Multi-walled carbon nanotubes (MWNTs) as an efficient catalyst for catalytic wet air oxidation of phenol

Multi-walled carbon nanotubes (MWNTs) were used as a catalyst for catalytic wet air oxidation (CWAO) of phenol in a batch reactor. SEM, TEM and FT-IR technique were applied to investigate the microstructure and the surface functional group of the MWNTs. When the carboxylic groups (–COOH) are grafted onto the surface of the MWNTs, the functionalized MWNTs exhibit a good catalytic activity in CWAO of phenol. At a reaction temperature of 160 °C, oxygen pressure of 2.0 MPa and a phenol concentration of 1000 mg/L, 100% phenol and 76% TOC are removed after 120 min reaction.     

A bimetallic molybdenum (VI) and stannum (IV) catalyst for the transesterification of dimethyl oxalate with phenol

The transesterification of dimethyl oxalate (DMO) with phenol to methyl phenyl oxalate (MPO) and diphenyl oxalate (DPO) was carried out in liquid phase under facile catalytic conditions. A series of bimetallic, MoO₃–SnO₂/SiO₂, catalysts with various Mo and Sn content were prepared by sequential impregnation of cationic Mo species and cationic Sn complexes using impregnation method. The effects of mass ratio of Mo:Sn, amount of Sn additive, and Mo(Sn) laoding amount on activities of transesterification of dimethyl oxalate with phenol were investigated. The evaluation results showed that MoO₃–SnO₂/SiO₂ catalyst with 14 wt% Mo(Sn) content performed best, giving 74.6% DMO conversion and 99.5% selectivity to MPO and DPO. This new heterogeneous catalyst provided not only an excellent selectivity (99% to MPO and DPO) and high yield of MPO and DPO but also a simple and practical protocol for DPC synthesis.     

Reactivity and surface properties of silica supported molybdenum oxide catalysts for the transesterification of dimethyl oxalate with phenol

A series of MoO₃/SiO₂ catalysts were prepared with Mo loadings ranging from 1 to 16 wt% and applied to the transesterification of dimethyl oxalate (DMO) with phenol. The results showed that the catalyst of MoO₃/SiO₂ with 1 wt% Mo content performed best, giving 54.6% conversion of DMO and 99.6% selectivity to target products, methyl phenyl oxalate (MPO) and diphenyl oxalate (DPO). The surface properties were investigated by means of X-ray diffraction (XRD), X-ray photoelectron (XPS), BET specific surface area, temperature-programmed desorption (TPD) of ammonia, and FTIR analysis of adsorbed pyridine. XPS and XRD analyses indicated that Mo(VI) species was highly dispersed at low Mo loading and MoO₃ of the crystal structure appeared at higher loading. NH₃-TPD characterization and FTIR analysis of adsorbed pyridine demonstrated that only Lewis weak acids were present on catalyst surface and the amount of Mo loading has little effect on the strength of the surface acid on MoO₃/SiO₂. The catalytic results exhibited that the synergetic effect of Mo active centers with weak Lewis acid sites catalyzed transesterification of DMO with phenol.     

负载型TiO2催化苯酚和草酸二甲酯酯交换反应

使用负载型TiO2/SiO2催化苯酚和草酸二甲酯酯交换反应合成草酸二苯酯.通过对TiO2/SiO2催化剂进行XRD、BET化学吸附、NH3-TPD、XPS等表征以及活性测试,结果表明在苯酚和草酸二甲酯酯交换反应中,负载型TiO2的催化性能与TiO2在载体表面的分散状态和催化剂的弱酸性密切相关.微晶态TiO2的产生会导致催化性能的下降.确定了较佳的焙烧温度为550℃,以该温度焙烧的TiO2/SiO2为催化剂,TiO2负载量为13%时,草酸二甲酯的转化率、甲基苯基草酸酯与草酸二苯酯的收率分别为53.1%、38.3%、14.5%.初步探讨了该反应条件下催化剂的失活.     

An effect of iron(III) oxides crystallinity on their catalytic efficiency and applicability in phenol degradation—A competition between homogeneous and heterogeneous catalysis

Catalytic efficiency, stability and environmental applicability of five iron(III) oxide nanopowders differing in surface area and crystallinity were tested in degradation of concentrated phenolic aqueous solutions (100 g/L) at mild temperature (30 °C), initially almost neutral pH and equimolar ratio of hydrogen peroxide and phenol. The catalyst properties were easily controlled by varying in reaction time during isothermal treatment of ferrous oxalate dihydrate in air at 175 °C. Although the catalytic efficiency clearly increases with the surface area of the nanopowders, it is not due to the solely heterogeneous catalytic mechanism as would be expected. The amorphous Fe₂O₃ nanopowders possessing the largest surface areas (401 m² g⁻¹, 386 m² g⁻¹) are the most efficient catalysts evidently due to their highest susceptibility to leaching in acidic environment arising as a consequence of phenol degradation products. Thus, these amorphous samples act partially as homogeneous catalysts, which was confirmed by a high concentration of leached Fe(III) ions in the solution (19 ppm). The crystalline hematite (α-Fe₂O₃) samples, varying in surface area between 337 m² g⁻¹ and 245 m² g⁻¹, are generally less efficient when compared to the amorphous powders, however their catalytic action is almost exclusively heterogeneous as only 3 ppm of leached Fe(III) was found in the reaction systems catalyzed by nanohematite samples. A significant difference in relative contributions of heterogeneous and homogenous catalysis was definitely established in buffered reaction systems catalyzed by amorphous Fe₂O₃ and nanocrystalline hematite. The nanohematite sample exhibiting the highest heterogeneous action was tested at decreased initial phenol concentration (10 g/L), which is closer to the real contents of phenol in waste waters, and at different hydrogen peroxide/phenol molar ratios to consider its environmental applicability. At the hydrogen peroxide/phenol ratio equal to 5, no traces of the leached iron were detected and the phenol conversion of 84% was reached. Moreover, such a high degree of conversion is accompanied by a decrease of the chemical oxygen demand (COD) from the initial value of 11.23 g/L to 4.22 g/L after 125 min. This fact indicates that the considerable fraction of primary reaction products was totally degraded.     

New approach for highly selective hydrogenation of phenol to cyclohexanone: Combination of rhodium nanoparticles and cyclodextrins

The effect of cyclodextrins on the activity and selectivity of a catalytic system based on rhodium nanoparticles stabilized by polyacrylic acid (PAA) in the hydrogenation of phenol in aqueous solution and ionic liquid was reported. It was found that the reaction medium and the nature of the cyclodextrin (CD) essentially affect the rate of reaction and the distribution of reaction products. The use of the system based on rhodium nanoparticles stabilized by cyclodextrins makes it possible to rapidly and efficiently prepare cyclohexanone from phenol with yields up to 100% under relatively mild conditions (1 h; T = 80°°C, p(H₂) = 10–40 bars).     

Preparation, characterization and catalytic properties of carbon nanofiber-supported Pt, Pd, Ru monometallic particles in aqueous-phase reactions

Carbon nanofibers (CNF) synthesized by catalytic chemical vapor deposition (CVD) method were used to prepare supported platinum, palladium and ruthenium monometallic (2.0 wt.%) catalysts by means of incipient-wetness impregnation method. The CNF support and catalysts were characterized by X-ray powder diffraction (XRD), nitrogen adsorption/desorption isotherms, volumetric chemisorption of hydrogen, temperature-programmed reduction (H₂-TPR) and scanning electron microscopy (SEM). Solids were tested in catalytic wet-air oxidation (CWAO) of phenol aqueous solution (180–240 °C and 10.0 bar of oxygen partial pressure) carried out in a continuous-flow trickle-bed reactor. Trends of phenol and total organic carbon (TOC) conversion demonstrate that the CNF support and CNF-Pt catalyst did not exhibit constant activity for CWAO of phenol. A decrease of catalyst activity, detection of carbon dioxide in the off-gas stream while examining catalyst stability and significant textural changes observed, provide an evidence that under net oxidizing reaction conditions gasification of the CNF support occurs. The prepared catalysts were also tested in liquid-phase thermal decarboxylation of formic acid in inert atmosphere (60–220 °C). Among solids examined, the CNF-Pd exhibited the highest activity. At the employed conditions, no decomposition of the CNF support was observed during the thermal decarboxylation of formic acid.     

Phenol degradation by Fenton's process using catalytic in situ generated hydrogen peroxide

The recent reported pathway using oxygen and formic acid at ambient conditions has been utilized to generate hydrogen peroxide in situ for the degradation of phenol. An alumina supported palladium catalyst prepared via impregnation was used for this purpose. Almost full destruction of phenol was carried out within 6 h corresponding to the termination of 100 mM formic acid at the same time. In addition, a significant mineralization (60%) was attained. A simulated conventional Fenton process (CFP) using continuous addition of 300 ppm H₂O₂ displayed maximum 48% mineralization. Study of different doses of formic acid showed that decreasing the initial concentration of formic acid caused faster destruction of phenol and its toxic intermediates. The catalytic in situ generation of hydrogen peroxide system demonstrated interesting ability to oxidize phenol without the addition of Fenton's catalyst (ferrous ion). Lower Pd content catalysts (Pd1/Al and Pd0.5/Al) despite of producing higher hydrogen peroxide amount for bulk purposes, did not reach the same efficiency as the Pd5/Al catalyst in phenol degradation. The later catalyst showed a remarkable repeatability so that more than 90% phenol degradation along with 57% mineralization was attained by the used catalyst after twice recovery. Higher temperature (45 °C) gave rise to faster degradation of phenol resulting to almost the same mineralization degree as obtained at ambient temperature. Meanwhile, Pd leaching studied by atomic adsorption proved excellent stability of the catalysts.     

Assessment of Fe2O3/SiO2 catalysts for the continuous treatment of phenol aqueous solutions in a fixed bed reactor

Different iron-containing catalysts have been tested for the oxidation of phenol aqueous solutions in a catalytic fixed bed reactor in the presence of hydrogen peroxide. All the catalysts consist of iron oxide, mainly crystalline hematite particles, over different silica supports (mesostructured SBA-15 silica and non-ordered mesoporous silica). The immobilization of iron species over different silica supports was addressed by direct incorporation of metal during the synthesis or post-synthesis impregnation. The synthesis conditions were tuned up to yield agglomerated catalysts with iron loadings between 10 and 15 wt.%. The influence of the preparation method and the type of silica support was evaluated in a catalytic fixed bed reactor for the continuous oxidation of phenol in terms of catalysts activity (phenol and total organic carbon degradation) as well as their stability (catalyst deactivation by iron leaching). Those catalysts prepared by direct synthesis, either in presence of a structure-directing agent (Fe₂O₃/SBA-15(DS)) or in absence (Fe₂O₃/SiO₂(DS)), achieved high catalytic performances (TOC reduction of 65% and 52%, respectively) with remarkable low iron leaching in comparison with their silica-based iron counterparts prepared by impregnation. Catalytic results have demonstrated that the synthesis method plays a crucial role in the dispersion and stability of active species and hence resulting in superior catalytic performances.     

Catalytic cracking of mixtures of model bio-oil compounds and gasoil

Key model bio-oil O-compounds representing some of the major oxygenate groups, such as acetic acid, hydroxyacetone and phenol, were mixed with a standard gasoil and tested under fluid catalytic cracking (FCC) conditions in a laboratory-scale unit using an industrial FCC equilibrium catalyst (E-CAT) and a mixture of E-CAT and ZSM-5 additive. As a general trend, acetic acid, phenol or hydroxyacetone when mixed with a conventional gasoil increased the overall conversion, defined as fraction of the feed converted into gases, gasoline and coke, reduced the coke yield and increased fuel gas, LPG and gasoline. The conversion of the gasoil itself over pure E-CAT was not altered significantly by the presence of these compounds. This result could be interpreted by a preferential adsorption of the feed on the catalytic surface instead of the oxygen containing compounds. On the other hand, the ZSM-5 additive effect was attenuated in the presence of the O-compounds, suggesting a preferential interaction of such compounds with the ZSM-5. Up to 10 wt.% of these O-compounds studied can be processed without major problems in a FCC unit except for phenol.     

Supplementation of DHA-Rich Microalgal Oil or Fish Oil During the Suckling Period in Mildly n-3 Fatty Acid-Deficient Rat Pups

Long-chain polyunsaturated fatty acids (LC-PUFA), particularly arachidonic acid (ARA) and docosahexaenoic acid (DHA), are considered critical for the development of infants and are commonly supplemented in infant formulae. In this study, two common sources of n-3 LC-PUFA, fish oil (FO) and DHA-rich microalgal oil (DMO), were fed to rat pups of mildly n-3 PUFA-deficient dams to compare changes in LC-PUFA of tissue phospholipids. The milk from dams fed a n-3 PUFA-deficient diet contained less n-3 LC-PUFA than that of dams fed a control diet (AIN-93G). The pups' were given orally 1 mg/g weight of either FO or DMO for 17 days between the ages of 5 and 21 days, the pups were weaned, and sacrificed 1 week later for analysis of fatty acid compositions of brain, heart, kidney, spleen, and thymus phospholipids. Although both FO and DMO brought about a recovery in the tissue DHA levels compared to those of the control group (pups from AIN-93G-fed dams), DMO was more effective at restoring tissue LC-PUFA status because it was richer in DHA than FO. FO had a slightly lower PUFA level than that required to bring the LC-PUFA status completely to normal levels in this experiment, and EPA did not accumulate in tissues under the conditions tested here. These results demonstrate the effectiveness of ingesting either FO or DMO in the pre-weaning period for improving mild n-3 PUFA deficiency.     

Behavior of Cu–Ce/AC catalyst–sorbent in dry oxidation of phenol

An activated carbon-supported copper and cerium catalyst–sorbent (Cu–Ce/AC) is studied for phenol adsorption from a water phase and catalytic oxidation of the adsorbed phenol under dry conditions. The Cu–Ce/AC has high phenol adsorption capacities and high phenol oxidation activities. The phenol saturation adsorption capacity of the fresh Cu–Ce/AC is about 209 mg/g. With increasing adsorption–oxidation cycles (repeat uses), the phenol adsorption capacity decreases consecutively to a stable value of about 78 mg/g when the oxidation is carried out at 250 °C for 2 h, which is better than that of other types of AC-based materials. The initial oxidation temperature for phenol is about 160 °C, which is 150 °C lower than the ignition temperature of the AC. The main oxidation products are CO₂ and H₂O with a small amount of desorbed phenol. The decrease in phenol adsorption capacity after the oxidation is caused by the formation of phenol polymeric residues, which block the micro-pore and perhaps cover the active sites.     

A recyclable thermo-responsive catalytic system based on poly(N-isopropylacrylamide)-coated POM@SBA-15 nanospheres

A nanoreactor with thermo-responsive poly(N-isopropylacrylamide) (PNIPAM) coated on the external pores of SBA-15 and a Keggin-type polyoxometalate (POM), molybdovanadophosphoric acid (H₅PV₂Mo₁₀O₄₀) loaded into the internal pores were fabricated. It showed excellent catalytic activity toward catalytic wet hydrogen peroxide oxidation (CWPO) of phenol at 25 °C (below lower critical solution temperature (LCST) of PNIPAM). When the temperature was 50 °C (above LCST), the rate of CWPO dropped significantly. These results indicated that the nanoreactor shows the repeated on/off catalytic activity switched by temperature control. The recyclable catalytic processes were successfully conducted.     

An improved process for the synthesis of titanium-rich titanium silicates (TS-1) under microwave irradiation

Microwave irradiation is efficiently employed for the synthesis of crystalline titanium silicates with MFI structure and high titanium content (Si/Ti = 10) at extremely faster reaction rates. The physico-chemical properties and the phenol oxidation activity of these catalytic materials are similar to the titanium silicates synthesized by the conventional heating method.     

Hydrodeoxygenation of bio-crude in supercritical hexane with sulfided CoMo and CoMoP catalysts supported on MgO: A model compound study using phenol

Hydrodeoxygenation (HDO) of bio-crude was investigated using phenol as a model compound in supercritical hexane at temperatures of 300–450 °C and cold pressure of hydrogen 5.0 MPa with MgO-supported sulfided CoMo with and without phosphorus as a catalyst promoter. The oily products after hydro-treatment were characterized by GC/MS and FTIR. Both MgO-supported catalysts proved to be effective for hydrodeoxygenation of phenol leading to significantly increased yields of reduced hydrocarbon products, such as benzene and cyclohexyl-aromatics, at temperatures higher than 350 °C, while CoMoP/MgO showed superior activity in HDO of phenol. With the presence of CoMoP/MgO for 60 min and at 450 °C, the treatment of phenol yielded a product containing approximately 65 wt.% benzene and >10 wt.% cyclohexyl-compounds. The fresh and spent catalysts were thoroughly characterized by ICP-AES, N₂ isothermal adsorption, XRD, XPS and TGA, and the effects of the phosphorus as the catalyst promoter and MgO as a basic support were discussed.     

Zeolite-encapsulated 2-(o-aminophenyl)benzimidazole complexes: synthesis,characterization and catalytic activity

Cobalt(II), copper(II) and zinc(II) complexes of 2-(o-aminophenyl)benzimidazole (AmPhBzlH) encapsulated in the super cages of zeolite-Y and ZSM-5 have been synthesized and characterized by spectroscopic studies (IR, UV/visible, EPR), elemental analyses, thermal studies and X-ray diffraction patterns. The catalytic activity of encapsulated complexes was investigated for the hydroxylation of phenol using 30% H₂O₂ as an oxidant. Under optimized reaction conditions, the hydroxylation of phenol yielded catechol and hydroquinone as the major products. All catalysts show good selectivity for diphenol products. A maximum conversion of phenol was obtained with [Cu(AmPhBzlH)]-Y as the catalyst. The results showed that conversion of phenol varies in the order [Cu(AmPhBzlH)]-Y > [Cu(AmPhBzlH)]-ZSM-5 > [Zn(AmPhBzlH)]-Y > [Co(AmPhBzlH)]-Y > [Zn(AmPhBzlH)]-ZSM-5 > [Co(AmPhBzlH)]-ZSM-5 after 6 h of reaction time. Test for the recyclability of the reaction was also carried out and the results indicate their recyclability.     

Experimental comparison of biomass chars with other catalysts for tar reduction

In this paper the potential of using biomass char as a catalyst for tar reduction is discussed. Biomass char is compared with other known catalysts used for tar conversion. Model tar compounds, phenol and naphthalene, were used to test char and other catalysts. Tests were carried out in a fixed bed tubular reactor at a temperature range of 700–900 °C under atmospheric pressure and a gas residence time in the empty catalyst bed of 0.3 s. Biomass chars are compared with calcined dolomite, olivine, used fluid catalytic cracking (FCC) catalyst, biomass ash and commercial nickel catalyst. The conversion of naphthalene and phenol over these catalysts was carried out in the atmosphere of CO₂ and steam. At 900 °C, the conversion of phenol was dominated by thermal cracking whereas naphthalene conversion was dominated by catalytic conversion. Biomass chars gave the highest naphthalene conversion among the low cost catalysts used for tar removal. Further, biomass char is produced continuously during the gasification process, while the other catalysts undergo deactivation. A simple first order kinetic model is used to describe the naphthalene conversion with biomass char.     

溶胶-凝胶法制备草酸二甲酯加氢Cu/SiO2催化剂及性能

以正硅酸乙酯为硅源,采用溶胶-凝胶法制备草酸二甲酯加氢合成乙二醇的Cu/SiO₂催化剂,并考察老化时间对Cu/SiO₂催化剂活性与结构的影响。用N2物理吸附、XRD、FT-IR和H₂-TPR等技术对Cu/SiO₂催化剂性能与结构进行表征。结果表明,溶胶-凝胶法制备的Cu/SiO₂催化剂中有层状硅酸铜形成,铜物种均匀分布在载体SiO₂上,易被还原,活性较高。合理的老化时间可抑制SiO₂对催化剂表面活性位的包覆,提高活性。在200 ℃、2.0 MPa、氢酯物质的量比60∶1、草酸二甲酯空速1.0 h^-1和老化时间1.5 h的条件下,草酸二甲酯转化率达99.51%,乙二醇选择性93.60%。
     

Tungstophosphoric acid supported on titania: A solid acid catalyst in benzylation of phenol with benzylalcohol

Benzylation of phenol with benzylalcohol was carried out in liquid phase over tungstophosphoric acid (TPA) supported on titania. The catalysts were prepared with different TPA (10–25%) loading by wet impregnation method, were calcined at 700 °C and characterized by XRD, surface area, FTIR and acidity of the catalysts was measured by temperature programmed desorption of NH₃–TPD, FTIR pyridine adsorption. The catalysts have been represented by a general formula as xPTiO₂₋y (where x = wt%, P = TPA, and y = calcination temperature in °C). The 20PTiO₂ catalyst calcined at various temperatures to know the effect of calcination temperature on activity of the catalyst and the 20PTiO₂-700 showed highest activity in benzylation of phenol with benzylalcohol because it had highest acidity. The effects of temperature, catalyst weight, mole ratio of the reactants on conversion of phenol and product selectivities have been optimized. 20PTiO₂-700 catalyst gave conversion of benzylalcohol (BA) 98% and the selectivity to benzyl phenol (BP) 83.6%, phenyl benzyl ether (PBE) 9.4%, benzylether (BE) 7% at 130 °C, phenol to benzylalcohol molar ratio 2 and in 1 h.     

Efficient Oxidation of 2,3,6-Trimethyl Phenol using Non-Exchanged and H<Superscript>+</Superscript> Exchanged Manganese Oxide Octahedral Molecular Sieves (K-OMS-2 and H–K-OMS-2) as Catalysts

Abstract  

A new and efficient oxidation process of 2,3,6-trimethyl phenol to 2,3,6-trimethyl benzoquinone (TMQ) is reported forthwith using non-exchanged and H⁺-exchanged manganese oxide octahedral molecular sieves (K-OMS-2 and H–K-OMS-2) as benign catalysts. The oxidation reaction is efficiently carried out using TBHP as oxidant and with catalytic amounts of OMS-2 achieving >95% conversion with excellent selectivity (~99%) to TMQ in 30 min.