化学反应。研究表明,采用前期浸渍方法制备活性炭时,原料表面的氢基团被钠置换,形成交联体,从而可获得较高的活性炭收率。而且,这些钠离子在二氧化碳活化阶段还起到催化作用。采用中期浸渍方法,氢氧化钠脱水后生成单质钠,夹杂在碳层中有利于微孔的形成,活化时与二氧化碳生成碳酸钠,可防止试样的过度烧失。采用后期浸渍方法时,由于氢氧化钠颗粒阻挡了活性炭的微孔通道,改变了活性炭的结构特性。但附着的氢氧化钠可通过生成亚硫酸钠,提高对二氧化硫的除去效果。     

Efficiently activated carbon fiber derived from grafted novoloid fiber

Graft copolymerization of methyl methacrylate onto novoloid fiber was carried out by the electron beam mutual irradiation method. The characteristics of the grafted fiber were almost the same as those of the original novoloid fiber. The grafted fiber was carbonized and activated to yield an efficiently activated carbon fiber. The yield and the specific surface area of the activated carbon fiber, derived from the grafted novoloid fiber, were much greater than those derived from the original novoloid fiber. This is because grafted poly(methyl methacrylate) decomposes into monomer and gaseous products, forming pores on the surface and inside of the novoloid fiber on heating. © 1993 John Wiley & Sons, Inc.     

生物质活性炭负载零价铁纳米晶簇直接催化还原NO

采用等体积浸渍法制备以生物质活性炭为载体的纳米铁基催化剂，利用TG、SEM、XPS、Raman等分析仪器对催化剂进行表征，探讨了活性炭负载零价铁和铁氧化物在无氧条件下脱硝的机理。结果表明：在750℃热还原条件下制得的铁基催化剂具备较高的活性，其活性中心是分散均匀的零价铁纳米晶簇。在280℃无氧条件下对NO的脱除效率达100%，且避免了活性炭载体的损耗。研究发现，催化剂快速失活是由于零价Fe被氧化为Fe₃O₄，因而降低了脱硝剂的活性。直接对失活催化剂进行热还原可以完全恢复活性，但这种方法会消耗炭载体；利用CO作为还原剂进行制备与再生，可以有效提高纳米晶簇的分散性，延长脱硝寿命并减少炭载体的损失，为零价Fe催化剂在实际应用中提供了可能性。     

Study of the NOχ reaction with reducing gases on Fe/ZrO2 catalyst

The Fe/ZrO₂ catalyst (1% Fe by weight) shows a strong adsorption capacity toward the nitric oxide (at room temperature the ratio NOFe is ca. 0.5) as a consequence of the formation of a highly dispersed iron phase after reduction at 500–773 K. Nitric oxide is adsorbed mainly as nitrosyl species on the reduced surface where the Fe²⁺ sites are prevailing, but it is easily oxidised by oxygen forming nitrito and nitrato species adsorbed on the support. However, in the presence of a reducing gas such as hydrogen, carbon monoxide, propane and ammonia at 473–573 K the Fe-nitrosyl species react producing nitrogen, nitrous oxide, carbon dioxide and water, as detected by FTIR and mass spectrometers. The results show that nitric oxide reduction is more facile with hydrogen containing molecules than with CO, probably due the co-operation of spillover effects. Experiments carried out with the same gases in the presence of oxygen show, however, a reduced dissociative activity of the surface iron sites toward the species NO_χ formed by NO oxidation and therefore the reactivity is shifted to higher temperatures.     

Effect of piezoelectric material on hydrogen adsorption

In hydrogen storage applications, the primary issue for physisorption of hydrogen onto solid-state materials is the weak interaction force between hydrogen molecules and the adsorbents. It is found that enhanced adsorption can be obtained under an external electric field, because it appears the electric field increases the hydrogen adsorption energy. Experiments were carried out to determine hydrogen adsorption on activated carbon using the piezoelectric material PMN-PT as the charge supplier under hydrogen pressure. Results indicate that more than 20% hydrogen adsorption enhancement was obtained. Parameters related to hydrogen adsorption enhancement include the amount of the charge and temperature. Higher voltage and lower temperature promote the increase of adsorption capacity but room temperature results are very encouraging.     

Heterogeneous photo-Fenton degradation of phenolic aqueous solutions over iron-containing SBA-15 catalyst

A novel iron-containing mesostructured material has been successfully tested for the heterogeneous photo-Fenton degradation of phenolic aqueous solutions using near UV–vis irradiation (higher than 313 nm) at room temperature and close to neutral pH. This catalyst is a composite material that contains crystalline hematite particles embedded into the mesostructured SBA-15 matrix in a wide distribution of size (30–300 nm) and well dispersed ionic iron species within the siliceous framework. The outstanding physico-chemical properties make this material a promising photocatalyst leading to better activity than other unsupported iron oxides. An experimental design model has been applied to assign the weight of catalyst and hydrogen peroxide concentrations in the photo-Fenton processes over this particular material. The catalytic performance has been monitored in terms of aromatics and total organic carbon (TOC) conversions, whereas the catalyst stability was evaluated according to the metal leached into the aqueous solution. Hydrogen peroxide concentration plays an important role in the stability of the iron species, preventing their leaching out into the solution, in contrast to the effect shown in typical dark-Fenton reaction. The homogeneous leached iron species result in very little contribution to the overall photocatalytic process. Catalyst loadings of 0.5 g/L and concentration of hydrogen peroxide close to the stoichiometric amount have yielded a total abatement of phenol and a remarkable organic mineralization.     

Development of novel nanocomposite adsorbent based on potassium nickel hexacyanoferrate-loaded polypropylene fabric

A nanocomposite adsorbent based on potassium nickel hexacyanoferrate-loaded polypropylene fabric was synthesized for selective removal of Cs ions from contaminated waters by a two-stage synthesis: radiation-induced graft polymerization of acrylic acid monomer onto the nonwoven polypropylene fabric surface with subsequent in situ formation of potassium nickel hexacyanoferrate (KNiHCF) nanoparticles within the grafted chains. Data of scanning electron microscopy, X-ray diffraction, and Fourier transform infrared spectroscopy confirmed the formation of KNiHCF homogeneous phase on the fabric surface, which consisted of crystalline cubic-shaped nanoparticles (70 to 100 nm). The efficiency of the synthesized adsorbent for removal of cesium ions was evaluated under various experimental conditions. It has demonstrated a rapid adsorption process, high adsorption capacity over a wide pH range, and selectivity in Cs ion removal from model solutions with high concentration of sodium ions.     

Study of the NOχ reaction with reducing gases on Fe/ZrO2 catalyst

The Fe/ZrO₂ catalyst (1% Fe by weight) shows a strong adsorption capacity toward the nitric oxide (at room temperature the ratio NOFe is ca. 0.5) as a consequence of the formation of a highly dispersed iron phase after reduction at 500–773 K. Nitric oxide is adsorbed mainly as nitrosyl species on the reduced surface where the Fe²⁺ sites are prevailing, but it is easily oxidised by oxygen forming nitrito and nitrato species adsorbed on the support. However, in the presence of a reducing gas such as hydrogen, carbon monoxide, propane and ammonia at 473–573 K the Fe-nitrosyl species react producing nitrogen, nitrous oxide, carbon dioxide and water, as detected by FTIR and mass spectrometers. The results show that nitric oxide reduction is more facile with hydrogen containing molecules than with CO, probably due the co-operation of spillover effects. Experiments carried out with the same gases in the presence of oxygen show, however, a reduced dissociative activity of the surface iron sites toward the species NO_χ formed by NO oxidation and therefore the reactivity is shifted to higher temperatures.     

Effect of hydrogen spillover on the hydrogenation of 1-hexene over diluted carbon molecular sieve supported Pt catalyst

Pt supported on a carbon molecular sieve (Pt/CMS) was prepared by pyrolysis of polyfurfuryl alcohol containing pre-reduced Pt particles. The catalysts were characterized by hydrogen chemisorption, XRD, N₂ adsorption/desorption and TEM. Hydrogen chemisorption showed that not all the Pt particles were exposed to H₂ molecules. Oxidation treatment made Pt particles more accessible to H₂. Catalyst activity was evaluated by hydrogenation of 1-hexene. Hydrogen spillover was demonstrated by diluting Pt/CMS with activated carbon or hydrogen type zeolite Y. The initial conversion of 1-hexene was increased from 86.5% to 98.5% and to 100% when Pt/CMS was diluted with activated carbon and hydrogen type zeolite, respectively. The high initial conversion was sustained for 6 h in the presence of diluents while the conversion decreased quickly for Pt/CMS alone.     

Potassium-Promoted Carbon-Based Iron Catalyst for Ammonia Synthesis. Effect of Fe Dispersion

Potassium-promoted iron catalysts supported on thermally modified, partly graphitized carbon were studied in the ammonia synthesis reaction. Iron nitrate was used as a precursor of the active phase and KOH or KNO₃ were used as promoters. The kinetic studies of NH₃ synthesis were carried out in a differential reactor under 63 bar and 90 bar pressure. Hydrogen chemisorption, X-ray diffraction and transmission electron microscopy experiments were performed to determine the dispersion of iron in the specimens. All the K⁺–Fe/C catalysts proved to be sensitive to ammonia, the NH₃ partial pressure dependencies of their reaction rates being close to that of the commercial magnetite catalyst (KM I, H. Topsoe). The catalytic properties of the promoted Fe particles on carbon were shown to be dependent upon the iron dispersion, i.e. smaller particles exhibited higher turnover frequency in NH₃ synthesis. It is suggested that either small Fe crystallites expose more highly active sites, e.g. C-7 (B-5) or the promotion of small crystallites by the alkali is more efficient.     

Catalytic oxidation of hydrogen sulphide on activated carbons

Activated carbon is a suitable adsorbent for removal of hydrogen sulphide from natural, synthesis or other product gases. The process depends predominantly on physical adsorption, though catalytic oxidation is also involved. During catalytic oxidation the H₂S is converted in the presence of oxygen to elemental sulphur, which is adsorbed onto the internal surface of the activated carbon, thus leading to a sulphur load of up to 120% by weight. The oxidation rate depends on the partial pressure of both reactants, H₂S and O₂ and is largely controlled by the characteristics of the activated carbon. The activity of the catalyst can be improved by impregnating the activated carbon with promoters such as iron and iodine. The regeneration of spent carbon is currently carried out using hot gas desorption methods at temperatures around 450 °C.     

The electrochemistry of nitrate-amide melts: Reactions of nickel and copper in nitrate-amide melts

Copper and nickel may be electrodeposited from their ions in solution in nitrate-amide melts at room temperature. In the ammonium nitrate-acetamide-urea melt at 23°C, the reduction to the metal competes with the corrosion reaction at low rates and with the reduction of the ammonium and nitrate ions of the melt at high current densities. Two distinct types of nickel complexes are found in solution. The nickel complex formed by the corrosion reaction is bound by at least one ammonia ligand. Nickel complexes formed by dissolving the halide in the melt show evidence of coordination by less strongly bounding ligands, probably by amides. Similarly, the visible spectra of copper chloride in solution suggest that the cupric ions are coordinated primarily by amides. The copper corrosion reaction produces a complex with a spectra distinctly different from that of cupric chloride in solution. The shift in absorption maxima suggests that the copper complex formed by the corrosion reaction has at least one ammonia ligand in the coordination sphere.     

零价铁活化过硫酸钠降解苯酚的研究

采用零价铁活化过硫酸钠的方式产生具有强氧化性的硫酸根自由基,以苯酚为目标污染物,考察了硫酸根自由基对苯酚的氧化降解行为。系统研究了零价铁投加量、过硫酸钠的投加量、不同温度、恒温震荡的时间、苯酚浓度、p H值对降解苯酚的影响。实验结果表明：在反应温度为35℃、p H为3、过硫酸钠用量为0.07g、零价铁用量为0.07g、苯酚浓度为10mg/L的条件下,恒温时间为90min时苯酚的降解情况最好,其降解率可以达到90.1%。     

Preparation of nickel coating on ZTA particles by electroless plating

With the aim to effectively improve the interface between ZrO₂ toughened Al₂O₃ (ZTA) particles and metal matrix, nickel was deposited on the surface of ZTA particles by electroless plating method. Formation mechanism of nickel coating and effects of the solution pH, loading capacity of ZTA particles and temperature on the nickel deposition were investigated. Microstructures, thickness and element distributions of nickel coating were analyzed by X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS). The results showed that the nickel was successfully deposited on the surface of ZTA particles by electroless plating without noticeable defects. The process of electroless nickel plating could be explained by combination of atomic hydrogen and electrochemistry theories. The interfacial nucleation of nickel is easier to form than spontaneous nucleation in the solution. Deposited Nickel has priority on the surface of ZTA particles comparing to that in solution. The optimal conditions to coat nickel on the surface of ZTA particles are: solution pH 4.7–4.8, loading capacity 15–20?g/L, and electroless plating temperature 85?°C. The ZTA particle reinforced iron matrix composites prepared by powder metallurgy could have better interfacial bonding between ZTA particle and iron matrix because of the nickel coating on the surface of ZTA particle. Nickel diffuses into the iron matrix during the sintering preparation of composite materials. The interface between ZTA particle and iron matrix presents the evidence of non-chemical bonding.     

Hydrogen storage on nickel catalysts supported on amorphous activated carbon

We have studied the hydrogen storage at room temperature and high pressure on nickel catalysts impregnated on an amorphous commercial activated carbon. The catalysts were studied by means of the BET method, XRD, metal surface area and temperature programmed desorption. It was shown that the catalysts could store significant amounts of hydrogen at room temperature and high pressure (up to 0.53% at 30 bars against 0.1% for the activated carbon). Various factors influencing the level of hydrogen uptake were examined and discussed. The hydrogen spillover would be the driving force for the hydrogen storage. Two mechanisms of hydrogen uptake are proposed.     

Styrene oxidation by H2O2 using Ni–Gd ferrites prepared by co-precipitation method

Gadolinium substituted nickel ferrites were prepared by co-precipitation method using NaOH at pH 14 at room temperature. Spinel phase formation was identified by taking the XRD pattern. DRIFT, TG, BET surface area and pore volume measurements, SEM and EDAX were the other characterization techniques used. Mössbauer analysis was performed to find out the site distribution of iron. Under optimized conditions, the prepared spinels were selectively forming benzaldehyde by the oxidation of styrene. Hydrogen peroxide was used as the oxidant. Effect of reaction temperature, reaction time, styrene to hydrogen peroxide molar ratio and effect of solvent medium were also studied.