过氧化氢氧化苯制苯酚的催化剂研究进展

综述了过氧化氢直接氧化苯制苯酚过程中相关催化剂的研究进展,重点介绍了含钛、钒、铁、铜的催化剂,同时给出了各种催化剂所达到的收率和选择性及其工业化前景。     

活性炭对苯酚废水的处理

在静态条件下,研究了活性炭对苯酚废水的处理．比较了不同条件下活性炭对苯酚废水的处理效果,确定了处理废水的振荡时间、活性炭用量、废水pH值、温度、废水中苯酚浓度对处理结果的影响。实验结果表明,活性炭在振荡时间3．5h、用量4．0g、温度30℃、pH值为3．6左右的条件下,对100 mL质量浓度为50mg/L的苯酚废水的吸附效果最好。进行了活性炭处理不同浓度废水的比较实验,结果表明,活性炭处理各种浓度苯酚废水的去除率都很高,适用于对出水要求较高的水处理工艺。     

The Advanced Oxidation Process of Phenol Solution by O3/H2O2 in a Rotating Packed Bed

This article presents experimental investigation on the oxidative treatment of phenol in water by O₃/H₂O₂ in a rotating packed bed (RPB). It was found that the phenol degradation ratio increased with increasing rotation speed, initial pH value of phenol solution, and temperature. The degradation ratio of phenol had a peak value with increasing H₂O₂ concentration. The optimum operating conditions in this study were determined as an H₂O₂ concentration of 6.5 mM and a rotation speed of 1200 rpm. Phenol degradation ratio reached 100% at an initial phenol concentration of 40 mg/L in the O₃/H₂O₂ process.     

Wet air oxidation of phenol using active carbon as catalyst

Catalytic wet air oxidation is a promising alternative for the treatment of phenolic waste water which cannot be treated in conventional sewage plants. Catalytic wet air oxidation of an aqueous phenol solution was conducted in a fixed bed reactor operating in trickle flow regime. Either active carbon or a commercial copper oxide supported over γ-alumina was used as catalyst. The performance of both materials was compared in terms of phenol conversion in 240 h tests. The results showed that the active carbon, without any active metal supported, gives the highest phenol conversion. The supported copper catalyst undergoes a rapid deactivation due to the dissolution of the metal active species in the acidic medium in which the reaction takes place. On the other hand, the active carbon maintains a higher activity throughout the test, although a decrease of the phenol conversion was also observed due to both the loss of active carbon by combustion and the reduction of its surface area. The phenol oxidation was proved to occur through a first order mechanism with respect to phenol. After the ten-day run, the catalytic activity of the active carbon was found to be about eight times higher than that of the commercial catalyst, also showing high selectivity to the production of carbon dioxide.     

金属改性的介孔硅材料FSM-16催化苯酚与H_2O_2合成苯二酚

研究了金属改性的介孔硅材料FSM-16在该反应中的催化性能。其中Fe和Cu改性的FSM-16表现出比较好的性能。在Fe-FSM-16的作用下,苯酚的转化率达到27.8%,对苯二酚和邻苯二酚选择性达到96.4%(邻/对=1.8)。FT-IR和XRD表征证明铜离子进入了FSM-16的骨架,并形成了Si—O—Cu键。     

Catalytic wet peroxide oxidation of phenol with a Fe/active carbon catalyst

A Fe on activated carbon catalyst has been prepared and tested for phenol oxidation with H₂O₂ in aqueous solution at low concentration (100 mg/L). Working at 50 °C, initial pH 3 and a dose of H₂O₂ corresponding to the stoichiometric amount (500 mg/L) complete removal of phenol and a high TOC reduction (around 85%) has been reached. Oxidation of phenol gives rise to highly toxic aromatic intermediates which finally disappear completely evolving to short-chain organic acids. Some of these last showed to be fairly resistant to oxidation being responsible for the residual TOC. In long-term continuous experiments the catalyst undergoes a significant loss of activity in a relatively short term (20–25 h) due to Fe leaching, this being related with the amount of oxalic acid produced. Deactivation may also be caused by active sites blockage due to polymeric deposits on whose formation some evidences were found. Washing with 1N NaOH solution allows to recover the activity although complete restoration was not achieved.     

Enhanced Bactericidal Effect of O3/H2O2 Followed by Cl2

With the appearance of chlorine resistant microorganisms such as Cryptosporidium parvum and Giardia lamblia in drinking water, significant attention has been drawn to the sequential application of multiple disinfectants including ozone, chlorine dioxide, and UV as a primary disinfectant. However, few studies have reported about the inactivation behavior of ozone-based AOP (advanced oxidation process) or its sequential application combined with other disinfectants. This is especially important since ozone itself experiences difficulty in the inactivation of these pathogens, especially at low temperatures: This study investigates the enhanced inactivation of Bacillus subtilis spores by the presence of an OH radical in the O₃/H₂O₂ system and the synergistically enhanced inactivation in the application of the O₃/H₂O₂ system followed by Cl₂. The results suggest that the O₃/H₂O₂ process can be considered as one of the viable alternatives when O₃ alone does not satisfy the disinfection requirement.     

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.     

Hydrogen production from CO2 reforming of methane over high pressure H2O2 modified different semi-cokes

H₂O₂ was used under different temperatures and pressures to activate three kinds of different semi-cokes. FTIR, BET, SEM and Boehm titration were used to analyze properties of the semi-cokes surfaces, finding that catalytic activities of these semi-cokes after modification by high temperature and high pressure H₂O₂ were improved. FTIR shows that the characteristic infrared absorption peak of functional groups on the semi-cokes surface does not change, but the absorption peak intensity of some functional groups is increased. The strength of OH absorption peak of Hongce lignite (HCL) semi-coke at 3444 cm⁻¹, carboxyl CO at 1598 cm⁻¹, aliphatic ether, cyclic ether and other organic functional groups at 1023 cm⁻¹ in the modified Shenmu bituminous(SMB) semi-coke and Jincheng anthracite (JCA) semi-coke are increased significantly. BET finds that the specific surface area and pore volume of three semi-cokes are increased after modification. Boehm titration shows that the basic functional group content in semi-coke is increased after modification, and the net alkali content is increased significantly. Compared with the raw semi-coke, SEM shows that the surface of semi-coke modified with H₂O₂ becomes rough. Modified JCA semi-coke surface pitted with holes, modified HCL and SMB semi-coke surface present porous.     

Preparation of NiCo2O4 Nanosheet Arrays and its High Catalytic Performance for H2O2 Electroreduction

Ni foam supporting‐NiCo₂O₄ nanosheet arrays (NiCo₂O₄/Ni foam) are successfully prepared by electrodeposition of the hydroxide precursor, followed by a thermal treatment in air without any template and surfactant. The morphology of NiCo₂O₄ nanosheet arrays is characterized by scanning electron microscope and transmission electron microscopy. The structure is analyzed using X‐ray diffractometer, X‐ray photoelectron spectroscopy and Fourier transform infrared spectroscopy. The catalytic performance of NiCo₂O₄/Ni foam electrode for H₂O₂ electroreduction in KOH solution is evaluated by means of cycle voltammetry and chronoamperometry, which exhibits an excellent catalytic performance and superior stability for H₂O₂ electroreduction. The reduction current density of H₂O₂ on NiCo₂O₄/Ni foam electrode is 0.378 A cm⁻² at –0.4 V in the solution containing 3.0 mol L⁻¹ KOH + 0.4 mol L⁻¹ H₂O₂, which is much larger than that on other metal oxides reported previously.     

Ozone/H2O2 Performance on the Degradation of Sulfamethoxazole

This work aims to analyze the contribution of H₂O₂ on ozonation of Sulfamethoxazole (SMX). A single ozonation was able to totally remove SMX. TOC and COD depletion rates after a transferred ozone dose of 60 mg/L was related to the formation and decomposition of H₂O₂. An increase on O₃ gas inlet concentration from 10 g/m³ to 20 g/m³ improved COD abatement from 11% to 36%. When the presence of H₂O₂ at the beginning of ozonation was tested, it was verified that COD and TOC degradation were enhanced, attaining maximum values of 76% and 32%, respectively, when compared with 35% and 15% reached in a single ozonation.     

Bactericidal Effectiveness of O3, O3/H2O2 and O3/TiO2 on Clostridium perfringens

The purpose of this research is to evaluate the bactericidal capacity of different Advanced Oxidation Treatments (AOTs) based on ozone: ozone, ozone/hydrogen peroxide and ozone/titanium dioxide on a wild strain of Clostridium perfringens, a fecal bacterial indicator in drinking water. The dose of ozone consumed ranges from 0.6 mg L^?1 min^?1 to 5.13 mg L^?1 min^?1 depending on the process and on the sample. In the treatments combined with O₃, H₂O₂ dose utilized is 0.04 mM and TiO₂ dose, 1 g L^?1. In order to evaluate the influence of natural organic matter and suspension solids over the disinfection rate, treatments are performed with two types of water – natural water from Ebro River (Zaragoza, Spain) and NaCl solution 0.9%. To achieve 4 log units of inactivation, 3.6 mg O₃ L^?1 is necessary in O₃ treatment, 4.25 mg O₃ L^?1 in O₃/TiO₂ system and 2.7 mg O₃ L^?1 in O₃/H₂O₂ after processing the natural water. In NaCl solution, to get the same inactivation, 0.42 mg O₃ L^?1 is necessary in O₃ treatment, 1.15 mg O₃ L^?1 in O₃/TiO₂ system and 0.06 mg O₃ L^?1 in O₃/H₂O₂ process. Even though the three treatments studied have a high bactericidal activity due to the number of surviving bacteria decreases to non-detectable levels, O₃/H₂O₂ is the most effective system for eliminating C. perfringens cells in a lower contact time, followed by O₃ and finally O₃/TiO₂ system.     

A comparison of ethanol and water as the liquid phase in the direct formation of H2O2 from H2 and O2 over a palladium catalyst

Ethanol and water have been compared as the media in which hydrogen peroxide is produced from the reaction of H₂ and O₂ over a palladium catalyst. There are significant differences between the reaction in the two media with respect to the net rate of H₂O₂ formation, the state of the active Pd and the mechanism of the reaction. The reactions were carried out at atmospheric pressure and at 10 °C, with O₂ and H₂ being introduced in a 4/1 ratio through a glass frit. In ethanol, using 50 mg of 5 wt % Pd/SiO₂, 1.8 wt% H₂O₂ was attained in 7 h; whereas, about half this amount was attained in water. In addition, the net formation rate did not remain constant in water. Both systems were 0.17 N in HCl, which facilitated the formation of colloidal Pd in water but not in ethanol. The loss of activity in water is attributed to the instability of the colloid, which has been shown previously to be the active state of Pd. By contrast, these results show that supported Pd is the active state of the metal in the ethanol system. The mechanism for the formation of the nonselective product, water, also is affected by the media in which the reaction is carried out. In ethanol, water is formed by the direct reaction of H₂ and O₂, while in the aqueous phase, water appears to be formed both by the direct pathway and by the reduction of H₂O₂.     

Cr2O3/SiO2催化苯酚与碳酸二乙酯邻位烷基化反应

以Cr(NO₃)₃?9H₂O为前体,采用等体积浸渍法制备了一系列不同Cr₂O₃负载量的Cr₂O₃/SiO₂催化剂;在固定床连续微反装置上,考察了Cr₂O₃/SiO₂催化剂对苯酚与碳酸二乙酯邻位烷基化反应的催化性能;采用XRD、NH₃-TPD、CO₂-TPD和吡啶吸附、红外等手段对催化剂进行了表征。实验结果表明,随着Cr₂O₃负载量的增加,苯酚的转化率和邻乙基苯酚的选择性均逐渐增加;当Cr₂O₃负载量达到7.5%时,苯酚的转化率和邻乙基苯酚的选择性均达到最大值,分别为48%和67%。催化剂的表征结果表明,L酸中心是苯酚邻位烷基化反应的活性中心,苯酚转化率和邻乙基苯酚选择性的变化主要是由催化剂的酸、碱中心数目变化引起的。     

Phosphotungstic acid containing ionic liquid immobilized on magnetic mesoporous silica rod catalyst for the oxidation of dibenzothiophene with H2O2

We have synthesized phosphotungstic acid (PA) containing ionic liquid 1-methyl-3-[(triethoxysilyl) propyl] imidazolium chloride (IL) immobilized on magnetic mesoporous silica rod to catalyze dibenzothiophene (DBT) for producing dibenzothiophene monoxide (DBTO) and dibenzothiophene dioxide (DBTO₂). The effects of reaction time and reaction temperature on the conversion of DBT were studied. It was demonstrated that the catalyst was extremely effective for the reaction and the catalyst could be easily separated from the reaction solution by applying an external magnetic field and recycled several times.     

Engineering the efficient three-dimension hollow cubic carbon from vacuum residuum with enhanced mass transfer ability towards H2O2 production

Constructing efficient carbon material with enhanced mass transfer ability from vacuum residuum (VR) is of prime industrial and scientific significance.Herein,we demonstrated a one-pot synthesis of metal-free and highly symmetric hollow carbon cubes (HCCs) using cost-efficient vacuum residuum (VR) as a C/N/S source.By multi-techniques such as TEM,SEM,Raman,XPS,and XRD,it is found that the CrAB surfactant plays an important role in emulsifying and forming oil-in-water suspension particles.Subsequently,high aromatics contents in VR favor the formation of HCCs shell by graphitization on the surface of NaCl tem-plate.Notably,heavy metals (e.g.,V,Ni) are not enriched in carbon skeleton due to the unique graphiti-zation mechanism.This metal-free HCCs catalyst showed good catalytic stability and high selectivity towards direct and local electrochemical production of hydrogen peroxide (H2O2) through two-electron O2 reduction due to enhanced mass transfer ability.The results provide a novel avenue to synthesize metal-free cubic carbon material from low-cost and plentiful VR,which are essential to the design of more efficient catalysts for O2 reduction to H2O2.     

Enhanced visible light-induced photoelectrocatalytic degradation of phenol by carbon nanotube-doped TiO2 electrodes

We used a modified sol-gel method to prepare titanium dioxide and multi-walled carbon nanotube (CNT) composites that we subsequently deposited onto indium tin oxide (ITO) conductive glass plates. We characterized these CNT-doped TiO₂ (CNT-TiO₂) films using X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and diffuse reflectance UV-vis spectroscopy. The photoelectrocatalytic (PEC) activity of the composites was evaluated through their ability to mediate the degradation of phenol. XRD measurements indicated that the TiO₂ component existed solely in the anatase phase and that the crystallinity of the CNTs was low. XPS indicated that carbon atoms could substitute for both oxygen and titanium atoms in the TiO₂ lattice to form Ti-C and Ti-O-C structures, which were responsible for the extra photoabsorption and PEC activity under illumination with visible light, in addition to those provided by the CNTs and carbonaceous and Ti³⁺ species. An interphase interaction between TiO₂ and the CNTs elevated the photoabsorbance of the composites in the visible light region. A sample of TiO₂ doped with 10% CNTs and calcined at 400 °C exhibited the highest photocurrent and PEC efficiency. We systematically investigated the effects of several parameters of the PEC process, including the applied potential and pH, on the phenol conversion.     

金属改性的FSM-16分子筛催化苯与过氧化氢合成苯酚

研究了金属改性的FSM-16分子筛在催化苯与过氧化氢合成苯酚反应中的应用,其中钒改性的FSM-16分子筛显示了较好的活性和高的选择性。当温度为323 K,反应时间为10 h,n(H2O2)∶n(C6H6)=1∶1,乙酸作溶剂,在催化剂V-FSM-16上得到苯的转化率为5.8%,苯酚的选择性为98.8%。催化剂的红外光谱和XRD的表征表明,钒进入了分子筛的骨架中。     

O3/H2O2 Treatment of Methyl-terf-Butyl Ether in Contaminated Waters: Effect of Background COD on the O3-Dose

The destruction of methyl-tert-butyl ether (MTBE) in contaminated waters by O₃/H₂0₂ process was studied and the influence background COD, alkalinity, and hydrogen peroxide and MTBE concentrations on process treatment efficiency and ozone dosage was investigated. The treatment efficiency was evaluated by an Efficiency Index, which is based on electrical energy requirement for ozone production. It was found that the treatment efficiency decreases linearly with increasing concentrations of MTBE at constant background COD and with background COD at constant MTBE concentration. A simplified kinetic scheme was presented to account for these observations.     

The influence of fuel type on carbon deposition over precious metal containing motorcycle catalysts

The influence of fuel type on carbon deposition over precious metal containing motorcycle catalysts was studied by SEM, EPMA, XPS, TG-DTA and FTIR. The results show that the carbonaceous species are in the form of C_xH_y if the vehicle is fueled with MTBE blended gasoline, whereas the carbonaceous species are C_xH_yO for blended ethanol fuel. The majority of the carbonaceous species are deposited on the PM sites. Further, aromatic rings, alkyl groups and their partial oxidation products are found in the carbonaceous deposit.