Degradation of polycyclic aromatic hydrocarbons by hydrogen peroxide catalyzed by heterogeneous polymeric metal chelates

Chelating sorbents with 8-hydroxyquinoline (IVa), 8-hydroxyquinoline-5-sulfonic acid (IVb), and tris(2-aminoethyl)amine (VI) ligands immobilized on macroporous methacrylate matrix were prepared and saturated with Co(II), Cu(II), and Fe(II). All these chelates catalyze cleavage of H₂O₂ yielding highly reactive hydroxyl radicals. All were able to degrade by this mechanism polycyclic aromatic hydrocarbons (anthracene, benzo[a]pyrene and benzo[k]fluoranthene). The most effective catalysts IVa-Fe, IVb-Fe, and VI-Cu (25 mg with 100 μmol H₂O₂) performed complete decomposition of 33 μg anthracene and benzo[a]pyrene during one 7-day catalytic cycle at 25 °C. The fastest decomposition proceeded during the 1st day of incubation; 75% of anthracene and 74% of benzo[a]pyrene were decomposed by IVb-Co within the first 24 h. More than 25% decomposition within the 1st day was also achieved with IVb-Fe, VI-Cu, IVa-Cu, and VI-Co for anthracene and more than 30% benzo[a]pyrene was decomposed by IVb-Fe, VI-Cu, IVa-Cu, and IVb-Cu during the same period. 1,4-Anthracenedione was the main product of anthracene oxidation by all catalysts. The catalysts were stable at pH 2–11 depending on their structure and able to perform sequential catalytic cycles without regeneration.     

Oxidation of hydrocarbons with hydrogen peroxide catalyzed by maltolato vanadium complexes covalently bonded to silica gel

The bis(maltolato)oxo complexes of vanadium(V) and vanadium(IV) both in a soluble form and anchored to chemically modified silica gel, when used in combination with pyrazine-2-carboxylic acid (PCA), catalyze the oxidation of benzene to phenol and alkanes to the corresponding alkyl hydroperoxides with H₂O₂ at 40–50 °C. Heterogenizing the complexes leads to changes in regioselectivity and bond selectivity parameters of the alkane oxidation, and this opens new routes to the enhancement of the selectivity in oxidation processes.     

钼过氧配合物催化过氧化氢氧化环己醇的研究

采用钼酸铵与含氧有机配体原位形成的络合物作为催化剂,以质量分数30%过氧化氢催化氧化环己醇合成环己酮.考察了草酸、水杨酸、苯甲酸、乙酸和丁二酸5种不同的配体对环己醇氧化反应的催化作用,并探索反应时间、反应温度和催化剂用量对环己酮收率的影响.研究结果表明,以草酸为配体时催化效果最好,环己酮收率最高,可达85%.催化氧化反应的最佳条件:Mo与草酸配体物质的量比=1:1,反应温度(85～90)℃,反应时间6 h.     

Selective oxidation of alcohols with hydrogen peroxide catalyzed by hexadentate binding 8-quinolinolato manganese(III) complexes

A series of hexadentate 8-quinolinolato manganese(III) complexes were synthesized and proven to own a distorted octahedral geometry via elemental analysis, solid UV–vis spectroscopy and Hartree–Fock/3-21G+ calculation. These Mn(III) complexes were found to be more efficient than their corresponding tetradentate 8-quinolinolato manganese(II) and salen-Mn^IIIOAc for the oxidation of alcohols in acetone medium, being due to their special hexadentate binding structures that could open an axial MnO bond to form the more active pentadentate structures in the presence of aqueous hydrogen peroxide, as supported by UV–vis spectra. The halogen substituents in ligand's aryl ring could significantly enhance the catalytic activities and 5-chloro-7-iodo-8-quinolinolato manganese(III) gave the highest turnover number (TON). A reasonable mechanism for the present catalytic system was proposed.     

改性V_2O_5催化过氧化氢氧化异丁香酚制香草醛

V₂O₅经甘油还原,再以邻苯二甲酸或其二钠盐溶液浸渍,制备了改性V₂O₅催化剂用于异丁香酚的过氧化氢氧化。运用FT-IR、紫外可见漫反射光谱（DR UV-Vis）、XRD等对催化剂进行了表征。结果表明,还原-浸渍法可以有效调变V₂O₅的价态与晶体结构从而提升其催化性能,其中以甘油在120 ℃还原V₂O₅所得前体浸渍邻苯二甲酸二钠所得催化剂 (PVO)-120性能较佳。考察了N,N-二甲基甲酰胺（DMF）等助剂、DMF用量和反应时间等对氧化反应的影响。最优反应条件为：以 (PVO)-120为催化剂,以DMF-CH₃COCH₃（20%,体积比）为介质,异丁香酚：H₂O₂=1∶2（摩尔比）,20 ℃反应4 h,异丁香酚转化率可达87.3%,香草醛收率达到78.0%。     

Oxidation of alkanes with hydrogen peroxide catalyzed by Schiff base complexes covalently anchored to polyoxometalate

The catalytic activity of a hybrid compound [Fe(salen)-POM] (1) consisting of metallosalen moiety, [Fe^III(salen)Cl], covalently linked to a Keggin type polyoxometalate, K₈SiW₁₁O₃₉ (POM), in the oxidation of hydrocarbons with hydrogen peroxide was investigated. Reaction products were identified by gas chromatography and satisfactory yields were obtained. While, the Fe(salen)-POM catalyst showed high catalytic activity and product selectivity in the oxidation reactions, the metallosalen alone, [Fe^III(salen)Cl], showed very poor catalytic activity in these reactions. The ability of various transition metal ions in this oxidation system was also investigated. Among a series of hybrid compounds, Fe(salen)-POM showed the highest activity.     

多环芳烃的加氢裂化

本文综述了近年来多环芳烃加氢裂化反应催化剂、反应网络及反应机理等方面的研究进展。     

水中多环芳烃(PAHs)的去除技术研究进展

从水中多环芳烃去除技术的角度,论述了物理法、化学法和生物法的应用现状和特点。为了更好的实现对水中多环芳烃的去除,各处理方法应该加强廉价高效降解材料和处理剂,降解过程和降解机理、复合降解方法以及对处理方法影响因素和条件的控制等方面的研究。     

水中多环芳烃(PAHs)的去除技术研究进展

从水中多环芳烃去除技术的角度,论述了物理法、化学法和生物法的应用现状和特点。为了更好的实现对水中多环芳烃的去除,各处理方法应该加强廉价高效降解材料和处理剂,降解过程和降解机理、复合降解方法以及对处理方法影响因素和条件的控制等方面的研究。     

Oxidation of hydrocarbons by hydrogen peroxide over Ti catalysts: Kinetics and mechanistic studies

n-hexane conversion to hexanols and hexanones as well as the conversion of 2- and 3-hexanol to 2- and 3- hexanone, by reaction with aqueous hydrogen peroxide on titanium silicalite were the objects of kinetic investigations. The choice of these reactions is justified on the basis of an analysis of literature dealing with partial oxidation reactions performed on Ti sites in silica environments. The kinetic analysis based on equations derived using the mathematical theory of linear graphs allows several conclusions on the nature of surface intermediates and on the reaction mechanism. These conclusions are discussed in terms of the partial oxidation of organic materials by hydrogen peroxide over Ti catalysts. This review paper relies mostly on work by the authors and it intends to make an integrated presentation of the kinetics of some critically significant catalytic oxidation reactions. The content was the subject of a plenary lecture at the 5^th symposium of the Romanian Catalysis Society.     

Solubilization of model polycyclic aromatic hydrocarbons by nonionic surfactants

Solubilization of model polycyclic aromatic hydrocarbons (PAHs) by the readily biodegradable nonionic surfactants, Tergitol 15-S-X (X=7,9 and 12), consisting of mixtures of secondary ethoxylated alcohols was investigated at temperatures below their cloud points. Their solubilization capacities for phenanthrene were compared to those of three other commonly used surfactants, e.g. Triton X-100 and Tween 20 as well as Tween 80. Correlation between the micelle-water partition coefficients and the octanol-water partition coefficients in Tergitol 15-S-7 solutions indicated that the hydrophobicity of PAHs, i.e., their octanol-water partition coefficients, could be used in predicting the solubilization efficiency of PAHs by this nonionic surfactant. Effects of temperature and salinity on solubilization capacity of Tergitol 15-S-7 surfactant for phenanthrene were also investigated along with the micellar properties. The change in hydrodynamic radius and aggregation number of micelles with temperature was measured by the dynamic and static laser light scattering techniques. Results showed that increasing aggregation number and micellar size at higher temperature when cloud point is approached gives rise to the higher solubilization capacity of this surfactant. Effect of salinity on the enhancement of phenanthrene solubility was also discussed in terms of conformation changes in the micelles due to the possible coordination of sodium cations and oxygen atoms on the ethylene oxide groups of the surfactant.     

Catalytic oxidation of olefins with hydrogen peroxide catalyzed by [Fe(III)(salen)Cl] complex covalently linked to polyoxometalate

The catalytic activity of a hybrid compound [Fe(salen)-POM] (1) consisting of Fe(III)(salen)Cl [H₂salen = N,N′-bis(salicylidene)ethylenediamine] complex covalently linked to a Keggin type polyoxometalate, K₈SiW₁₁O₃₉, (POM) was studied in the oxidation of various olefins in acetonitrile, using hydrogen peroxide as oxygen source. While, [Fe(salen)-POM] catalyst showed moderate to good catalytic activity and product selectivity in the oxidation reactions, the complex Fe(III)(salen)Cl showed poor catalytic activity in these reactions. The effect of other parameters such solvent, oxidant, temperature and the metal type in Schiff base complex were also investigated.     

Iron(II, III)-Catalyzed Oxidation of Limonene by Dioxygen

Labile iron(II) and iron(III) complexes {[Fe^II(bpy)₂²⁺]_solv and [Fe^III(bpy)₂³⁺]_solv} in acetonitrile activate dioxygen for the oxidation of limonene to produce mainly carvone, carveol, limonene oxide, and perillaldehyde. Iron(III) complex is reduced by the substrate to iron(II) one, which activates dioxygen. Probably the catalyst interacts with substrate prior to the oxidation process. Perillaldehyde is likely formed directly from oxidation of methyl group (not via alcohol). However, the aldehyde is also reduced to perillyl alcohol by the reduced form of the catalyst.     

Iron(III)-induced activation of hydrogen peroxide for oxidation of 2-methylnaphthalene in glacial acetic acid

Simple iron(III) salts activate hydrogen peroxide to oxidize 2-methylnaphthalene to 2-methyl-1-naphthol in glacial acetic acid. 2-Methyl-1-naphthol is then oxidized to 2-methyl-1,4-naphthoquinone by hydrogen peroxide without influence of the catalyst. This is in contrast to the previous reports, which excluded the formation of 2-methyl-1-naphthol as an intermediate product in the process of 2-methylnaphthalene oxidation to 2-methyl-1,4-naphthoquinone. The process, however, mimics the microbial conversion of 2-methylnaphthalene to 2-methyl-1,4-naphthoquinone. The presence of chloride in the system causes exclusively the formation of 2-methyl-1-chloronaphthalene.     

Oxidation of Pt(II) to Pt(IV) complex with hydrogen peroxide in glycols

The reaction of cis, cis-[Pt^II(9-fm)(dmpda)] (9-fm=9-fluorenylidenemalonate, dmpda=2,2-dimethyl-1,3-propanediamine) with hydrogen peroxide in ethyleneglycol produces cis,trans,cis-[Pt^IV(9-fm)(OCH₂CH₂OH)(OH)(dmpda)]. Its crystal structure shows that the local geometry around the platinum atom approximates a typical octahedral arrangement with the added OCH₂CH₂OH/OH ligands in trans coordination sites. The molecules are packed in a two-dimensional assembly via van der Waals interactions, where the hydrophobic fluorenyl groups are arranged on both faces of the assembly plate whereas the hydrophilic groups fill up the inner part of the plate. The compound bearing both “inorganic OH” and “organic OH” is a potential precursor for further various functionalizations.     

Oxidation of dibenzothiophene by hydrogen peroxide in the presence of bis(acetylacetonato)oxovanadium(IV)

In the presence of bis(acetylacetonato)oxovanadium(IV), dibenzothiophene was oxidized by hydrogen peroxide to form sulfoxide and sulfone products. The percentage of dibenzothiophene remaining after the oxidation and the ratio of these oxidation products, as determined by ¹H NMR spectroscopy, was largely dependent on the solvent used. Reactions in acetonitrile consumed more than 99% of the dibenzothiophene in the reaction and yielded the sulfone as the major product. The efficacy of biphasic oxidations performed in heptane and acetonitrile were dependent on the ratio of acetonitrile to heptane with a higher proportion of acetonitrile resulting in greater consumption of dibenzothiophene. After multiple oxidations, all of the dibenzothiophene was removed from the heptane solution.     

Elimination of polycyclic aromatic hydrocarbons by bleaching of olive pomace oil

A detailed study of the efficacy of the bleaching process for elimination of polycyclic aromatic hydrocarbons in Spanish olive pomace oils has been carried out. For this purpose active carbon with bleaching earth was used as absorbent. The amount of benzo‐(α)‐pyrene was determined by reversed‐phase high‐performance liquid chromatography with a Fluorimetric detector. The use of exhausted filter‐cakes in countercurrent processes with a cake formed of active carbon and bleaching earth is very efficient for reducing the initial content of benzo‐(α)‐pyrene before the addition of fresh adsorbent, thus reducing the amounts of carbon and earth required.     

Multiphase oxidation of alcohols and sulfides with hydrogen peroxide catalyzed by heteropolyacids

This work describes the application of a multiphase system for the oxidation of alcohols to ketones or aldehydes, and the selective conversion of sulfides to sulfoxides or sulfones using Keggin-type heteropolyacids and hydrogen peroxide. Benzylic and secondary alcohols were oxidized to ketones or aldehydes at 70 °C in good yield and selectivity. Similarly, sulfides were converted to sulfoxides or sulfones at room temperature with high yields and selectivity.     

稠环芳烃裂化研究进展

稠环芳烃物种含有大量的芳烃资源,由于苯环间的共轭效应,难以将其直接转化。随着原油芳烃含量的逐年增高,在工业规模如何有效地处理稠环芳烃备受关注。对稠环芳烃的加氢裂化和催化裂化反应机理进行总结对比,并通过介绍裂化催化剂的研究进展为稠环芳烃的催化裂化拓展新思路。