Ozonation of 1,3,6‐naphthalenetrisulfonic acid in presence of heavy metals

A study was conducted of the mechanisms by which heavy metals, commonly present in industrial effluents, increase the purification effectiveness of ozone in the removal of organic contaminants of low biodegradability. For this purpose, the ozonation of 1,3,6‐naphthalenetrisulfonic acid (NTS) in the presence of Ni(II), Fe(II), Mn(II), Zn(II), Sr(II), Cr(III), Cd(II), Hg(II), and Cu(II) was examined. The presence of small amounts of Mn(II), Fe(II), Ni(II), Zn(II), and Cr(III) was observed in the system, increasing the degradation rate of the NTS and transforming the dissolved organic matter into CO₂. The mineralization of the organic matter was highly favored, especially in the first minutes of treatment. The results obtained appear to indicate that the activity of the metals in the NTS ozonation process is related to their reduction potential. Thus, metals susceptible to oxidation by ozone are potential promoters of NTS ozonation. The presence of Fe(II) or Mn(II) during NTS ozonation increased its degradation rate by 79% and 72% respectively. Moreover, the reaction kinetics of metal oxidation with ozone controls the increase in the purification effectiveness of these systems. The presence of radical scavengers (tert‐butanol or bicarbonate) in the medium during the promoted ozonation of NTS showed a negative effect on this process, and the NTS degradation rate decreased with an increasing concentration of these inhibitors in the system. These results confirm that the degradation of NTS by ozone in the presence of heavy metals occurs by a radical mechanism. O₃/Zn(II) and O₃/Fe(II) systems were applied to the decontamination of urban waste waters. The presence of Zn(II) or Fe(II) during the ozonation produced a reduction during the first 5 min of treatment of 20% or 44%, respectively, in the concentration of dissolved organic matter present in the system. These results show that ozonation in the presence of heavy metals is a highly promising system for the purification of waste waters and industrial effluents. Copyright © 2004 Society of Chemical Industry     

Advanced oxidation processes for the degradation of p‐hydroxybenzoic acid 1: Photo‐assisted ozonation

The oxidation of p‐hydroxybenzoic acid in aqueous solution by UV radiation and by photo‐assisted ozonation (UV+O₃) has been studied. The effects of temperature (10, 20, 30 and 40 °C), pH (2, 5, 7 and 9) and ozone partial pressure (0.10–0.38 kPa) on the conversion of p‐hydroxybenzoic acid were established. Experimental results indicated that the kinetics for both oxidation processes fit pseudo‐first‐order kinetics well. In the combined process, the overall kinetic rate constant was split into two components: direct oxidation by UV radiation (photolysis) and oxidation by free radicals (mainly OH·) generated in the system. The importance of these two reaction paths for each specific value of ozone partial pressure, temperature and pH was quantified. Lastly, a general expression is proposed for the reaction rate which takes into account the two reaction pathways and is a function of known operating variables. © 2001 Society of Chemical Industry     

微波强化臭氧氧化降解苯酚水溶液

The degradation of phenol in aqueous solution with the combination of microwave and ozone（MW/O₃）was studied with laboratory-scale experiments.Effects of ozone dose,pH value,initial phenol concentration and reaction temperature on the reaction kinetics were investigated.In all cases,the degradation of phenol follows a pseudo-first-order kinetics relation.MW/O₃ combined technology is favorable for enhancing the removal efficiency of phenol,with the enhancement factor of the first-order kinetics constant being around 3.6.Experimental results showed that the synergetic effect of MW/O3 combined technology was obvious and up to 99 % of phenol was removed after 30 min reaction with initial phenol concentration of 100 mg·L^-1,ozone dose of 1.1 mg·min^-1,pH value of 9—11,and reaction temperature of 25℃.     

臭氧与2，4-二氯苯氧乙酸的直接反应动力学

随着现代农业的发展,农药大量研制及施用,农药污染日益严重,对农药污染的控制成为环境研究领域努力探索的课题．2,4-D（2,4-二氯苯氧乙酸）是使用较广的除草剂,具有非挥发性和可溶性,自然降解较慢,施用后易淋溶迁移导致地下水或地表水污染．2,4-D及其代谢产物如2,4-二氯苯酚等不仅有生物毒性,还能导致基因伤害,已对人类健康和自然环境构成了明显威胁．     

Ozonation of 1,3,6-naphthalenetrisulphonic acid catalysed by activated carbon in aqueous phase

This paper presents experimental results of the ozonation of a model aromatic sulphonic compound, 1,3,6-naphthalenetrisulphonic acid (NTS), in the presence of different activated carbons with different physical and chemical surface properties. Carbons used were commercial activated carbons (Ceca AC40, Norit, Merck, Witco, Ceca GAC, Filtrasorb 400, Sorbo) with or without demineralisation pre-treatment. Carbon samples were texturally and chemically characterised using N₂ adsorption isotherms, mercury porosimetry, pH_PZC, selective neutralisation and elemental analysis. Results show that NTS was degraded by ozone at a faster rate in the presence of activated carbon, especially in the case of Sorbo, Ceca GAC and Norit carbons, which display catalytic activity, probably by enhancing ozone decomposition in aqueous phase in highly oxidative species. These catalytic properties seem to be favoured by both the basicity of the carbon surface and the higher macropore volume. Dissolved total organic carbon from the NTS degradation compounds was removed in the presence of activated carbon through both the catalytic activity of activated carbon to mineralise organic matter and the adsorption of these organic compounds on activated carbon.     

Kinetics and mechanism of the reaction between ozone and hydrogen peroxide in aqueous solutions

A kinetic model has been developed, taking into account both decomposition of ozone molecules and interactions between ozone and hydrogen peroxide for formation of hydroxyl radical and subsequent reactions. Experiments were carried out at 25°C in the pH range of 3 to 13, indicating that the depletion rate of ozone increases with the concentrations of ozone, hydrogen peroxide and hydroxyl ion, as predicted by the kinetic model. Adverse scavenging reactions, however, also play significant roles at sufficient concentration ratios of hydrogen peroxide to ozone and high concentrations of hydroxyl ion in reducing the depletion rate. Results of this research suggest, that it is most desirable to conduct the peroxone oxidation for pollutant destruction by the hydroxyl radical reaction in alkaline solutions of pH below 11, while maintaining about the same concentration of ozone and hydrogen peroxide.     

Advanced oxidation processes for the degradation of p‐hydroxybenzoic acid 2: Photo‐assisted Fenton oxidation

Oxidation of p‐hydroxybenzoic acid in aqueous solution by the photo‐assisted Fenton reaction (Fe²⁺ + H₂O₂ + UV) has been studied. The effects of ferrous ion concentration (0.05, 0.14 and 0.29 mmol dm^?3), temperature (10, 20, 30 and 40 °C), and initial hydrogen peroxide concentration (0.7, 1.4, 2.2 and 2.9 mmol dm^?3) on the p‐hydroxybenzoic acid conversion were established. Experimental results indicate that the kinetics of this oxidation process fits pseudo‐first‐order kinetics well. The overall kinetic rate constant was split into two components: direct oxidation by UV radiation (photolysis) and oxidation by free radicals (mainly OH·) generated in the system. The importance of these two reaction paths for each specific value of ferrous ion concentration, temperature and initial hydrogen peroxide concentration was evaluated. A semi‐empirical expression is proposed for the overall reaction rate which takes into account both oxidation pathways and is a function of operating variables. © 2001 Society of Chemical Industry     

The oxidation of valeric acid in aqueous solution

The liquid phase oxidation of an aqueous solution of a lower fatty acid, valeric (pentanoic) acid, has been studied at high temperatures (240?325°C) and pressures (10.3-10.4 MPa) in a batch autoclave reactor. The objective of the study was to develop a mechanistic understanding of the wet oxidation of industrial wastewaters contaminated with vegetable oils. Valeric acid was chosen as the prototype molecule. High performance liquid chromatography (HPLC) has been used to identify the liquid products and estimate their concentrations as a function of the extent of oxidation. Moreover the technique of GC-MS has also been used to obtain information on specific intermediate oxidation products that could not be identified by HPLC. The gaseous products of the reaction have been also identified and quantified. A detailed reaction mechanism is proposed based on free radical reactions.     

活性炭强化臭氧氧化丙烯酸及酯废水的研究

生化后的丙烯酸及酯废水COD为550 mg/L,需进行深度处理才能达标排放。研究了活性炭强化的臭氧氧化工艺对该废水的处理效能,考察了废水碱度、活性炭装填高度、臭氧浓度和废水柱外循环流量对COD去除率的影响。实验结果表明,在最佳条件下反应2 h,废水COD可降至35 mg/L,达到《污水综合排放标准》(GB 8978—1996)中的一级标准要求。     

臭氧处理柠檬酸废水的实验研究

通过实验研究臭氧氧化法处理柠檬酸废水,探讨了废水的处理时间、臭氧的消耗量对CODCr和色度去除的影响,得到了最佳工艺参数.实验结果表明,当臭氧消耗量在30 mg/L,反应时间为5min时,废水的CODCr去除率为18.4%,色度去除率达73.3%.臭氧具有优良的脱色能力,同时提高了废水的可生化性,为进一步的生化处理提供了保证.     

Plasma-assisted oxidation of benzoic acid

Plasma-assisted oxidation of organic compounds is one of the developing technologies for wastewater treatment. Plasmas effectively accelerate degradation processes due to plasma generated reactive species and ultra-violet radiation. Oxidation of BA in aqueous solutions by the atmospheric pressure glow discharge and underwater diaphragm discharge was studied and monitored by fluorescence and spectrophotometric methods. Discharge type and solution pH affect the formation rates of mono- and dihydroxybenzoic acids. Dihydroxyl derivatives were formed only by glow discharge action. The yields of hydroxyl radical were estimated on the kinetics data for the hydroxylation of benzoic acid. The steps of the hydroxylation processes and further oxidation were described.     

臭氧催化氧化深度处理焦化废水的试验研究

针对生化后焦化废水COD_(cr)无法达标的问题,通过中试研究了臭氧催化氧化技术深度处理焦化废水的效果,考察了臭氧投加量、反应时间、pH值、催化剂对COD_(cr)去除率的影响,确定了最佳运行参数。结果表明:连续运行68 d,当进水CODcr为140~200 mg/L,反应时间为1.5 h,臭氧投加量为80mg/(L·h)时,COD_(cr)平均去除率大于60%,出水满足《炼焦化学工业污染物排放标准》(GB 16171—2012)的要求。运行费用仅1.30元/m~3,是强制混凝沉淀技术的1/4~1/2。工艺运行稳定、可靠,催化剂使用前后,比表面积、孔结构等均未发生明显变化,催化剂未发生失活现象。     

Electric‐oxidation kinetics of molybdenite concentrate in acidic NaCl solution

The electric‐oxidation kinetics of molybdenite concentrate in NaCl electrolyte was investigated in this study. The effects of liquid‐to‐solid ratio, stirring speed, and concentration of NaCl on the dissolution rate were determined. It was found that the dissolution rate increases with increase in liquid‐to‐solid ratio, stirring speed, and concentration of NaCl. A shrinking particle model is presented to describe the dissolution and to analyse the data. The apparent activation energy of this dissolution process was found to be 8.2 kJ/mol; it was established that the leaching process is mainly controlled by diffusion, and the kinetics formula of this research system can be expressed as: .     

Kinetics of homogeneous 5‐hydroxymethylfurfural oxidation to 2,5‐furandicarboxylic acid with Co/Mn/Br catalyst

2,5‐furandicarboxylic acid (FDCA) is a potential non‐phthalate based bio‐renewable substitute for terephthalic acid‐based plastics. Herein, we present an investigation of the oxidation rate of 5‐hydroxymethylfurfural (HMF) to FDCA in acetic acid medium using Co/Mn/Br catalyst. Transient concentration profiles of the reactant (HMF), intermediates [2,5‐diformylfuran (DFF), 5‐formyl‐2‐furancarboxylic acid (FFCA)], and the desired product (FDCA) were obtained for this relatively fast reaction in a stirred semi‐batch reactor using rapid in‐line sampling. Comparison of the effective rate constants for the series oxidation steps with predicted gas–liquid mass transfer coefficients reveals that except for the FFCA → FDCA step, the first two oxidation steps are subject to gas–liquid mass transfer limitations even at high stirrer speeds. Novel reactor configurations, such as a reactor in which the reaction mixture is dispersed as fine droplets into a gas phase containing oxygen, are required to overcome oxygen starvation in the liquid phase and further intensify FDCA production. © 2016 American Institute of Chemical Engineers AIChE J, 63: 162–171, 2017     

Kinetics of azo‐initiated 1‐vinyl‐2‐pyrrolidone polymerizations at low conversions in aqueous media

The free‐radical polymerization behavior of 1‐vinyl,2‐pyrrolidone (NVP) was studied at low conversions, using capillary dilatometry. The aqueous media were kept at neutral pH and the studies were conducted isothermally, at 40 or 45°C. The azo‐type initiators used were 4,4′‐azobis‐4‐cyanopentanoic acid (ACPA), 2,2′‐azobisisobutyronitrile (AZBN), and 2,2′‐azobis[2‐(2‐imidazolin‐2‐yl)propane dihydrochloride] (ABDH). The monomer concentration and initiator concentration ranges were 1.17–2.34 mol L⁻¹ and 1–8 mmol L⁻¹, respectively. The rates of polymerization (R_p) and orders of reaction with respect to NVP and the initiator were evaluated and the kinetic equations were found to be R_p ∝ [NVP] [ACPA]^1.2; R_p ∝ [NVP] [AZBN]^1.1; and R_p ∝ [NVP]^2.2 [ABDH]^1.1. The polymers obtained were characterized by their viscosity numbers and correlation of the viscosity average molecular weights made with the type and amount of the azo initiator. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 239–246, 2000     

Role of Metal Oxide Nanomaterials on Thermal Stability of 1,3,6‐Trinitrocarbazole

The thermal behaviour of 1,3,6‐trinitrocarbazole (TENT) in the form of pure and nanocomposite explosives was examined by differential scanning calorimetry (DSC) and thermogravimetry (TG). Thermoanalytical data revealed that thermal decomposition of pure TENT is significantly different from the investigated nanocomposites. The results confirmed that pure TENT decomposed completely in a single stage in the temperature range 400–450 °C. Though, addition of the nanoparticles to the TENT powder leads to higher thermal stability in comparison with the pure TENT. Decomposition kinetics of the pure TENT and the nanocomposites were studied by non‐isothermal DSC at diverse heating rates. The resulted thermokinetic and thermodynamic parameters for the thermal decomposition of pure TENT were compared with the nanocomposites.     

Novel modification of polybut‐1‐ene using auto‐oxidation controlled by addition of limonene monomer

Free radical graft polymerization has been used as a modification method to incorporate functional groups into polyolefins using a melt‐mixing process. The presence of oxygen simultaneously brings about auto‐oxidation during the polymerization. Although functional groups such as ketones are easily incorporated into polyolefin chains by auto‐oxidation, the method is rarely employed because of the difficulty of handling. In the study reported here, a novel modification of polybut‐1‐ene (PB) was performed using auto‐oxidation controlled by the addition of limonene monomer. The modified PB samples were prepared using 2,2′‐azobis(2‐methylpropionitrile), benzyl peroxide, tert‐butyl peroxide (TBPO) and Nd₂O₃/dicumyl peroxide (DCP) radical initiators in air. It was found that excessive auto‐oxidation was suppressed by the presence of the limonene, and that the greatest numbers of grafted groups were contained in the modified PB samples prepared using TBPO and Nd₂O₃/DCP. The samples obtained showed slower crystallization behavior and slower crystal–crystal transformation rates, respectively. In addition, the modified PB sample prepared using Nd₂O₃/DCP showed less ductile behavior than that prepared using TBPO because of a much slower transformation rate. Copyright © 2009 Society of Chemical Industry     

3, 4‐Dihydroxymandelic acid amides of alkylamines as antioxidants for lipids

The antioxidative and radical scavenging activity of the 3, 4‐dihydroxymandelic acid (DHMA) amides of hexylamine, 2‐ethylhexylamine, octylamine, and cyclohexylamine was determined by several physicochemical test systems. The amides were synthesized by protecting group‐free coupling of in situ prepared N‐hydroxysuccinimidylester of DHMA and the amines. The radical scavenging activity was determined using the DPPH (2, 2‐diphenyl‐1‐picrylhydrazyl) method and by quenching superoxide anions generated using a horse radish peroxidase/H₂O₂ system. In the DPPH assay, all amides show higher radical scavenging activity (EC₅₀ 0.09‐0.12 mol/mol_DPPH) compared to the standard antioxidants ascorbic acid (EC₅₀ 0.27 mol/mol_DPPH) and tocopherol (EC₅₀ 0.25 mol/mol_DPPH). The amides are also more potent superoxide radical scavengers (IC₅₀ < 600 nm) than standard ascorbic acid (IC₅₀ 700 nm). Activity against lipid peroxidation was determined by accelerated autoxidation of highly unsaturated oils and squalene using the Rancimat. Again, the antioxidative potentials of the DHMA amides against lipid oxidation as determined by the Rancimat, are at least equal or higher compared to the standard lipid antioxidants tocopherol, BHT, BHA, and ascorbylpalmitate (concentration in soybean oil 0.05%, all other oils 0.025%, squalene 0.005%). In squalene, an equi‐amount mixture of DHMA octylamide and α‐tocopherol shows a synergistic effect. Last but not least, the amides are able to protect an emulsion of linoleic acid/β‐carotene against oxidation initiated by N, N‐azodiisobutyramidine dihydrochloride (IC₅₀ 0.19‐0.77 mmol/l, ascorbic acid > 0.9, tocopherol 0.08). The DHMA octylamide in combination with ascorbic acid shows a synergistic antioxidative effect in the emulsion model. In conclusion, the new alkylamides of DHMA are easy to synthesize, potent radical scavengers and protect lipids, in particular the highly unsaturated, both in bulk and in emulsions against autoxidation.     

Photocatalytic degradation of 3‐nitrobenzenesulfonic acid in aqueous TiO2 suspensions

The photocatalytic degradation of 3‐nitrobenzenesulfonic acid in the presence of solar radiation and artificial UV radiation with suspended TiO₂ was studied in a batch and continuous annular reactor, respectively. The effects of catalyst loading, pH, presence of anions and cations and initial concentration on the rate of photocatalytic degradation were investigated. Concentration–time data were correlated with the rate equation d[C_t=0]/dt = k_rK[C_t=0]/(1 + K[C_t=0]). Studies were carried out to compare the photolytic, photochemical and photocatalytic methods of degradation. Copyright © 2005 Society of Chemical Industry