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Sample records for alkaline wet oxidation

  1. Combined wet oxidation and alkaline hydrolysis of polyvinylchloride

    DEFF Research Database (Denmark)

    Sørensen, E.; Bjerre, A.B.

    1992-01-01

    In view of the widespread aversion to burning polyvinylchloride (PVC) together with municipal waste, we have attempted an alternative approach to its decomposition. This paper describes a combined wet oxidation/alkaline hydrolysis yielding water soluble, biodegradable products. Experiments were...... carried out at temperatures from 180-260 degree C and reaction times of 8-24 min. The chloride liberated provides information on the rate constants. Considering the measured Cl- and Chemical Oxygen Demand (COD) values, we find hydrolysis and oxidation processes to be interdependent. The main products...

  2. Characterization of degradation products from alkaline wet oxidation of wheat straw

    DEFF Research Database (Denmark)

    Klinke, H.B.; Ahring, B.K.; Schmidt, A.S.

    2002-01-01

    Alkaline wet oxidation pre-treatment (water, sodium carbonate, oxygen, high temperature and pressure) of wheat straw was performed as a 2(4-1) fractional factorial design with the process parameters: temperature, reaction time, sodium carbonate and oxygen. Alkaline wet oxidation was an efficient...... pre-treatment of wheat straw that resulted in solid fractions with high cellulose recovery (96%) and high enzymatic convertibility to glucose (67%). Carbonate and temperature were the most important factors for fractionation of wheat straw by wet oxidation. Optimal conditions were 10 min at 195...... the solid fraction (62%) did not provide a corresponding increase in the phenol monomer content but was correlated to high carboxylic acid concentrations. The degradation products in the hemicellulose fractions co-varied with the pre-treatment conditions in the principal component analysis according...

  3. Comparison of the chemical properties of wheat straw and beech fibers following alkaline wet oxidation and laccase treatments

    DEFF Research Database (Denmark)

    Schmidt, A. S.; Mallon, S.; Thomsen, Anne Belinda;

    2002-01-01

    Wheat straw (Triticum aestivum) and beech (Fagus sylvatica), were used to evaluate the effects of two pre-treatment processes (alkaline wet oxidation and enzyme treatment with laccase) on lignocellulosic materials for applications in particleboards and fiberboards. Wheat straw and beech fibers...... reacted differently in the two processes. The chemical composition changed little following enzyme treatment. After alkaline wet oxidation, fibers enriched in cellulose were obtained. With both materials, almost all hemicellulose (80%) together with a large portion of the lignin were solubilised...... by alkaline wet oxidation, but essentially all cellulose remained in the solid fraction. Following enzyme treatment most material remained as a solid. For wheat straw, reaction with acetic anhydride indicated that both treatments resulted in more hydroxyl groups being accessible for reaction. The enzyme...

  4. Alkaline peroxide assisted wet air oxidation pretreatment approach to enhance enzymatic convertibility of rice husk.

    Science.gov (United States)

    Banerjee, Saumita; Sen, Ramkrishna; Mudliar, Sandeep; Pandey, R A; Chakrabarti, Tapan; Satpute, Dewanand

    2011-01-01

    Pretreatment of rice husk by alkaline peroxide assisted wet air oxidation (APAWAO) approach was investigated with the aim to enhance the enzymatic convertibility of cellulose in pretreated rice husk. Rice husk was presoaked overnight in 1% (w/v) H(2)O(2) solution (pH adjusted to 11.5 using NaOH) (equivalent to 16.67 g H(2)O(2) and 3.63 g NaOH per 100 g dry, untreated rice husk) at room temperature, followed by wet air oxidation (WAO). APAWAO pretreatment resulted in solubilization of 67 wt % of hemicellulose and 88 wt % of lignin initially present in raw rice husk. Some amount of oligomeric glucose (˜8.3 g/L) was also observed in the APAWAO liquid fraction. APAWAO pretreatment resulted in 13-fold increase in the amount of glucose that could be obtained from otherwise untreated rice husk. Up to 86 wt % of cellulose in the pretreated rice husk (solid fraction) could be converted into glucose within 24 hours, yielding over 21 g glucose per 100 g original rice husk. Scanning electron microscopy was performed to visualize changes in biomass structure following the APAWAO pretreatment. Enzymatic cellulose convertibility of the pretreated slurry at high dry matter loadings was also investigated.

  5. Catalytic wet oxidation of o-chlorophenol at mild temperatures under alkaline conditions.

    Science.gov (United States)

    Kojima, Yoshihiro; Fukuta, Tadashi; Yamada, Takehisa; Onyango, Maurice S; Bernardo, Eileen C; Matsuda, Hitoki; Yagishita, Kohichi

    2005-01-01

    Wet oxidation of a 100 ppm aqueous solution of o-chlorophenol (o-CP) was performed in a lab-scale batch reactor using 3% Ru/TiO(2) catalyst at 373 and 413 K, and a partial oxygen pressure of 0.1 MPa. The experiments were conducted by varying the initial pH values of o-CP solution from pH 6.3 to 9.8 and 11.8. From the results, it was revealed that the catalytic decomposition of o-CP occurred most effectively at 413 K and at the initial pH of 9.8. Complete decomposition and dechlorination of o-CP were almost achieved within 1h, and about 85% of TOC was removed in 3.0 h. On the other hand, the catalytic wet oxidation of o-CP at a higher pH value of 11.8 was not effective in the removal of TOC. The incomplete removal of TOC at the initial pH of 11.8 is likely attributed to a low pK(a) of carboxylic acids formed during the wet oxidation of o-CP.

  6. Pretreatment of wheat straw using combined wet oxidation and alkaline hydrolysis resulting in convertible cellulose and hemicellulose

    DEFF Research Database (Denmark)

    Bjerre, A.B.; Bjerring Olesen, A.; Fernqvist, T.

    1996-01-01

    addition readily oxidizes lignin from wheat straw facilitating the polysaccharides for enzymatic hy drolysis. By using a specially constructed autoclave system, the wet oxidation process was optimized with respect to both reaction time and temperature. The best conditions (20 g/L straw, 170 degrees C, 5...

  7. Wet oxidation of quinoline

    DEFF Research Database (Denmark)

    Thomsen, A.B.; Kilen, H.H.

    1998-01-01

    The influence of oxygen pressure (0.4 and 2 MPa). reaction time (30 and 60 min) and temperature (260 and 280 degrees C) on the wet oxidation of quinoline has been studied. The dominant parameters for the decomposition of quinoline were oxygen pressure and reaction temperature. whereas the reaction...... time was less important within the range studied. Nitrifying bacteria were used to measure the inhibition from wet oxidative-treated samples to study the effect of the (wet oxidation) reaction conditions. Wet oxidation made quinoline more toxic to Nitrosomonas. This was observed for Nitrobacter as well....... The combined wet oxidation and biological treatment of reaction products resulted in 91% oxidation of the parent compound to CO2 and water. Following combined wet oxidation and biological treatment the sample showed low toxicity towards Nitrosomonas and no toxicity towards Nitrobacter. (C) 1998 Elsevier...

  8. Inhibiting Wet Oxidation of Ammonia

    Science.gov (United States)

    Onisko, D. B. L.

    1985-01-01

    Simple modification of wet-oxidation process for treating organicwaste reduces loss of fixed nitrogen, potentially valuable byproduct of process. Addition of sufficient sulfuric acid to maintain reaction pH below 3 greatly reduces oxidation of ammonia to free nitrogen. No equipment modification required.

  9. Wet oxidation of a spacecraft model waste

    Science.gov (United States)

    Johnson, C. C.; Wydeven, T.

    1985-01-01

    Wet oxidation was used to oxidize a spacecraft model waste under different oxidation conditions. The variables studied were pressure, temperature, duration of oxidation, and the use of one homogeneous and three heterogeneous catalysts. Emphasis is placed on the final oxidation state of carbon and nitrogen since these are the two major components of the spacecraft model waste and two important plant nutrients.

  10. Optimization of wet oxidation pretreatment of wheat straw

    DEFF Research Database (Denmark)

    Schmidt, A.S.; Thomsen, A.B.

    1998-01-01

    The wet oxidation process (water; oxygen and elevated temperature) was investigated under alkaline conditions for fractionation of hemicellulose, cellulose, and lignin from wheat straw. At higher temperature and longer reaction time, a purified cellulose fraction (69% w/w) was produced with high ...... for by saccharides and carboxylic acids; hence, a significant proportion of reaction products remained unidentified. (C) 1998 Elsevier Science Ltd. All rights reserved....

  11. Catalytic wet oxidation of black liquor

    OpenAIRE

    Viader Riera, Gerard

    2012-01-01

    The major aspects of wet air oxidation and catalytic wet air oxidation have been reviewed in this work paying special attention to the reaction mechanisms, kinetics and the industrial process. In the experimental section a set of heterogeneous catalysts have been tested in the wet oxidation of non-wood black liquor. The oxidation runs were performed batchwise in a laboratory-scale mechanically stirred slurry reactor for 1 h at a temperature of 170°C and total pressure of 12 bar. Pure oxygen w...

  12. Advanced methods for the treatment of organic aqueous wastes: wet air oxidation and wet peroxide oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Debellefontaine, Hubert; Chakchouk, Mehrez; Foussard, Jean Noel [Institut National des Sciences Appliquees (INSA), 31 - Toulouse (France). Dept. de Genie des Procedes Industriels; Tissot, Daniel; Striolo, Phillipe [IDE Environnement S.A., Toulouse (France)

    1993-12-31

    There is a growing concern about the problems of wastes elimination. Various oxidation techniques are suited for elimination of organic aqueous wastes, however, because of the environmental drawbacks of incineration, liquid phase oxidation should be preferred. `Wet Air Oxidation` and `Wet Peroxide Oxidation`are alternative processes which are discussed in this paper. 17 refs., 13 figs., 4 tabs.

  13. Oxidation catalysts on alkaline earth supports

    Energy Technology Data Exchange (ETDEWEB)

    Mohajeri, Nahid

    2017-03-21

    An oxidation catalyst includes a support including particles of an alkaline earth salt, and first particles including a palladium compound on the support. The oxidation catalyst can also include precious metal group (PMG) metal particles in addition to the first particles intermixed together on the support. A gas permeable polymer that provides a continuous phase can completely encapsulate the particles and the support. The oxidation catalyst may be used as a gas sensor, where the first particles are chemochromic particles.

  14. COMPARISON BETWEEN WET OXIDATION AND STEAM EXPLOSION AS PRETREATMENT METHODS FOR ENZYMATIC HYDROLYSIS OF SUGARCANE BAGASSE

    OpenAIRE

    Carlos Martín; Marcelo Marcet; Anne Belinda Thomsen

    2008-01-01

    Alkaline wet oxidation and steam explosion pretreatments of sugarcane bagasse were compared with regard to biomass fractionation, formation of by-products, and enzymatic convertibility of the pretreated material. Wet oxidation led to the solubilisation of 82% of xylan and 50% of lignin, and to a two-fold increase of cellulose content in the pretreated solids, while steam explosion solubilised only 60% of xylan and 35% of lignin and increased cellulose content in the solid material by one thir...

  15. Wet oxidation of salicylic acid solutions.

    Science.gov (United States)

    Collado, Sergio; Garrido, Laura; Laca, Adriana; Diaz, Mario

    2010-11-15

    Salicylic acid is a frequent pollutant in several industrial wastewaters. Uncatalyzed wet air oxidation, which is a promising technique for the treatment of phenolic effluents, has not been analyzed yet for the removal of salicylic acid. The effect of different conditions of pH (1.3-12.3), pressure (1.0-4.1 MPa), temperature (413-443 K), and initial concentrations (1.45-14.50 mM) on the wet oxidation of salicylate/salicylic acid solutions have here been investigated. The pH value of the reaction media was found to be a key parameter for the rate of the oxidation process with an optimum at pH 3.1, when the concentrations of salicylic acid and salicylate were similar. The oxidation reaction followed pseudofirst-order kinetics with respect to salicylic acid and 0.82 order with respect to dissolved oxygen. Additionally, the evolution of the color during the wet oxidation was analyzed and discussed in relation with the formation of intermediate compounds. Then, a reaction pathway for the noncatalytic wet oxidation of the salicylic acid was proposed.

  16. Progress of catalytic wet air oxidation technology

    Directory of Open Access Journals (Sweden)

    Guolin Jing

    2016-11-01

    Full Text Available Catalytic wet air oxidation (CWAO is one of the most economical and environmental-friendly advanced oxidation process for high strength, toxic, hazardous and non-biodegradable contaminants under milder conditions, which is developed on the basic of wet air oxidation. Various heterogeneous catalysts including noble metals and metal oxides have been extensively studied to enhance the efficiency of CWAO. The advances in the research on wastewater treatment by CWAO process are summarized in aspects of reaction mechanism investigation, reaction kinetics study and catalyst development. It is pointed out that the preparation of active and stable catalysts, the investigation on reaction mechanisms and the study on reaction kinetics models are very important for the promotion of CWAO application.

  17. Comparison between wet oxidation and steam explosion as pretreatment methods for enzymatic hydrolysis of sugarcane bagasse

    DEFF Research Database (Denmark)

    Medina, Carlos Martín; Marcet, M.; Thomsen, Anne Belinda

    2008-01-01

    Alkaline wet oxidation and steam explosion pretreatments of sugarcane bagasse were compared with regard to biomass fractionation, formation of by-products, and enzymatic convertibility of the pretreated material. Wet oxidation led to the solubilisation of 82% of xylan and 50% of lignin......, and to a two-fold increase of cellulose content in the pretreated solids, while steam explosion solubilised only 60% of xylan and 35% of lignin and increased cellulose content in the solid material by one third. Wet oxidation formed more aliphatic acids and phenolics, and less furan aldehydes in the liquid...... fraction than steam explosion did. A better enzymatic convertibility of cellulose was achieved for the wet-oxidised material (57.4 %) than for the steam-exploded material (48.9 %). Cellulose convertibility was lower for the whole slurry than for the washed solids in both pretreatments, but more...

  18. Dissolution of Uranium Oxides Under Alkaline Oxidizing Conditions

    Energy Technology Data Exchange (ETDEWEB)

    Smith, S.C.; Peper, S.M.; Douglas, M.; Ziegelgruber, K.L. [PNNL, PO Box 999, MS P8-08, Richland, WA 99352 (United States)

    2009-06-15

    Understanding the dissolution of uranium oxides is critical for designing and optimizing next-generation spent nuclear fuel (SNF) reprocessing methods. Bench scale experiments were conducted to determine the optimal dissolution parameters for size-fractionated aliquots of UO{sub 2}, UO{sub 3}, and U{sub 3}O{sub 8} powders in aqueous peroxide-carbonate solutions. Experimental parameters included; peroxide and carbonate concentrations, and temperature. Solution pH was varied with ammonium hydroxide. We will present details of the dissolution experiment set-up as well as information on the kinetics of dissolution of the various U-oxides as a function of the above variables. We will also discuss efforts to characterize solution and solid-state complexes in peroxide-carbonate systems. This study will demonstrate the applicability of peroxide-containing alkaline solutions for effectively dissolving SNF, and will enhance the current level of understanding of actinide behavior in peroxide-containing alkaline solutions. (authors)

  19. Wet peroxide oxidation and catalytic wet oxidation of stripped sour water produced during oil shale refining.

    Science.gov (United States)

    Prasad, Jaidev; Tardio, James; Jani, Harit; Bhargava, Suresh K; Akolekar, Deepak B; Grocott, Stephen C

    2007-07-31

    Catalytic wet oxidation (CWO) and wet peroxide oxidation (WPO) of stripped sour water (SSW) from an oil shale refinery was investigated. Greater than 70% total organic carbon (TOC) removal from SSW was achieved using Cu(NO(3))(2) catalysed WO under the following conditions using a glass lined reaction vessel: 200 degrees C, pO(2)=0.5MPa, 3h, [Cu(NO(3))(2)]=67mmol/L. Significant TOC removal ( approximately 31%) also occurred in the system without added oxygen. It is proposed that this is predominantly due to copper catalysed oxidative decarboxylation of organics in SSW based on observed changes in copper oxidation state. Greater than 80% TOC removal was achieved using WPO under the following conditions: 150 degrees C, t=1.5h, [H(2)O(2)]=64g/L. Significantly more TOC could be removed from SSW by adding H(2)O(2) in small doses as opposed to adding the same total amount in one single dose. It was concluded that WPO was a far more effective process for removing odorous compounds from SSW.

  20. [Research on synergy of combining electrochemical oxidation and catalytic wet oxidation].

    Science.gov (United States)

    Wang, Hua; Li, Guang-Ming; Zhang, Fang; Huang, Ju-Wen

    2009-07-15

    A new catalytic wet oxidation fixed-bed reactor combined with three-dimensional electric-field was developed to investigate catalytic wet oxidation, electrochemical oxidation and electroassisted catalytic wet oxidation of the solution containing phenol in the presence of a catalyst Mn-Sn-Sb-3/gamma-Al2O3. Good electroassisted catalytic wet oxidation efficiency was obtained in the setup for the combination system even at mild conditions (T = 130 degrees C, po2 = 1.0 MPa) that the phenol conversion and TOC reduction were up to 94.0% and 88.4% after 27 min treatment, respectively. The result also shows that the rate constants of electroassisted catalytic wet oxidation are much higher than that of not only both catalytic wet oxidation and electrochemical oxidation process alone but also additive efficiencies of catalytic wet oxidation and electrochemical oxidation processes, which indicates an apparent synergetic effect between CWO and ECO processes.

  1. Potential inhibitors from wet oxidation of wheat straw and their effect on ethanol production of Saccharomyces cerevisiae: Wet oxidation and fermentation by yeast

    DEFF Research Database (Denmark)

    Klinke, Helene Bendstrup; Olsson, Lisbeth; Thomsen, A.B.;

    2003-01-01

    Alkaline wet oxidation (WO) (using water, 6.5 g/L sodium carbonate and 12 bar oxygen at 195degreesC) was used as pretreatment method for wheat straw (60 g/L), resulting in a hydrolysate and a cellulosic solid fraction. The hydrolysate consisted of soluble hemicellulose (8 g/L), low......-molecular-weight carboxylic acids (3.9 g/L), phenols (0.27 g/L = 1.7 mM) and 2-furoic acid (0.007 g/L). The wet oxidized wheat straw hydrolysate caused no inhibition of ethanol production by Saccharomyces cerevisiae ATCC 96581. Nine phenols and 2-furoic acid, identified to be present in the hydrolysate, were each tested...

  2. COMPARISON BETWEEN WET OXIDATION AND STEAM EXPLOSION AS PRETREATMENT METHODS FOR ENZYMATIC HYDROLYSIS OF SUGARCANE BAGASSE

    Directory of Open Access Journals (Sweden)

    Carlos Martín

    2008-08-01

    Full Text Available Alkaline wet oxidation and steam explosion pretreatments of sugarcane bagasse were compared with regard to biomass fractionation, formation of by-products, and enzymatic convertibility of the pretreated material. Wet oxidation led to the solubilisation of 82% of xylan and 50% of lignin, and to a two-fold increase of cellulose content in the pretreated solids, while steam explosion solubilised only 60% of xylan and 35% of lignin and increased cellulose content in the solid material by one third. Wet oxidation formed more aliphatic acids and phenolics, and less furan aldehydes in the liquid fraction than steam explosion did. A better enzymatic convertibility of cellulose was achieved for the wet-oxidised material (57.4 % than for the steam-exploded material (48.9 %. Cellulose convertibility was lower for the whole slurry than for the washed solids in both pretreatments, but more significantly in steam explosion. This investigation demonstrates the potential of wet oxidation as a promising pretreatment method for enzyme-based bagasse-to-ethanol processes.

  3. Wet-air oxidation cleans up black wastewater

    Energy Technology Data Exchange (ETDEWEB)

    1993-09-01

    Sterling Organics produces the analgesic paracetamol (acetaminophen) at its Dudley, England, plant. The wastewater from the batch process contains intermediates such as para-aminophenol (PAP) and byproducts such as thiosulfates, sulfites and sulfides. To stay ahead of increasingly strict environmental legislation, Sterling Organics installed a wet-air oxidation system at the Dudley facility in August 1992. The system is made by Zimpro Environmental Inc. (Rothschild, Wis.). Zimpro's wet-air oxidation system finds a way around the limitations of purely chemical or physical processes. In the process, compressed air at elevated temperature and pressure oxidizes the process intermediates and byproducts and removes the color from the wastewater.

  4. Simulation of wet oxidation of silicon based on the interfacial silicon emission model and comparison with dry oxidation

    OpenAIRE

    Uematsu, Masashi; Kageshima, Hiroyuki; Shiraishi, Kenji

    2001-01-01

    Silicon oxidation in wet ambients is simulated based on the interfacial silicon emission model and is compared with dry oxidation in terms of the silicon-atom emission. The silicon emission model enables the simulation of wet oxidation to be done using the oxidant self-diffusivity in the oxide with a single activation energy. The amount of silicon emission from the interface during wet oxidation is smaller than that during dry oxidation. The small emission rate for wet oxidation is responsibl...

  5. Ethanol production from wet oxidized corn straw by simultaneous saccharification and fermentation

    DEFF Research Database (Denmark)

    Zhang, Q.; Yin, Y.; Thygesen, Anders

    2010-01-01

    In order to find out the appropriate process for ethanol production from corn straw, alkaline wet-oxidation pretreatment (195°C, 15 min, Na2CO3 2 g/L, O2 1200 kPa) and simultaneous saccharification and fermentation (SSF) were adopted to produce ethanol. The results showed that 90% of cellulose...... was obtained. The estimated total ethanol production was 262.7 kg/t raw material by assuming the consumption of both C-6 and C-5. No obvious inhibition effect occurred during SSF. These offered experiment evidences for ethanol production from corn straw....

  6. Catalytic wet Air Oxidation of o-Chlorophenol in Wastewater

    Institute of Scientific and Technical Information of China (English)

    徐新华; 汪大翬

    2003-01-01

    Catalytic wet air oxidation (CWAO) was investigated in laboratory-scale experiments for the treatment of o-chlorophenol in wastewater. Experimental results showed that wet air oxidation (WAO) process in the absence of catalyst was also effective for o-chlorophenol in wastewater treatment. Up to 80% of the initial CODCr was removed by wet air oxidation at 270℃ with twice amount of the required stoichiometric oxygen supply. At temperature of 150℃, the removal rate of CODCr was only 30%. Fe2(SO4)3, CuSO4, Cu(NO3)2 and MnSO4 exhibited high catalytic activity. Higher removal rate of CODCr was obtained by CWAO. More than 96% of the initial CODCr was removed at 270℃ and 84.6%-93.6% of the initial CODCr was removed at 150℃. Mixed catalysts had better catalytic activity for the degradation of o-chlorophenol in wastewater.

  7. Removal of ammonia solutions used in catalytic wet oxidation processes.

    Science.gov (United States)

    Hung, Chang Mao; Lou, Jie Chung; Lin, Chia Hua

    2003-08-01

    Ammonia (NH(3)) is an important product used in the chemical industry, and is common place in industrial wastewater. Industrial wastewater containing ammonia is generally either toxic or has concentrations or temperatures such that direct biological treatment is unfeasible. This investigation used aqueous solutions containing more of ammonia for catalytic liquid-phase oxidation in a trickle-bed reactor (TBR) based on Cu/La/Ce composite catalysts, prepared by co-precipitation of Cu(NO(3))(2), La(NO(3))(2), and Ce(NO(3))(3) at 7:2:1 molar concentrations. The experimental results indicated that the ammonia conversion of the wet oxidation in the presence of the Cu/La/Ce composite catalysts was determined by the Cu/La/Ce catalyst. Minimal ammonia was removed from the solution by the wet oxidation in the absence of any catalyst, while approximately 91% ammonia removal was achieved by wet oxidation over the Cu/La/Ce catalyst at 230 degrees C with oxygen partial pressure of 2.0 MPa. Furthermore, the effluent streams were conducted at a liquid hourly space velocity of under 9 h(-1) in the wet catalytic processes, and a reaction pathway was found linking the oxidizing ammonia to nitric oxide, nitrogen and water. The solution contained by-products, including nitrates and nitrites. Nitrite selectivity was minimized and ammonia removal maximized when the feed ammonia solution had a pH of around 12.0.

  8. CATALYSED ALKALINE OXIDATION AS A WOOD FRACTIONATION TECHNIQUE

    Directory of Open Access Journals (Sweden)

    Stella Rovio,

    2012-01-01

    Full Text Available Alkaline oxidation (AlkOx is an effective fractionation technique for lignocellulosic raw materials. The efficiency of the AlkOx treatment can further be enhanced by using a catalyst (CatOx. Both CatOx and AlkOx provide a fiber fraction containing readily hydrolysable carbohydrates that can be utilized in biotechnical processes and a liquid fraction containing solubilized lignin and reaction products from various biomass components. The effects of different fractionation conditions on yields and chemical composition of solubilized and insoluble fractions were investigated. Two temperatures and two reaction times were studied with and without a catalyst. The composition and content of carbohydrates in the fiber and liquid fractions were examined. The generation of aliphatic carboxylic acids as oxidation products was also investigated. The catalytically assisted oxidation was more efficient than the alkaline counterpart in dissolution of wood components under a four-hour treatment period resulting in higher dissolution of hemicelluloses. A longer reaction time of 20 hours leveled out the differences between the oxidation processes. Comparison of different bases showed that similar solubilisation of dry matter was obtained with NaOH, KOH, and Na2CO3. Oxidation in Na2CO3 caused higher dissolution of glucomannan and greater acid production. The dissolution of hemicellulose and lignin, and their oxidation to acids was most efficient in the first 4 hours of oxidation.

  9. Evaluation of wet oxidation pretreatment for enzymatic hydrolysis of softwood

    DEFF Research Database (Denmark)

    Palonen, H.; Thomsen, A.B.; Tenkanen, M.;

    2004-01-01

    The wet oxidation pretreatment (water, oxygen, elevated temperature, and pressure) of softwood (Picea abies) was investigated for enhancing enzymatic hydrolysis. The pretreatment was preliminarily optimized. Six different combinations of reaction time, temperature, and pH were applied......, and the compositions of solid and liquid fractions were analyzed. The solid fraction after wet oxidation contained 58-64% cellulose, 2-16% hemicellulose, and 24-30% lignin. The pretreatment series gave information about the roles of lignin and hemicellulose in the enzymatic hydrolysis. The temperature...

  10. Electrical Conductivity of Alkaline-reduced Graphene Oxide

    Institute of Scientific and Technical Information of China (English)

    WANG Huan; TIAN Hong-wei; WANG Xin-wei; QIAO Liang; WANG Shu-min; WANG Xing-li; ZHENG Wei-tao; LIU Yi-chun

    2011-01-01

    A green route using a very simple and straightforward ultrasonic process under alkaline conditions,rather than a general chemical reduction process using hydrazine,was utilized to obtain the hydrophilic reduced graphene oxide(RGO) sheets,via removing oxygen functional groups from graphene oxide(GO) and repairing the aromatic structure.It is found that the conductivity of the obtained RGO could be tuned by changing pH value in alkaline solution,and the current-voltage(Ⅰ-Ⅴ) curves of both GO and RGO are nonlinear and slightly asymmetric.Under the same applied voltage,the current of RGO is much larger than that of GO,indicating a pronounced increase in the electrical conductivity of RGO,compared to that of GO.

  11. Wet Oxidation of PVA-Containing Desizing Wastewater

    Institute of Scientific and Technical Information of China (English)

    雷乐成; 汪大翬

    2000-01-01

    Polyvinyl alcohol (PVA)-containing desizing wastewater was treated by various wet oxidation methods.Parameters such as reaction temperature, initial solution pH, and the dosage of H2O2 were investigated in terms of chemical oxygen demand (CODcr) and total organic carbon (TOC) removal rate. Up to 90% of the initial CODcr was removed by wet air oxidation(WAO) at 270℃ with stoichiometric oxygen supply, while at temperature of 200℃, the CODcr removal rate was found to be 80%. Similar results were obtained by Promoted WAO (PWAO) and wet peroxide oxidation(WPO) at a lower temperature of 150℃. Reaction temperature was found to have a significant effect on the oxidation performance for all the methods. Initial solution pH was observed to play a significant role in PWAO and WPO where H2O2 was employed. Comparison of WAO, CWAO(catalytic wet air oxidation), PWAO and WPO shows that the rate of CODcr removal increases in the order: WAO, CWAO, PWAO and WPO.

  12. Kinetics of wet oxidation of formic acid and acetic acid

    Energy Technology Data Exchange (ETDEWEB)

    Shende, R.V.; Mahajani, V.V. [Univ. of Mumbai (India). Dept. of Chemical Technology

    1997-11-01

    Oxidation of lower molecular weight carboxylic acids such as formic, acetic, glyoxalic, and oxalic acids is often the rate-controlling step during wet oxidation (WO) of an aqueous waste stream exhibiting very high chemical oxygen demand (COD). The kinetics of WO of formic acid was studied in the absence and presence of a cupric sulfate as catalyst in the temperature range 150--240 C and oxygen partial pressure range 0.345--1.380 MPa. Wet oxidation of acetic acid was carried out in the presence of cupric sulfate in the temperature range 215--235 C. Homogeneous copper sulfate was found to be a very good catalyst for oxidation of formic acid and acetic acid.

  13. The applicability of the catalytic wet-oxidation to CELSS

    Science.gov (United States)

    Takahashi, Y.; Nitta, K.; Ohya, H.; Oguchi, M.

    1987-01-01

    The wet oxidation catalysis of Au, Pd, Pt, Rh or Ru on a ceramic honeycomb carrier was traced in detail by 16 to 20 repetitive batch tests each. As a result, Pt or Pd on a honeycomb carrier was shown to catalyze complete nitrogen gasification as N2. Though the catalysts which realize both complete nitrogen gasification and complete oxidation could not be found, the Ru+Rh catalyst was found to be most promising. Ru honeycomb catalyzed both nitrification and nitrogen gasification.

  14. Development of chemical and biological processes for production of bioethanol. Optimization of the wet oxidation process and characterization of products

    Energy Technology Data Exchange (ETDEWEB)

    Bjerre, A.B.; Skammelsen Schmidt, A.

    1997-02-01

    The combination of the wet oxidation pretreatment process and alkaline hydrolysis was investigated in order to efficiently solubilize the hemicellulose, degrade the lignin, and open the solid crystalline cellulose structure of wheat straw lignocellulose without generating fermentation inhibitors. The effects of temperature, oxygen pressure, reaction time, and concentration of straw were evaluated. The degree of lignin degradation and hemicellulose solubilization increased with the reaction temperature and time. The optimum conditions were 15 minutes at 185 deg. C, producing 9.8 g/L hemicellulose. For quantification of the solubilized hemicellulose the best overall acid hydrolysis was obtained by treatment with 4 %w/v sulfuric acid for 10 minutes. The Aminex HPX-87H column was less sensitive towards impurities than the Aminex HPX-87P column. HPX-87H gave improved recovery and reproducibility, and was chosen for routine quantification of hydrolyzed hemicellulose sugars. The purity of the solid cellulose fraction also improved with higher temperature. The optimum condition for obtaining enzymatic convertible cellulose (90%) was 10 minutes at 170 deg. C using a high carbonate concentration. The hemicellulose yield and recovery were significantly reduced under these conditions indicating that a simultaneous optimal utilization of the hemicellulose and cellulose was difficult. The oxygen pressure and sodium carbonate concentration had little effect on the solubilization of hemicellulose, however, by combining wet oxidation with alkaline hydrolysis the formation of 2-furfural, a known microbial inhibitor, was minimal. Much more hemicellulose and lignin were solubilized from the straw by wet oxidation than by steaming(an alternative process). More cellulose was solubilized (and degraded) by steaming than by wet oxidation. Overall carbohydrates `losses` of 20.1% for steaming and 16.2% for wet oxidation were found. More 2-furfural was formed by steaming than by wet oxidation.

  15. Evolution of toxicity upon wet catalytic oxidation of phenol.

    Science.gov (United States)

    Santos, A; Yustos, P; Quintanilla, A; García-Ochoa, F; Casas, J A; Rodríguez, J J

    2004-01-01

    This work reports on the evolution of the toxicity of phenol-containing simulated wastewater upon catalytic wet oxidation with a commercial copper-based catalyst (Engelhard Cu-0203T). The results of the study show that this catalyst enhances detoxification, in addition to its effect on the oxidation rate. The EC50 values of the intermediates identified throughout the oxidation route of phenol have been determined and used to predict the evolution of toxicity upon oxidation. The predicted values have been compared with the ones measured directly from the aqueous solution during the oxidation process. To learn about the evolution of toxicity through out the routes of phenol oxidation, experiments have been performed with simulated wastewaters containing separately phenol, catechol, and hydroquinone as original pollutants. The significant increase of toxicity observed during the early stages of phenol oxidation is not directly related to the development of the brown color that derives mainly from catechol oxidation. This increase of toxicity is caused by the formation of hydroquinone and p-benzoquinone as intermediates, the former showing the highest toxicity. Furthermore, synergistic effects, giving rise to a significant increase of toxicity, have been observed. These effects derive from the interactions among copper leached from the catalyst and catechol, hydroquinone, and p-benzoquinone and demand that close attention be paid to this potential problem in catalytic wet oxidation.

  16. Process of forming catalytic surfaces for wet oxidation reactions

    Science.gov (United States)

    Jagow, R. B. (Inventor)

    1977-01-01

    A wet oxidation process was developed for oxidizing waste materials, comprising dissolved ruthenium salt in a reactant feed stream containing the waste materials. The feed stream is introduced into a reactor, and the reactor contents are then raised to an elevated temperature to effect deposition of a catalytic surface of ruthenium black on the interior walls of the reactor. The feed stream is then maintained in the reactor for a period of time sufficient to effect at least partial oxidation of the waste materials.

  17. Wet oxidation as a waste treatment in closed systems

    Science.gov (United States)

    Onisko, B. L.; Wydeven, T.

    1981-01-01

    The chemistry of the wet oxidation process has been investigated in relation to production of plant nutrients from plant and human waste materials as required for a closed life-support system. Hydroponically grown lettuce plants were used as a model plant waste and oxygen gas was used as oxidant. Organic nitrogen content was decreased 88-100% depending on feed material. Production of ammonia and nitrogen gas account for all of the observed decrease in organic nitrogen content. No nitrous oxide (N2O) was detected. The implications of these results for closed life-support systems are discussed.

  18. Wet Oxidation as a Waste Treatment Method in Closed Systems

    Science.gov (United States)

    Onisko, B. L.; Wydeven, T.

    1982-01-01

    The chemistry of the wet oxidation process was investigated in relation to production of plant nutrients from plant and human waste materials as required for a closed life support system. Hydroponically grown lettuce plants were used as a model plant waste, and oxygen gas was used as an oxidant. Organic nitrogen content was decreased 88-100%, depending on feed material. Production of ammonia and nitrogen gas accounted for all of the observed decrease in organic nitrogen content. No nitrous oxide (N2O) was detected. The implications of these results for closed life support systems are discussed.

  19. Kinetics studies of oxidation of niacinamide by alkaline potassium permanganate

    Directory of Open Access Journals (Sweden)

    Sandipsingh Gour

    2012-04-01

    Full Text Available The oxidation of niacinamide in alkaline media is carried out using potassium permanganate as a oxiding agent. The reaction was monitored using UV-Visible spectrophotometer at 525 nm. It was found to be zero order with respect to oxidant,, fractional order with respect to hydrogen ion concentration and first order with respect to substrate. The thermodynamic parameters(were determinied . The average (?G# was found to be 87.60 KJ/mol. The values ?S# was found to be -0.2132 KJ/mole and energy of activation was found to be 23.95 KJ/mole. A suitable mechanism is proposed based on the experimental conditions.

  20. Electrochemical Impedance of Ethanol Oxidation in Alkaline Media

    Institute of Scientific and Technical Information of China (English)

    DANAEE Iman; JAFARIAN Majid; GOBAL Fereydoon; SHARAFI Mahboobeh; MAHJANI Mohammad-ghasem

    2012-01-01

    Nickel modified NiOOH electrodes were used for the electrocatalytic oxidation of ethanol in alkaline solutions.The electro-oxidation of ethanol in a 1 mol/L NaOH solution at different concentrations of ethanol was studied by ac impedance spectroscopy.Electrooxidation of ethanol on Ni shows negative resistance on impedance plots.The impedance shows different patterns at different applied anodic potential.The influence of the electrode potential on impedance was studied and a quantitative explanation for the impedance of ethanol oxidation was given by means of a proposed mathematical model.At potentials higher than 0.52 V(vs.Ag/AgCl),a pseudoinductive behavior was observed,but at those higher than 0.57 V,impedance patterns were reversed to the second and third quadrants.The conditions required for the reversing of impedance pattern were delineated with the impedance model.

  1. Wet oxidation of real coke wastewater containing high thiocyanate concentration.

    Science.gov (United States)

    Oulego, Paula; Collado, Sergio; Garrido, Laura; Laca, Adriana; Rendueles, Manuel; Díaz, Mario

    2014-01-01

    Coke wastewaters, in particular those with high thiocyanate concentrations, represent an important environmental problem because of their very low biodegradability. In this work, the treatment by wet oxidation of real coke wastewaters containing concentrations of thiocyanate above 17 mM has been studied in a 1-L semi-batch reactor at temperatures between 453 and 493 K, with total oxygen pressures in the range of 2.0-8.0 MPa. A positive effect of the matrix of real coke wastewater was observed, resulting in faster thiocyanate degradation than was obtained with synthetic wastewaters. Besides, the effect of oxygen concentration and temperature on thiocyanate wet oxidation was more noticeable in real effluents than in synthetic wastewaters containing only thiocyanate. It was also observed that the degree of mineralization of the matrix organic compounds was higher when the initial thiocyanate concentration increased. Taking into account the experimental data, kinetic models were obtained, and a mechanism implying free radicals was proposed for thiocyanate oxidation in the matrix considered. In all cases, sulphate, carbonates and ammonium were identified as the main reaction products of thiocyanate wet oxidation.

  2. Study on mechanism of wet air oxidation of emulsification wastewater.

    Science.gov (United States)

    Tang, Wen W; Zeng, Xin P; Xiao, Yao M; Gu, Guo W

    2009-04-01

    Wet air oxidation (WAO) can effectively be used to treat high-concentration, non-biodegradable emulsification wastewater that contains nonionic matters. Gas chromatograph analysis of emulsification wastewater after oxidation indicated that a catalyst increased production of fatty acids but could not promote its oxidation between 160 and 180 degrees C. When the temperature was greater than or equal to 220 degrees C, the catalyst not only increased production of fatty acids initially but effectively promoted its oxidation in later stages and significantly reduced the concentration of residual surfactants. Experiments proved that fatty acids (especially acetic acid) were the primary intermediate products and that oxidation of these acids was the rate-limiting step. During the process of catalytic WAO of emulsification wastewater, active oxygen molecules attacked organic matters resulting in production of fatty acids, ketone, alcohol, hydrocarbon, and oligo-polyether through radical chain reactions.

  3. Microwave assisted wet oxidation of p-nitrophenol

    Institute of Scientific and Technical Information of China (English)

    BO; Longli; CHEN; Shuo; QUAN; Xie; LIU; Xitao; ZHAO; Huimin

    2005-01-01

    Aqueous solution of p-nitrophenol (PNP) was treated continuously by microwave assisted wet oxidation while flowing through a granular activated carbon (GAC) fixed bed. PNP was pre-adsorbed onto GAC prior to being put into the reactor so as to prevent PNP adsorption on GAC during microwave irradiation. PNP solutions with different initial concentration (218.6 mg/L and 1200 mg/L) were treated under conditions of microwave power 500 W, liquid flow 6.4 mL/min and air flow 40 mL/min or 60 mL/min. The results indicated that the removal of PNP was higher than 90% and more than 65% PNP was mineralized. Phenol, nitrobenzene, hydroquinone and benzoquinone occurred as course products during the operation process, which were degraded further. The biodegradability of the outflow was improved greatly by microwave assisted wet oxidation.

  4. Development studies of a novel wet oxidation process

    Energy Technology Data Exchange (ETDEWEB)

    Rogers, T.W.; Dhooge, P.M. [Delphi Research, Inc., Albuquerque, NM (United States)

    1995-10-01

    Many DOE waste streams and remediates contain complex and variable mixtures of organic compounds, toxic metals, and radionuclides. These materials are often dispersed in organic or inorganic matrices, such as personal protective equipment, various sludges, soils, and water. Incineration and similar combustive processes do not appear to be viable options for treatment of these waste streams due to various considerations. The objective of this project is to develop a novel catalytic wet oxidation process for the treatment of multi-component wastes. The DETOX process uses a unique combination of metal catalysts to increase the rate of oxidation of organic materials.

  5. Wet-oxidation waste management system for CELSS

    Science.gov (United States)

    Takahashi, Y.; Ohya, H.

    1986-01-01

    A wet oxidation system will be useful in the Closed Ecological Life Support System (CELSS) as a facility to treat organic wastes and to redistribute inorganic compounds and elements. However at rather higher temperatures needed in this reaction, for instance, at 260 deg C, only 80% of organic in a raw material can be oxidized, and 20% of it will remain in the liquid mainly as acetic acid, which is virtually noncombustible. Furthermore, nitrogen is transformed to ammonium ions which normally cannot be absorbed by plants. To resolve these problems, it becomes necessary to use catalysts. Noble metals such as Ru, Rh and so on have proved to be partially effective as these catalysts. That is, oxidation does not occur completely, and the unexpected denitrification, instead of the expected nitrification, occurs. So, it is essential to develop the catalysts which are able to realize the complete oxidation and the nitrification.

  6. Dissolution of Uranium Oxides Under Alkaline Oxidizing Conditions

    Energy Technology Data Exchange (ETDEWEB)

    Smith, Steven C.; Peper, Shane M.; Douglas, Matthew; Ziegelgruber, Kate L.; Finn, Erin C.

    2009-11-01

    Bench scale experiments were conducted to determine the dissolution characteristics of uranium oxide powders (UO2, U3O8, and UO3) in aqueous peroxide-carbonate solutions. Experimental parameters included H2O2 concentration, carbonate counter cation (NH4+, Na+, K+, and Rb+), and pH. Results indicate the dissolution rate of UO2 in 1 M (NH4)2CO3 increases linearly with peroxide concentration ranging from 0.05 – 2 M. The three uranium oxide powders exhibited different dissolution patterns however, UO3 exhibited prompt complete dissolution. Carbonate counter cation affected the dissolution kinetics. There is minimal impact of solution pH, over the range 8.8 to 10.6, on initial dissolution rate.

  7. High solid simultaneous saccharification and fermentation of wet oxidized corn stover to ethanol

    DEFF Research Database (Denmark)

    Varga, E.; Klinke, H.B.; Reczey, K.

    2004-01-01

    In this study ethanol was produced from corn stover pretreated by alkaline and acidic wet oxidation (WO) (195 degreesC, 15 min, 12 bar oxygen) followed by nonisothermal simultaneous saccharification and fermentation (SSF). In the first step of the SSF, small amounts of cellulases were added at 50....../L) were present in the hemicellulose rich hydrolyzate at subinhibitory levels, thus no detoxification was needed prior to SSF of the whole slurry. Based on the cellulose available in the WO corn stover 83% of the theoretical ethanol yield was obtained under optimized SSF conditions. This was achieved...... with a substrate concentration of 12% dry matter (DM) acidic WO corn stover at 30 FPU/g DM (43.5 FPU/g cellulose) enzyme loading. Even with 20 and 15 FPU/g DM (corresponding to 29 and 22 FPU/g cellulose) enzyme loading, ethanol yields of 76 and 73%, respectively, were obtained. After 120 h of SSF the highest...

  8. Catalytic properties of carbon materials for wet oxidation of aniline.

    Science.gov (United States)

    Gomes, Helder T; Machado, Bruno F; Ribeiro, Andreia; Moreira, Ivo; Rosário, Márcio; Silva, Adrián M T; Figueiredo, José L; Faria, Joaquim L

    2008-11-30

    A mesoporous carbon xerogel with a significant amount of oxygen functional groups and a commercial activated carbon, were tested in the catalytic wet air oxidation of aniline at 200 degrees C and 6.9 bar of oxygen partial pressure. Both carbon materials showed high activity in aniline and total organic carbon removal, a clear increase in the removal efficiency relatively to non-catalytic wet air oxidation being observed. The best results in terms of aniline removal were obtained with carbon xerogel, an almost complete aniline conversion after 1h oxidation with high selectivity to non-organic compounds being achieved. The materials were characterized by thermogravimetric analysis, temperature programmed desorption, N(2) adsorption and scanning electron microscopy, in order to relate their performances to the chemical and textural characteristics. It was concluded that the removal efficiency, attributed to both adsorption and catalytic activity, is related to the mesoporous character of the materials and to the presence of specific oxygen containing functional groups at their surface. The effect of catalytic activity was found to be more important in the removal of aniline than the effect of adsorption at the materials surface. The results obtained indicate that mesoporous carbon xerogels are promising catalysts for CWAO processes.

  9. Catalytic properties of carbon materials for wet oxidation of aniline

    Energy Technology Data Exchange (ETDEWEB)

    Gomes, Helder T. [Laboratorio de Catalise e Materiais (LCM), Laboratorio Associado LSRE/LCM, Departamento de Engenharia Quimica, Faculdade de Engenharia, Universidade do Porto, Rua Dr. Roberto Frias, 4200-465 Porto (Portugal); Departamento de Tecnologia Quimica e Biologica, Escola Superior de Tecnologia e de Gestao, Instituto Politecnico de Braganca, Campus de Santa Apolonia, 5300-857 Braganca (Portugal); Machado, Bruno F.; Ribeiro, Andreia; Moreira, Ivo; Rosario, Marcio; Silva, Adrian M.T.; Figueiredo, Jose L. [Laboratorio de Catalise e Materiais (LCM), Laboratorio Associado LSRE/LCM, Departamento de Engenharia Quimica, Faculdade de Engenharia, Universidade do Porto, Rua Dr. Roberto Frias, 4200-465 Porto (Portugal); Faria, Joaquim L. [Laboratorio de Catalise e Materiais (LCM), Laboratorio Associado LSRE/LCM, Departamento de Engenharia Quimica, Faculdade de Engenharia, Universidade do Porto, Rua Dr. Roberto Frias, 4200-465 Porto (Portugal)], E-mail: jlfaria@fe.up.pt

    2008-11-30

    A mesoporous carbon xerogel with a significant amount of oxygen functional groups and a commercial activated carbon, were tested in the catalytic wet air oxidation of aniline at 200 deg. C and 6.9 bar of oxygen partial pressure. Both carbon materials showed high activity in aniline and total organic carbon removal, a clear increase in the removal efficiency relatively to non-catalytic wet air oxidation being observed. The best results in terms of aniline removal were obtained with carbon xerogel, an almost complete aniline conversion after 1 h oxidation with high selectivity to non-organic compounds being achieved. The materials were characterized by thermogravimetric analysis, temperature programmed desorption, N{sub 2} adsorption and scanning electron microscopy, in order to relate their performances to the chemical and textural characteristics. It was concluded that the removal efficiency, attributed to both adsorption and catalytic activity, is related to the mesoporous character of the materials and to the presence of specific oxygen containing functional groups at their surface. The effect of catalytic activity was found to be more important in the removal of aniline than the effect of adsorption at the materials surface. The results obtained indicate that mesoporous carbon xerogels are promising catalysts for CWAO processes.

  10. Surface wrinkling on polydimethylsiloxane microspheres via wet surface chemical oxidation.

    Science.gov (United States)

    Yin, Jian; Han, Xue; Cao, Yanping; Lu, Conghua

    2014-07-16

    Here we introduce a simple low-cost yet robust method to realize spontaneously wrinkled morphologies on spherical surfaces. It is based on surface chemical oxidation of aqueous-phase-synthesized polydimethylsiloxane (PDMS) microspheres in the mixed H2SO4/HNO3/H2O solution. Consequently, curvature and overstress-sensitive wrinkles including dimples and labyrinth patterns are successfully induced on the resulting oxidized PDMS microspheres. A power-law dependence of the wrinkling wavelength on the microsphere radius exists. The effects of experimental parameters on these tunable spherical wrinkles have been systematically investigated, when the microspheres are pre-deposited on a substrate. These parameters include the radius and modulus of microspheres, the mixed acid solution composition, the oxidation duration, and the water washing post-treatment. Meanwhile, the complicated chemical oxidation process has also been well studied by in-situ optical observation via the microsphere system, which represents an intractable issue in a planar system. Furthermore, we realize surface wrinkled topographies on the whole microspheres at a large scale, when microspheres are directly dispersed in the mixed acid solution for surface oxidation. These results indicate that the introduced wet surface chemical oxidation has the great potential to apply to other complicated curved surfaces for large-scale generation of well-defined wrinkling patterns, which endow the solids with desired physical properties.

  11. Wet air and catalytic wet air oxidation of several azodyes from wastewaters: the beneficial role of catalysis.

    Science.gov (United States)

    Rodríguez, A; García, J; Ovejero, G; Mestanza, M

    2009-01-01

    Degradation of several azo dyes, Acid Orange 7 (AO7), Acid Orange 74 (AO74), Direct Blue 71 (DB71), Reactive Black 5 (RB5) and Eriochrome Blue Black B (EBBB), well-known non-biodegradable mono, di and tri azo dyes has been studied using, wet-air oxidation (WAO) and catalytic wet air oxidation (CWAO). The efficiency of substrate decolorization and mineralization in each process has been comparatively discussed by evolution concentration, chemical oxygen demand, total organic carbon content and toxicity of dyes solutions. The most efficient method on decolorization and mineralization (TOC) was observed to be CWAO process. Mineralization efficiency with wet air and catalytic wet air oxidation essays was observed in the order of mono-azo > di-azo > tri-azo dye. Final solutions of CWAO applications after 180 min treatment can be disposed safely to environment.

  12. Comparison of alkaline- and fungi-assisted wet-storage of corn stover.

    Science.gov (United States)

    Cui, Zhifang; Shi, Jian; Wan, Caixia; Li, Yebo

    2012-04-01

    Storage of lignocellulosic biomass is critical for a year-round supply of feedstock for a biorefinery. Compared with dry storage, wet storage is a promising alternative technology, providing several advantages including reduced dry matter loss and fire risk and improved feedstock digestibility after storage. This study investigated the concurrent pretreatment and wet-storage of corn stover with the assistance of NaOH or a lignin-degrading fungus, Ceriporiopsis subvermispora, during a 90-d period. Compared with ensilage, adding NaOH or inoculation with C. subvermispora significantly enhanced the enzymatic degradability of corn stover by 2-3-fold after 90-d wet storage. Lignin and xylan removal during NaOH pretreatment and wet-storage were influenced by NaOH loading and moisture. NaOH pretreatment retarded the production of organic acids during storage and the acetate release correlated with lignin and xylan removal. Further study is needed to reduce cellulose degradation during the late stage of fungal treatment.

  13. Potential inhibitors from wet oxidation of wheat straw and their effect on ethanol production of Saccharomyces cerevisiae

    DEFF Research Database (Denmark)

    Klinke, H.B.; Olsson, L.; Thomsen, A.B.;

    2003-01-01

    Alkaline wet oxidation (WO) (using water, 6.5 g/L sodium carbonate and 12 bar oxygen at 195degreesC) was used as pretreatment method for wheat straw (60 g/L), resulting in a hydrolysate and a cellulosic solid fraction. The hydrolysate consisted of soluble hemicellulose (8 g/L), low......-molecular-weight carboxylic acids (3.9 g/L), phenols (0.27 g/L = 1.7 mM) and 2-furoic acid (0.007 g/L). The wet oxidized wheat straw hydrolysate caused no inhibition of ethanol production by Saccharomyces cerevisiae ATCC 96581. Nine phenols and 2-furoic acid, identified to be present in the hydrolysate, were each tested...

  14. Potential inhibitors from wet oxidation of wheat straw and their effect on growth and ethanol production by Thermoanaerobacter mathranii

    DEFF Research Database (Denmark)

    Klinke, Helene Bendstrup; Thomsen, A.B.; Ahring, Birgitte Kiær

    2001-01-01

    Alkaline wet oxidation (WO) (using water, 6.5 g/l sodium carbonate, and 12 bar oxygen at 195 degreesC) was used for pre-treating wheat straw (60 g/l), resulting in a hemicellulose-rich hydrolysate and a cellulose-rich solid fraction. The hydrolysate consisted of soluble hemicellulose (9 g....../l), aliphatic carboxylic acids (6 g/l), phenols (0.27 g/l or 1.7 mM), and 2-furoic acid (0.007 g/l). The wet-oxidized wheat straw hydrolysate caused no inhibition of ethanol yield by the anaerobic thermophilic bacterium Thermoanaerobacter mathranii. Nine phenols and 2-furoic acid, identified to be present...

  15. Catalytic wet hydrogen peroxide oxidation of a petrochemical wastewater.

    Science.gov (United States)

    Pariente, M I; Melero, J A; Martínez, F; Botas, J A; Gallego, A I

    2010-01-01

    Continuous Catalytic Wet Hydrogen Peroxide Oxidation (CWHPO) for the treatment of a petrochemical industry wastewater has been studied on a pilot plant scale process. The installation, based on a catalytic fixed bed reactor (FBR) coupled with a stirred tank reactor (STR), shows an interesting alternative for the intensification of a continuous CWHPO treatment. Agglomerated SBA-15 silica-supported iron oxide (Fe(2)O(3)/SBA-15) was used as Fenton-like catalyst. Several variables such as the temperature and hydrogen peroxide concentration, as well as the capacity of the pilot plant for the treatment of inlet polluted streams with different dilution degrees were studied. Remarkable results in terms of TOC reduction and increased biodegradability were achieved using 160 degrees C and moderate hydrogen peroxide initial concentration. Additionally, a good stability of the catalyst was evidenced for 8 hours of treatment with low iron leaching (less than 1 mg/L) under the best operating conditions.

  16. Kinetics of wet air oxidation (WAO) of alcaloide factory wastewater.

    Science.gov (United States)

    Kunukcu, Y Kaçar

    2005-01-01

    Wet air oxidation (WAO) of Afyon alcaloide factory wastewater, a typical high strength industrial wastewater, was carried out. The process was performed in a specifically designed titanium bubble reactor at temperatures in the range of 140-160 degrees C. The kinetics of WAO of alcaloide factory wastewater was modeled by assuming two distinct steps. The rates of destruction were measured with respect to reduction in COD. The oxidation reaction was found to be first order with respect to COD concentration and also second order with respect to oxygen concentration in both steps. The values of activation energies were found to be in the range of 4.93 x 10(4)-7.85 x 10(4) kJ/kmol.

  17. Catalytic wet air oxidation of high concentration pharmaceutical wastewater.

    Science.gov (United States)

    Zhan, Wei; Wang, Xiaocong; Li, Daosheng; Ren, Yongzheng; Liu, Dongqi; Kang, Jianxiong

    2013-01-01

    In this study, we investigated the pretreatment of a high concentration pharmaceutical wastewater by catalytic wet air oxidation (CWAO) process. Different experiments were conducted to investigate the effects of the catalyst type, operating temperature, initial system pH, and oxygen partial pressure on the oxidation of the wastewater. Results show that the catalysts prepared by the co-precipitation method have better catalytic activity compared to others. Chemical oxygen demand (COD) conversion increased with the increase in temperature from 160 to 220 °C and decreased with the increase in pH. Moreover, the effect of the oxygen partial pressure on the COD conversion was significant only during the first 20 min of the reaction. Furthermore, the biodegradability of the wastewater improved greatly after CWAO, the ratio of BOD5/COD increased less than 0.1-0.75 when treated at 220 °C (BOD: biochemical oxygen demand).

  18. Wet oxidation kinetics of refractory low molecular mass carboxylic acids

    Energy Technology Data Exchange (ETDEWEB)

    Shende, R.V.; Levec, J.

    1999-10-01

    Wet oxidation kinetics of aqueous solutions of formic, acetic, oxalic, and glyoxalic acids was studied in a titanium autoclave at a temperature range of 150--320 C and oxygen partial pressures between 8 and 60 bar. Oxidation reactions obeyed a first-order kinetics with respect to concentration of all substrates. On the basis of acid concentration decay, the activation energy for acetic, oxalic, and glyoxalic acid oxidation was 178, 137, and 97 kJ/mol, respectively; whereas on the total organic carbon (TOC) conversion basis, these values were slightly higher, namely 182, 141, and 104 kJ/mol. The activation energy for formic acid took a unique value of 149 kJ/mol regardless of the type of concentration used. The rate of oxidation was proportional to a square root of oxygen concentration (partial pressure) for acetic, formic, and oxalic acids, whereas it was linearly proportional for glyoxalic acid. When sufficiently high oxygen partial pressure was applied ({ge}22 bar), the individual acid conversion in a mixture of these acids was well predicted by the rate expression derived for that acid. The lumped TOC concentration of mixtures did not obey a first-order kinetic behavior, although underlying TOC kinetics for each individual acid was linear. The oxidation results are also discussed in a view of speculated reaction pathways and the reactor material.

  19. Pretreatment of apramycin wastewater by catalytic wet air oxidation

    Institute of Scientific and Technical Information of China (English)

    YANG Shao-xia; FENG Yu-jie; WAN Jia-feng; LIN Qing-ying; ZHU Wan-peng; JIANG Zhan-peng

    2005-01-01

    The pretreatment technology of wet air oxidation(WAO) and coagulation and acidic hydrolysis for apramycin wastewater was investigated in this paper. The COD, apramycin, NH4+ concentration, and the ratio of BOD5/COD were analyzed, and the color and odor of the effluent were observed. WAO of apramycin wastewater, without catalyst and with RuO2/Al2 O3 and RuO2-CeO2/Al2 O3 catalysts, was carried out at degradation temperature of 200℃ and the total pressure of 4 MPa in a 1 L batch reactor. The result showed that the apramycin removals were respectively 50.2% and 55.0%, COD removals were 40.0% and 46.0%, and the ratio of BOD5/COD was increased to 0.49 and 0.54 with RuO2/Al2 O3 and RuO2-CeO2/Al2 O3 catalysts in catylytic wet air oxidation(CWAO) after the reaction of 150 min. With the pretreatment of coagulation and acidic hydrolysis, COD and apramycin removals were slight decreased, and the ratio of BOD5/COD was increased to 0.45, and the effluents was not suitable to biological treatment. The color and odor of the wastewater were the apramycin wastewater. The addition of CeO2 could promote the activity and stability of RuO2/Al2 O3 in WAO of apramycin wastewater.

  20. Wet air oxidation of seedcorn wastes containing pesticides and insecticides

    Energy Technology Data Exchange (ETDEWEB)

    Sievers, M.; Schlaefer, O.; Onyeche, T.I.; Schroeder, C.; Bormann, H.; Schaefer, S. [CUTEC-Inst. GmbH (Clausthal Environment Technology Inst.), Clausthal-Zellerfeld (Germany)

    2003-07-01

    Wet air oxidation as an alternative treatment process to pyrolysis and combustion of seedcorn wastes was investigated in lab-scale experiments. Due to solid condition of the seed corn waste, the process has been adapted by repeated spraying of water on the seed corn bulk to avoid the production of sludge and its subsequent dewatering. Original seed corns from industrial production plants were used for a degradation kinetic study under smooth wet air oxidation conditions. The temperatures were between 80 and 150 C, the pressure from 1 to 4.5 bar and the pH at different values from 3 to 13. Degradation rates for five different compounds of pesticides and insecticides, namely Imidacloprid, Thiram, Hymexazol, Carbofuran and Tefluthrin were conducted. These compounds represent the recently used in agricultural seedcorn applications. The degradation rate depends linearly on temperature between 80 and 150 C. At 120 C the lowest degradation rate was found for Tefluthrin by 25 mg/h per L reaction volume while the highest degradation rate to be conducted was for Imidacloprid at 363 mg/h L. (orig.)

  1. Wet air oxidation of epoxy acrylate monomer industrial wastewater.

    Science.gov (United States)

    Yang, Shaoxia; Liu, Zhengqian; Huang, Xiaohui; Zhang, Beiping

    2010-06-15

    Epoxy acrylate monomer industrial wastewater contained highly concentrated and toxic organic compounds. The wet air oxidation (WAO) and catalytic wet air oxidation (CWAO) were used to eliminate pollutants in order to examine the feasibility of the WAO/CWAO as a pre-treatment method for the industrial wastewater. The results showed that in the WAO 63% chemical oxygen demand (COD) and 41% total organic carbon (TOC) removals were achieved and biological oxygen demand (BOD(5))/COD ratio increased from 0.13 to 0.72 after 3h reaction at 250 degrees C, 3.5MPa and the initial concentration of 100g(COD)/L. Among homogenous catalysts (Cu(2+), Fe(2+), Fe(3+) and Mn(2+) salts), Cu(2+) salt exhibited better performance. CuO catalyst was used in the CWAO of the wastewater, COD and TOC conversion were 77 and 54%, and good biodegradability was achieved. The results proved that the CWAO was an effective pre-treatment method for the epoxy acrylate monomer industrial wastewater.

  2. Catalytic wet air oxidation of chlorophenols over supported ruthenium catalysts.

    Science.gov (United States)

    Li, Ning; Descorme, Claude; Besson, Michèle

    2007-07-31

    A series of noble metal (Pt, Pd, Ru) loaded zirconia catalysts were evaluated in the catalytic wet air oxidation (CWAO) of mono-chlorophenols (2-CP, 3-CP, 4-CP) under relatively mild reaction conditions. Among the investigated noble metals, Ru appeared to be the best to promote the CWAO of CPs as far as incipient-wetness impregnation was used to prepare all the catalysts. The position of the chlorine substitution on the aromatic ring was also shown to have a significant effect on the CP reactivity in the CWAO over 3wt.% Ru/ZrO(2). 2-CP was relatively easier to degradate compared to 3-CP and 4-CP. One reason could be the higher adsorption of 2-CP on the catalyst surface. Further investigations suggested that 3wt.% Ru/ZrO(2) is a very efficient catalyst in the CWAO of 2-CP as far as high 2-CP conversion and TOC abatement could still be reached at even lower temperature (393K) and lower total pressure (3MPa). Additionally, the conversion of 2-CP was demonstrated to increase with the initial pH of the 2-CP solution. The dechlorination reaction is promoted at higher pH. In all cases, the adsorption of the reactants and the reaction intermediates was shown to play a major role. All parameters that would control the molecule speciation in solution or the catalyst surface properties would have a key effect.

  3. Transformation and removal of wood extractives from pulp mill sludge using wet oxidation and thermal hydrolysis.

    Science.gov (United States)

    Baroutian, Saeid; Robinson, Murray; Smit, Anne-Marie; Wijeyekoon, Suren; Gapes, Daniel

    2013-10-01

    In order to remove wood extractive compounds from pulp mill sludge and thereby enhancing anaerobic digestibility, samples were subjected to either oxidative hydrothermal treatment (wet oxidation) or non-oxidative hydrothermal treatment (thermal hydrolysis). Treatments were carried out at 220 °C with initial pressure of 20 bar. More than 90% destruction of extractive compounds was observed after 20 min of wet oxidation. Wet oxidation eliminated 95.7% of phenolics, 98.6% fatty acids, 99.8% resin acids and 100% of phytosterols in 120 min. Acetic acid concentration increased by approximately 2 g/l after 120 min of wet oxidation. This has potential for rendering sludge more amenable to anaerobic digestion. In contrast thermal hydrolysis was found to be ineffective in degrading extractive compounds. Wet oxidation is considered to be an effective process for removal of recalcitrant and inhibitive compounds through hydrothermal pre-treatment of pulp mill sludge.

  4. Wet air oxidation induced enhanced biodegradability of distillery effluent.

    Science.gov (United States)

    Malik, S N; Saratchandra, T; Tembhekar, P D; Padoley, K V; Mudliar, S L; Mudliar, S N

    2014-04-01

    The present study reports the feasibility of Wet Air Oxidation (WAO) as a pretreatment option for enhanced biodegradation of complex distillery effluent. Initially, the distillery effluent was pretreated by WAO at different process conditions (pressure, temperature and time) to facilitate enhancement in the biodegradability index (BI = BOD5: COD ratio). The biodegradability of WAO pretreated effluent was evaluated by subjecting it to aerobic biodegradation and anaerobic followed by aerobic biodegradation. Aerobic biodegradation of pretreated effluent with enhanced biodegradability index (BI = 0.4-0.8) showed enhanced COD reduction of up to 67.7%, whereas the untreated effluent (BI = 0.17) indicated poor COD reduction of only 22.5%. Anaerobic followed by aerobic biodegradation of pretreated effluent has shown up to 87.9% COD reduction, while the untreated effluent has shown only 43.1% COD reduction. Bio-kinetic parameters also confirmed the increased rate of bio-oxidation at enhanced BIs. The results indicate that the WAO pretreatment facilitates enhanced bio-oxidation/bio-degradation of complex effluents like the distillery spent wash.

  5. Homogeneous catalytic wet air oxidation for the treatment oftextile wastewaters

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    An extensive series of experiments was carried out in order to identify suitable catalysts to boost the reaction rate of wet air oxidation of real textile wastewaters at relatively mild temperature and pressure. Experimental results indicated that all catalysts tested in this investigation had shown an impressive increase in the initial COD and TOC removal rate as well as the COD and TOC removal levels in two hours reaction. Among all the catalysts tested, copper salts were more effective than the rest. Anions of the salt soluffonsalso played a role in the catalytic process with nitrate ions having better effect than sulfate ions. Hence copper nitrates were more effective than copper sulfates. It was also found that a mixture of salts with different metals performed better than either of the component single salt alone.

  6. Wet oxidation pretreatment of rape straw for ethanol production

    DEFF Research Database (Denmark)

    Arvaniti, Efthalia; Bjerre, Anne Belinda; Schmidt, Jens Ejbye

    2012-01-01

    Rape straw can be used for production of second generation bioethanol. In this paper we optimized the pretreatment of rape straw for this purpose using Wet oxidation (WO). The effect of reaction temperature, reaction time, and oxygen gas pressure was investigated for maximum ethanol yield via...... Simultaneous Saccharification and Fermentation (SSF). To reduce the water use and increase the energy efficiency in WO pretreatment features like recycling liquid (filtrate), presoaking of rape straw in water or recycled filtrate before WO, skip washing pretreated solids (filter cake) after WO, or use of whole...... slurry (Filter cake + filtrate) in SSF were also tested. Except ethanol yields, pretreatment methods were evaluated based on achieved glucose yields, amount of water used, recovery of cellulose, hemicellulose, and lignin.The highest ethanol yield obtained was 67% after fermenting the whole slurry...

  7. Oxidation of anthracene using waste Mn oxide minerals: the importance of wetting and drying sequences.

    Science.gov (United States)

    Clarke, Catherine; Tourney, Janette; Johnson, Karen

    2012-02-29

    PAHs are a common problem in contaminated urban soils due to their recalcitrance. This study presents results on the oxidation of anthracene on synthetic and natural Mn oxide surfaces. Evaporation of anthracene spiked Mn oxide slurries in air results in the oxidation of 30% of the anthracene to anthraquinone. Control minerals, quartz and calcite, also oxidised a small but significant proportion of the anthracene (4.5% and 14% conversion, respectively) when spiked mineral slurries were evaporated in air. However, only Mn oxide minerals showed significant anthracene oxidation (5-10%) when evaporation took place in the absence of oxygen (N2 atmosphere). In the fully hydrated systems where no drying took place, natural Mn oxides showed an increase in anthracene oxidation with decreasing pH, with a conversion of 75% anthracene at pH 4. These results show both acidification and drying favor the oxidation of anthracene on Mn oxide mineral surfaces. It has also been demonstrated that non-redox active mineral surfaces, such as calcite, may play a role in contaminant breakdown during wetting and drying sequences. Given that climate changes suggest that wetting and drying sequences are likely to become more significant these results have important implications for contaminated land remediation technologies.

  8. Degradation of paracetamol by catalytic wet air oxidation and sequential adsorption - Catalytic wet air oxidation on activated carbons

    Energy Technology Data Exchange (ETDEWEB)

    Quesada-Penate, I. [Universite de Toulouse, INPT, UPS, Laboratoire de Genie Chimique, 4, Allee Emile Monso, F-31432 Toulouse (France); CNRS, Laboratoire de Genie Chimique, F-31432 Toulouse (France); Julcour-Lebigue, C., E-mail: carine.julcour@ensiacet.fr [Universite de Toulouse, INPT, UPS, Laboratoire de Genie Chimique, 4, Allee Emile Monso, F-31432 Toulouse (France); CNRS, Laboratoire de Genie Chimique, F-31432 Toulouse (France); Jauregui-Haza, U.J. [Instituto Superior de Tecnologias y Ciencias Aplicadas, Ave. Salvador Allende y Luaces, Habana (Cuba); Wilhelm, A.M.; Delmas, H. [Universite de Toulouse, INPT, UPS, Laboratoire de Genie Chimique, 4, Allee Emile Monso, F-31432 Toulouse (France); CNRS, Laboratoire de Genie Chimique, F-31432 Toulouse (France)

    2012-06-30

    Highlights: Black-Right-Pointing-Pointer Three activated carbons (AC) compared as adsorbents and oxidation catalysts. Black-Right-Pointing-Pointer Similar evolution for catalytic and adsorptive properties of AC over reuses. Black-Right-Pointing-Pointer Acidic and mesoporous AC to be preferred, despite lower initial efficiency. Black-Right-Pointing-Pointer Oxidative degradation of paracetamol improves biodegradability. Black-Right-Pointing-Pointer Convenient hybrid adsorption-regenerative oxidation process for continuous treatment. - Abstract: The concern about the fate of pharmaceutical products has raised owing to the increasing contamination of rivers, lakes and groundwater. The aim of this paper is to evaluate two different processes for paracetamol removal. The catalytic wet air oxidation (CWAO) of paracetamol on activated carbon was investigated both as a water treatment technique using an autoclave reactor and as a regenerative treatment of the carbon after adsorption in a sequential fixed bed process. Three activated carbons (ACs) from different source materials were used as catalysts: two microporous basic ACs (S23 and C1) and a meso- and micro-porous acidic one (L27). During the first CWAO experiment the adsorption capacity and catalytic performance of fresh S23 and C1 were higher than those of fresh L27 despite its higher surface area. This situation changed after AC reuse, as finally L27 gave the best results after five CWAO cycles. Respirometry tests with activated sludge revealed that in the studied conditions the use of CWAO enhanced the aerobic biodegradability of the effluent. In the ADOX process L27 also showed better oxidation performances and regeneration efficiency. This different ageing was examined through AC physico-chemical properties.

  9. Catalytic wet air oxidation for the treatment of emulsifying wastewater

    Institute of Scientific and Technical Information of China (English)

    ZHAO Jian-fu; CHEN Ling; LU Yi-cheng; TANG Wen-wei

    2005-01-01

    The wet air oxidation (WAO) and catalytic WAO (CWAO) of the high strength emulsifying wastewater containing nonionic surfactants have been investigated in terms of COD and TOC removal. The WAO and homogeneous CWAO processes were carried out at the temperature from 433 K to 513 K, with initial oxygen pressure 1.2 MPa. It was found that homogeneous catalyst copper(Cu ( NO3 )2 )had an fairly good catalytic activity for the WAO process, and the oxidation was catalyzed when the temperature was higher than 473 K.Moreover, several heterogeneous catalysts were proved to be effective for the WAO process. At the temperature 473 K, after 2 h reaction,WAO process could achieve about 75% COD removal and 66% TOC removal, while catalysts Cu/Al2O3 and Mn-Ce/Al2O3 elevated the COD removal up to 86%-89% and that of TOC up to 82%. However, complete elimination of COD and TOC was proved to be difficult even the best non-noble catalyst was used. Therefore, the effluent from WAO or CWAO process need to be further disposed. The bioassay proved that the effluent from WAO process was amenable to the biochemical method.

  10. Copper on activated carbon for catalytic wet air oxidation

    Directory of Open Access Journals (Sweden)

    Nora Dolores Martínez

    2009-03-01

    Full Text Available Textile industry is an important source of water contamination. Some of the organic contaminants cannot be eliminated by nature in a reasonable period. Heterogeneous catalytic wet air oxidation is one of the most effective methods to purify wastewater with organic contaminants. In this work, catalysts based on copper supported on activated carbon were synthesized. The activated carbons were obtained from industrial wastes (apricot core and grape stalk of San Juan, Argentina. These were impregnated with a copper salt and thermically treated in an inert atmosphere. Analysis of specific surface, pore volume, p zc, acidity, basicity and XRD patterns were made in order to characterize the catalysts. The catalytic activity was tested in the oxidation of methylene blue (MB and polyvinyl alcohol (PVA in aqueous phase with pure oxygen. Reaction tests were carried out in a Parr batch reactor at different temperatures, with a 0.2 MPa partial pressure of oxygen. The amount of unconverted organics was measured by spectrophotometry. Higher temperatures were necessary for the degradation of PVA compared to those for methylene blue.

  11. Wet oxidation of activated sludge: transformations and mechanisms.

    Science.gov (United States)

    Urrea, José Luis; Collado, Sergio; Laca, Amanda; Díaz, Mario

    2014-12-15

    Wet oxidation (WO) is an interesting alternative for the solubilization and mineralization of activated sludge. The effects of different temperatures (160-200 °C) and pressures (4-8 MPa), on the evolution of chemical composition and rheological characteristics of a thickened activated sludge during WO are analyzed in this work. Soluble COD increases initially to a maximum and then diminishes, while the apparent viscosity of the mixture falls continuously throughout the experiment. Based on the experimental evolution of the compositions and rheological characteristics of the sludge, a mechanism consisting of two stages in series is proposed. Initially, the solid organic compounds are solubilized following a pseudo-second order kinetic model with respect to solid COD. After that, the solubilized COD was oxidized, showing a pseudofirst kinetic order, by two parallel pathways: the complete mineralization of the organic matter and the formation of highly refractory COD. Kinetic parameters of the model, including the activation energies are mentioned, with good global fitting to the experiments described.

  12. Treatment of hydraulic fracturing wastewater by wet air oxidation.

    Science.gov (United States)

    Wang, Wei; Yan, Xiuyi; Zhou, Jinghui; Ma, Jiuli

    2016-01-01

    Wastewater produced by hydraulic fracturing for oil and gas production is characterized by high salinity and high chemical oxygen demand (COD). We applied a combination of flocculation and wet air oxidation technology to optimize the reduction of COD in the treatment of hydraulic fracturing wastewater. The experiments used different values of flocculant, coagulant, and oxidizing agent added to the wastewater, as well as different reaction times and treatment temperatures. The use of flocculants for the pretreatment of fracturing wastewater was shown to improve treatment efficiency. The addition of 500 mg/L of polyaluminum chloride (PAC) and 20 mg/L of anionic polyacrylamide (APAM) during pretreatment resulted in a COD removal ratio of 8.2% and reduced the suspended solid concentration of fracturing wastewater to 150 mg/L. For a solution of pretreated fracturing wastewater with 12 mL of added H2O2, the COD was reduced to 104 mg/L when reacted at 300 °C for 75 min, and reduced to 127 mg/L when reacted at the same temperature for 45 min while using a 1 L autoclave. An optimal combination of these parameters produced treated wastewater that met the GB 8978-1996 'Integrated Wastewater Discharge Standard' level I emission standard.

  13. USING WET AIR OXIDATION TECHNOLOGY TO DESTROY TETRAPHENYLBORATE

    Energy Technology Data Exchange (ETDEWEB)

    Adu-Wusu, K; Daniel McCabe, D; Bill Wilmarth, B

    2007-04-04

    A bench-scale feasibility study on the use of a Wet Air Oxidation (WAO) process to destroy a slurry laden with tetraphenylborate (TPB) compounds has been undertaken. WAO is an aqueous phase process in which soluble and/or insoluble waste constituents are oxidized using oxygen or oxygen in air at elevated temperatures and pressures ranging from 150 C and 1 MPa to 320 C and 22 MPa. The products of the reaction are CO{sub 2}, H{sub 2}O, and low molecular weight oxygenated organics (e.g. acetate, oxalate). Test results indicate WAO is a feasible process for destroying TPB, its primary daughter products [triphenylborane (3PB), diphenylborinic acid (2PB), and phenylboronic acid (1PB)], phenol, and most of the biphenyl byproduct. The required conditions are a temperature of 300 C, a reaction time of 3 hours, 1:1 feed slurry dilution with 2M NaOH solution, the addition of CuSO{sub 4}.5H{sub 2}O solution (500 mg/L Cu) as catalyst, and the addition of 2000 mL/L of antifoam. However, for the destruction of TPB, its daughter compounds (3PB, 2PB, and 1PB), and phenol without consideration for biphenyl destruction, less severe conditions (280 C and 1-hour reaction time with similar remaining above conditions) are adequate.

  14. Solid state oxidation of phenols to quinones with sodium perborate on wet montmorillonite K10

    Energy Technology Data Exchange (ETDEWEB)

    Hashemi, Mohammed M.; Eftekhari-Sis, Bagher; Khalili, Behzad; Karimi-Jaberi, Zahed [Sharif University of Technology, Tehran (Iran, Islamic Republic of). Dept. of Chemistry]. E-mail: mhashemi@sharif.edu

    2005-09-15

    Phenols were oxidized to quinones using sodium perborate (SPB) on wet montmorillonite as oxidant. The reaction was carried out at ambient temperature on the solid phase under solvent free conditions. (author)

  15. Thermal wet oxidation improves anaerobic biodegradability of raw and digested biowaste

    DEFF Research Database (Denmark)

    Lissens, G.; Thomsen, Anne Belinda; De Baere, L.;

    2004-01-01

    profits. The objective of this research was to enhance the anaerobic biodegradability and methane yields from different biowastes (food waste, yard waste, and digested biowaste already treated in a full-scale biogas plant (DRANCO, Belgium)) by assessing thermal wet oxidation. The biodegradability...... of the waste was evaluated by using biochemical methane potential assays and continuous 3-L methane reactors. Wet oxidation temperature and oxygen pressure (T, 185-220 degreesC; O-2 pressure, 0-12 bar; t, 15 min) were varied for their effect on total methane yield and digestion kinetics of digested biowaste....... Measured methane yields for raw yard waste, wet oxidized yard waste, raw food waste, and wet oxidized food waste were 345, 685, 536, and 571 mL of CH4/g of volatile suspended solids, respectively. Higher oxygen pressure during wet oxidation of digested biowaste considerably increased the total methane...

  16. Degradation of paracetamol by catalytic wet air oxidation and sequential adsorption - Catalytic wet air oxidation on activated carbons.

    Science.gov (United States)

    Quesada-Peñate, I; Julcour-Lebigue, C; Jáuregui-Haza, U J; Wilhelm, A M; Delmas, H

    2012-06-30

    The concern about the fate of pharmaceutical products has raised owing to the increasing contamination of rivers, lakes and groundwater. The aim of this paper is to evaluate two different processes for paracetamol removal. The catalytic wet air oxidation (CWAO) of paracetamol on activated carbon was investigated both as a water treatment technique using an autoclave reactor and as a regenerative treatment of the carbon after adsorption in a sequential fixed bed process. Three activated carbons (ACs) from different source materials were used as catalysts: two microporous basic ACs (S23 and C1) and a meso- and micro-porous acidic one (L27). During the first CWAO experiment the adsorption capacity and catalytic performance of fresh S23 and C1 were higher than those of fresh L27 despite its higher surface area. This situation changed after AC reuse, as finally L27 gave the best results after five CWAO cycles. Respirometry tests with activated sludge revealed that in the studied conditions the use of CWAO enhanced the aerobic biodegradability of the effluent. In the ADOX process L27 also showed better oxidation performances and regeneration efficiency. This different ageing was examined through AC physico-chemical properties.

  17. Development studies for a novel wet oxidation process. Phase 2

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1994-07-01

    DETOX{sup SM} is a catalyzed wet oxidation process which destroys organic materials in an acidic water solution of iron at 373 to 473 K. The solution can be used repeatedly to destroy great amounts of organic materials. Since the process is conducted in a contained vessel, air emissions from the process can be well controlled. The solution is also capable of dissolving and concentrating many heavy and radioactive metals for eventual stabilization and disposal. The Phase 2 effort for this project is site selection and engineering design for a DETOX demonstration unit. Site selection was made using a set of site selection criteria and evaluation factors. A survey of mixed wastes at DOE sites was conducted using the Interim Mixed Waste Inventory Report. Sites with likely suitable waste types were identified. Potential demonstration sites were ranked based on waste types, interest, regulatory needs, scheduling, ability to provide support, and available facilities. Engineering design for the demonstration unit is in progress and is being performed by Jacobs Applied Technology. The engineering design proceeded through preliminary process flow diagrams (PFDs), calculation of mass and energy balances for representative waste types, process and instrumentation diagrams (P and IDs), preparation of component specifications, and a firm cost estimate for fabrication of the demonstration unit.

  18. Purification of carbon nanotube by wet oxidation; Shisshiki sanka ni yoru carbon nanotube no seisei

    Energy Technology Data Exchange (ETDEWEB)

    Morishita, K.; Takarada, T. [Gunma University, Gunma (Japan)

    1997-07-10

    In order to efficiently recover carbon nanotubes, the purification method by wet oxidation with orthoperiodic acid and perchloric acid is investigated. The reactivity of the carbonaceous material toward the acids depends on the type of carbon. Carbon nanotubes are selectively recovered under the mild oxidation conditions. The degree of purification depends on the concentration of orthoperiodic acid. It is suggested that wet oxidation is an effective method for purification of carbon nanotubes. 17 refs., 6 figs.

  19. THE BIOENERGETICS OF AMMONIA AND HYDROXYLAMINE OXIDATION IN NITROSOMONAS-EUROPAEA AT ACID AND ALKALINE PH

    NARCIS (Netherlands)

    FRIJLINK, MJ; ABEE, T; LAANBROEK, HJ; DEBOER, W; KONINGS, WN

    1992-01-01

    Autotrophic ammonia oxidizers depend on alkaline or neutral conditions for optimal activity. Below pH 7 growth and metabolic activity decrease dramatically. Actively oxidizing cells of Nitrosomonas europaea do not maintain a constant internal pH when the external pH is varied from 5 to 8. Studies of

  20. [Degradation of beta-naphthol by catalytic wet air oxidation].

    Science.gov (United States)

    Liu, Jie; Yu, Chao-Ying; Zhao, Pei-Qing; Chen, Ge-Xin

    2012-11-01

    A series of MnO(x)/nano-TiO2 catalysts were prepared and their application in degradation of beta-naphthol by catalytic wet air oxidation (CWAO) was investigated. The catalysts preparation conditions, reaction conditions and its stability were tested. The catalysts had been characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and temperature-programmed reduction (TPR) measurements. The results showed that the decrease of the COD removal for the degradation of beta-naphthol at high Mn loading was due to the aggregation of the highly dispersed Mn species and the formation of the correlated crystals. The decline of the COD removal at high calcination temperature was probably attributed to the weak electron transfer between Mn2O3 and MnO2 and the formation of the inactive Mn2O3. The COD removal had been falling slightly when the catalyst was used 6 times, and this was likely related to the decrease of the diffraction peaks. The catalyst had a high activity when the Mn loading (mass fraction) was 4% and the calcination temperature was 450 degrees C. The COD removal was up to 96.4% at 110 degrees C and 0.5 MPa with this catalyst. The COD removal of 92.4% could be obtained with the MnO(x)/nano-TiO2 catalyst was recycled 6 times. The Mn leaching at 50, 80, 110 and 150 degrees C were all less than 9.3 mg x L(-1) by means of Atomic Absorption Spectroscopy (AAS). The probable degradation pathway was proposed according to some publications.

  1. Oxidative dissolution of spent nuclear fuel in aqueous alkaline solutions - An alternative to the Purex process?

    Energy Technology Data Exchange (ETDEWEB)

    Runde, Wolfgang; Peper, Shane; Brodnax, Lia; Crooks, William; Zehnder, Ralph; Jarvinen, Gordon

    2004-07-01

    As an alternative to acidic reprocessing of spent nuclear, oxidative dissolution of UO{sub 2} into aqueous alkaline solutions and subsequent separation of fission products is considered. The efficacy of such a method is limited by the kinetics of the UO{sub 2} dissolution and the capacity of alkaline solutions for dissolved U(VI) species. We performed a series of dissolution studies on UO{sub 2} and U{sub 3}O{sub 8} in aqueous alkaline solutions applying various oxidants. Among the oxidative agents commonly used to transform low-valence actinides into their higher oxidation states, H{sub 2}O{sub 2} has proven to be the most effective in basic media. Consequently, we investigated the dissolution of UO{sub 2} and U{sub 3}O{sub 8} in NaOH-H{sub 2}O{sub 2} and Na{sub 2}CO{sub 3}-H{sub 2}O{sub 2} solutions and determined the dissolution kinetics as a function of peroxide and hydroxide (carbonate) concentrations. Methods to remove fission products, e.g., Cs, Sr, Ba and Zr, from alkaline solutions will be evaluated based upon their decontamination factors. We will discuss the feasibility of using chemically oxidizing alkaline solutions as an alternative spent nuclear fuel reprocessing method based on results from experimental quantitative investigations. (authors)

  2. Catalytic wet air oxidation with Ni- and Fe-doped mixed oxides derived from hydrotalcites.

    Science.gov (United States)

    Ovejero, G; Rodríguez, A; Vallet, A; Gómez, P; García, J

    2011-01-01

    Catalytic wet air oxidation of Basic Yellow 11 (BY11), a basic dye, was studied in a batch reactor. Layered double hydroxides with the hydrotalcite-like structure containing nickel or iron cations have been prepared by coprecipitation and subsequently calcined leading to Ni- and Fe-doped mixed oxides, respectively. Compared with the results in the wet air oxidation of BY11, these catalysts showed high activity for total organic carbon (TOC), toxicity and dye removal at 120 degrees C and 50 bars after 120 min. It has been demonstrated that the activity depended strongly on the presence of catalyst. The results show that catalysts containing nickel provide a higher extent of oxidation of the dye whereas the reaction carried out with the iron catalyst is faster. The Ni and Fe dispersion determined from the TPR results was higher for the catalysts with a lower Ni or Fe content and decreased for higher Ni or Fe contents. On the basis of activity and selectivity, the Ni containing catalyst with the medium (3%) Ni content was found to be the best catalyst. Finally, a relationship between metal content of the catalyst and reaction rate has been established.

  3. A novel advanced oxidation process——wet electrocatalytic oxidation for high concentrated organic wastewater treatment

    Institute of Scientific and Technical Information of China (English)

    DAI QiZhou; ZHOU MingHua; LEI LeCheng; ZHANG Xing Wang

    2007-01-01

    A novel advanced oxidation process-wet electrocatalytic oxidation(WEO)was studied with p-nitrophenol as model pollutant and β-PbO2 electrode as the anode.Compared with the effect of the individual wet air oxidation(WAO)and electrochemical oxidation(EO),the effect of WEO showed synergistic effect on COD removal under the conditions of temperature 160℃,C=1000mg·L-1,PN2=0.50MPa,Po2=0.9 MPa,current density=3 mA·cm-2,Na2SO4 3 g·L-1.And the synergistic factor got the best value of 0.98 within 120 min after 180 min treatment.The synergistic factor was studied after 120 min treatment at 100℃,120℃,140℃and 160℃,and the effect of 120℃was the best with the value of 1.26.Possible mechanism for the synergistic effect was discussed based on the analysis of free-radical generation and intermediates detected by HPLC and GC/MS.

  4. Selective oxidation of methanol to hydrogen over gold catalysts promoted by alkaline-earth-metal and lanthanum oxides

    NARCIS (Netherlands)

    Hereijgers, B.P.C.; Weckhuysen, B.M.

    2009-01-01

    A series of alumina-supported gold catalysts was investigated for the CO-free production of hydrogen by partial oxidation of methanol. The addition of alkaline-earth metal oxide promoters resulted in a significant improvement of the catalytic performance. The methanol conversion was ca. 85 % with al

  5. The Study of LeachateTreatment by Using Three Advanced Oxidation Process Based Wet air Oxidation

    Directory of Open Access Journals (Sweden)

    Behroz Karimi

    2013-01-01

    Full Text Available Wet air oxidation is regarded as appropriate options for wastewater treatment with average organic compounds. The general purpose of this research is to determine the efficiency of three wet air oxidation methods, wet oxidation with hydrogen peroxide and absorption with activated carbon in removing organic matter and nitrogenous compounds from Isfahan's urban leachate. A leachate sample with the volume of 1.5 liters entered into a steel reactor with the volume of three liters and was put under a 10-bar pressure, at temperatures of 100, 200, and 300[degree sign] as well as three retention times of 30, 60, and 90 minutes. The sample was placed at 18 stages of leachate storage ponds in Isfahan Compost Plant with the volume of 20 liters, using three WPO, WAO methods and a combination of WAO/GAC for leachate pre-treatment. Thirty percent of pure oxygen and hydrogen peroxide were applied as oxidation agents. The COD removal efficiency in WAO method is 7.8-33.3%, in BOD is 14.7-50.6%, the maximum removal percentage (efficiency for NH4-N is 53.3% and for NO3-N is 56.4-73.9%. The removal efficiency of COD and BOD5 is 4.6%-34 and 24%-50 respectively in WPO method. Adding GAC to the reactor, the removal efficiency of all parameters was improved. The maximum removal efficiency was increased 48% for COD, 31%-43.6 for BOD5 by a combinational method, and the ratio of BOD5/COD was also increased to 90%. In this paper, WAO and WPO process was used for Leachate pre-treatment and WAO/GAC combinational process was applied for improving the organic matter removal and leachate treatment; it was also determined that the recent process is much more efficient in removing resistant organic matter.

  6. The study of leachate treatment by using three advanced oxidation process based wet air oxidation.

    Science.gov (United States)

    Karimi, Behroz; Ehrampoush, Mohammad Hassan; Ebrahimi, Asghar; Mokhtari, Mehdi

    2013-01-02

    Wet air oxidation is regarded as appropriate options for wastewater treatment with average organic compounds. The general purpose of this research is to determine the efficiency of three wet air oxidation methods, wet oxidation with hydrogen peroxide and absorption with activated carbon in removing organic matter and nitrogenous compounds from Isfahan's urban leachate. A leachate sample with the volume of 1.5 liters entered into a steel reactor with the volume of three liters and was put under a 10-bar pressure, at temperatures of 100, 200, and 300° as well as three retention times of 30, 60, and 90 minutes. The sample was placed at 18 stages of leachate storage ponds in Isfahan Compost Plant with the volume of 20 liters, using three WPO, WAO methods and a combination of WAO/GAC for leachate pre-treatment. Thirty percent of pure oxygen and hydrogen peroxide were applied as oxidation agents. The COD removal efficiency in WAO method is 7.8-33.3%, in BOD is 14.7-50.6%, the maximum removal percentage (efficiency) for NH4-N is 53.3% and for NO3-N is 56.4-73.9%. The removal efficiency of COD and BOD5 is 4.6%-34 and 24%-50 respectively in WPO method. Adding GAC to the reactor, the removal efficiency of all parameters was improved. The maximum removal efficiency was increased 48% for COD, 31%-43.6 for BOD5 by a combinational method, and the ratio of BOD5/COD was also increased to 90%. In this paper, WAO and WPO process was used for Leachate pre-treatment and WAO/GAC combinational process was applied for improving the organic matter removal and leachate treatment; it was also determined that the recent process is much more efficient in removing resistant organic matter.

  7. A kinetic model of municipal sludge degradation during non-catalytic wet oxidation.

    Science.gov (United States)

    Prince-Pike, Arrian; Wilson, David I; Baroutian, Saeid; Andrews, John; Gapes, Daniel J

    2015-12-15

    Wet oxidation is a successful process for the treatment of municipal sludge. In addition, the resulting effluent from wet oxidation is a useful carbon source for subsequent biological nutrient removal processes in wastewater treatment. Owing to limitations with current kinetic models, this study produced a kinetic model which predicts the concentrations of key intermediate components during wet oxidation. The model was regressed from lab-scale experiments and then subsequently validated using data from a wet oxidation pilot plant. The model was shown to be accurate in predicting the concentrations of each component, and produced good results when applied to a plant 500 times larger in size. A statistical study was undertaken to investigate the validity of the regressed model parameters. Finally the usefulness of the model was demonstrated by suggesting optimum operating conditions such that volatile fatty acids were maximised.

  8. Wet deposition of oxidized nitrogen in the United States Pacific Northwest for 2002

    Data.gov (United States)

    U.S. Geological Survey, Department of the Interior — This spatial data set was created by the U.S. Geological Survey (USGS) to represent the amount of wet deposition of oxidized nitrogen in the Pacific Northwest region...

  9. Graphene oxide as an effective catalyst for wet air oxidation of phenol.

    Science.gov (United States)

    Yang, Shaoxia; Cui, Yuhong; Sun, Yu; Yang, Hongwei

    2014-09-15

    The graphene oxide (GO) and chemically reduced graphene oxides, used as catalysts in absence of any metals, were investigated in the catalytic wet air oxidation (CWAO) of phenol in a batch reactor. The characterization of the materials was measured with scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman, fourier transform infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS). The carbon materials exhibited good phenol and total organic compounds (TOC) removals in the CWAO of phenol. The GO had the highest catalytic activity, total phenol removal was achieved after 40 min, and ca. 84% TOC removal was obtained after 120 min at reaction temperature of 155°C, total pressure of 2.5 MPa and catalyst loading of 0.2 gL(-1).

  10. Decision criteria for the selection of wet oxidation and conventional biological treatment.

    Science.gov (United States)

    Collado, Sergio; Laca, Adriana; Diaz, Mario

    2012-07-15

    The suitability of wet oxidation or biological treatments for the degradation of industrial wastewaters is here discussed. Advantages of these operations, either singly or in combination, are discussed on the basis of previous experimental results from laboratory and industry. Decision diagrams for the selection of conventional biological treatment, wet oxidation or a combination of both techniques are suggested according to the type of pollutant, its concentration and the wastewater flow rate.

  11. CuO impregnated activated carbon for catalytic wet peroxide oxidation of phenol.

    Science.gov (United States)

    Liou, Rey-May; Chen, Shih-Hsiung

    2009-12-15

    This paper presents an original approach to the removal of phenol in synthetic wastewater by catalytic wet peroxide oxidation with copper binding activated carbon (CuAC) catalysts. The characteristics and oxidation performance of CuAC in the wet hydrogen peroxide catalytic oxidation of phenol were studied in a batch reactor at 80 degrees C. Complete conversion of the oxidant, hydrogen peroxide, was observed with CuAC catalyst in 20 min oxidation, and a highly efficient phenol removal and chemical oxygen demand (COD) abatement were achieved in the first 30 min. The good oxidation performance of CuAC catalyst was contributed to the activity enhancement of copper oxide, which was binding in the carbon matrix. It can be concluded that the efficiency of oxidation dominated by the residual H2O2 in this study. An over 90% COD removal was achieved by using the multiple-step addition in this catalytic oxidation.

  12. Kinetics study on catalytic wet air oxidation of phenol by several metal oxide catalysts

    Institute of Scientific and Technical Information of China (English)

    WAN Jia-feng; FENG Yu-jie; CAI Wei-min; YANG Shao-xia; SUN Xiao-jun

    2004-01-01

    Four metal oxide catalysts composed of copper (Cu), stannum (Sn), copper-stannum (Cu-Sn) and copper-cerium(Cu-Ce) respectively were prepared by the co-impregnation method, and γ-alumina(γ-Al2O3) is selected as support. A first-order kinetics model was established to study the catalytic wet air oxidation of phenol at different temperature when these catalysts were used. The model simulations are good agreement with present experimental data. Results showed that the reaction rate constants can be significantly increased when catalysts were used, and the catalyst of 6% Cu-10%Ce/γ-Al2O3 showed the best catalytic activity. This is consistent with the result of catalytic wet air oxidation of phenol and the COD removal can be arrived at 98.2% at temperature 210℃, oxygen partial pressure 3 MPa and reaction time 30 min. The activation energies of each reaction with different catalysts are nearly equal, which is found to be about 42 kJ/mol and the reaction in this study is proved to be kinetics control.

  13. A laboratorial study on influence of alkaline and oxidative environment on preservation of Pinus tabulaeformis pollen

    Institute of Scientific and Technical Information of China (English)

    Fang TIAN; Xianyong CAO; Qinghai XU; Yuecong LI

    2009-01-01

    Different sedimentary settings can influence preservation of pollens, which would lead to mis-interpretation of fossil pollen spectrum. This study investigates the influence on the preservation of Pinus tabulaeformis pollen by simulating alkaline and oxidative environment in the laboratory. There was no obvious change in the content ofPinus tabulaeformis pollen while comparing the original with the ones that were immersed with 10% NaOH liquor for ten days, or boiled for five hours, and or boiled with 20%-30% NaOH for one hour,respectively. However, the pollen fossils were obviously corroded and eroded after being boiled with 40% NaOH for one hour and were seriously corroded after five hours. The result indicates that Pinus tabulaeformis pollen is quite durable in alkaline environment and heating condition within a shorter period of time, although alkaline environment has a disadvantage for its preservation. We also tested the influence of oxidation on Pinus tabulae-formis pollen preservation with KMnO4 as oxidant. The result presents that the number of remaining Pinus tabulaeformis pollen grains decreased quickly after being dipped in KMnO4 along with extending the reaction time and reinforcing oxidant. The rate of remnant pollen grains was less than 1% after being dipped with 2% KMnO4 for one hour. It is suggested that oxidative environment has stronger influence on Pinus tabulaeformis pollen preserva tion than alkaline environment.

  14. A review of wet air oxidation and Thermal Hydrolysis technologies in sludge treatment.

    Science.gov (United States)

    Hii, Kevin; Baroutian, Saeid; Parthasarathy, Raj; Gapes, Daniel J; Eshtiaghi, Nicky

    2014-03-01

    With rapid world population growth and strict environmental regulations, increasingly large volumes of sludge are being produced in today's wastewater treatment plants (WWTP) with limited disposal routes. Sludge treatment has become an essential process in WWTP, representing 50% of operational costs. Sludge destruction and resource recovery technologies are therefore of great ongoing interest. Hydrothermal processing uses unique characteristics of water at elevated temperatures and pressures to deconstruct organic and inorganic components of sludge. It can be broadly categorized into wet oxidation (oxidative) and thermal hydrolysis (non-oxidative). While wet air oxidation (WAO) can be used for the final sludge destruction and also potentially producing industrially useful by-products such as acetic acid, thermal hydrolysis (TH) is mainly used as a pre-treatment method to improve the efficiency of anaerobic digestion. This paper reviews current hydrothermal technologies, roles of wet air oxidation and thermal hydrolysis in sludge treatment, and challenges faced by these technologies.

  15. Magnetic carbon xerogels for the catalytic wet peroxide oxidation of 4-nitrophenol solutions

    OpenAIRE

    Ribeiro, R.; Silva, Adrián; Faria, Joaquim; Gomes, Helder

    2015-01-01

    Catalytic wet peroxide oxidation (CWPO) is a well-known advanced oxidation process for the removal of organic pollutants from industrial process waters and wastewater. Specifically, CWPO employs hydrogen peroxide (H2O2) as oxidation source and a suitable catalyst to promote its decomposition via formation of hydroxyl radicals (HO•), which exhibit high oxidizing potential and serve as effective species in the destruction of a huge range of organic pollutants

  16. Oxidative Alkaline leaching of Americium from simulated high-level nuclear waste sludges

    Energy Technology Data Exchange (ETDEWEB)

    Reed, Wendy A.; Garnov, Alexander Yu.; Rao, Linfeng; Nash, Kenneth L.; Bond, Andrew H.

    2004-01-23

    Oxidative alkaline leaching has been proposed to pre-treat the high-level nuclear waste sludges to remove some of the problematic (e.g., Cr) and/or non-radioactive (e.g., Na, Al) constituents before vitrification. It is critical to understand the behavior of actinides, americium and plutonium in particular, in oxidative alkaline leaching. We have studied the leaching behavior of americium from four different sludge simulants (BiPO{sub 4}, BiPO{sub 4 modified}, Redox, PUREX) using potassium permanganate and potassium persulfate in alkaline solutions. Up to 60% of americium sorbed onto the simulants is leached from the sludges by alkaline persulfate and permanganate. The percentage of americium leached increases with [NaOH] (between 1.0 and 5.0 M). The initial rate of americium leaching by potassium persulfate increases in the order BiPO{sub 4} sludge < Redox sludge < PUREX sludge. The data are most consistent with oxidation of Am{sup 3+} in the sludge to either AmO{sub 2}{sup +} or AmO{sub 2}{sup 2+} in solution. Though neither of these species is expected to exhibit long-term stability in solution, the potential for mobilization of americium from sludge samples would have to be accommodated in the design of any oxidative leaching process for real sludge samples.

  17. Desorption of acetone from alkaline-earth exchanged Y zeolite after propane selective oxidation

    NARCIS (Netherlands)

    Xu, Jiang; Mojet, B.L.; Ommen, van J.G.; Lefferts, L.

    2004-01-01

    The desorption of products from a series of alkaline-earth exchanged Y zeolites after room-temperature propane selective oxidation was investigated by in situ infrared and mass spectroscopy. The intermediate product, isopropylhydroperoxide (IHP), did not desorb during temperature-programmed-desorpti

  18. Propane selective oxidation on alkaline earth exchanged zeolite Y: room temperature in situ IR study

    NARCIS (Netherlands)

    Xu, Jiang; Mojet, Barbara L.; Ommen, van Jan G.; Lefferts, Leon

    2003-01-01

    The effect of zeolite Y ion-exchanged with a series of alkaline-earth cations on selective propane oxidation at room temperature was studied with in situ infrared spectroscopy. Isopropylhydroperoxide was observed as a reaction intermediate and can be decomposed into acetone and water. Contrary to pr

  19. Potential inhibitors from wet oxidation of wheat straw and their effect on growth and ethanol production by ¤Thermoanaerobacter mathranii¤

    DEFF Research Database (Denmark)

    Klinke, H.B.; Thomsen, A.B.; Ahring, B.K.

    2001-01-01

    Alkaline wet oxidation (WO) (using water, 6.5 g/l sodium carbonate, and 12 bar oxygen at 195 degreesC) was used for pre-treating wheat straw (60 g/l), resulting in a hemicellulose-rich hydrolysate and a cellulose-rich solid fraction. The hydrolysate consisted of soluble hemicellulose (9 g....../l), aliphatic carboxylic acids (6 g/l), phenols (0.27 g/l or 1.7 mM), and 2-furoic acid (0.007 g/l). The wet-oxidized wheat straw hydrolysate caused no inhibition of ethanol yield by the anaerobic thermophilic bacterium Thermoanaerobacter mathranii. Nine phenols and 2-furoic acid, identified to be present...

  20. The Nature of Surface Oxides on Corrosion-Resistant Nickel Alloy Covered by Alkaline Water

    Directory of Open Access Journals (Sweden)

    Gervasio DF

    2010-01-01

    Full Text Available Abstract A nickel alloy with high chrome and molybdenum content was found to form a highly resistive and passive oxide layer. The donor density and mobility of ions in the oxide layer has been determined as a function of the electrical potential when alkaline water layers are on the alloy surface in order to account for the relative inertness of the nickel alloy in corrosive environments.

  1. An approach to modeling of silicon oxidation in a wet ultra-diluted ambient

    NARCIS (Netherlands)

    Kovalgin, A.Y.; Hof, A.J.; Schmitz, J.

    2005-01-01

    In this work, we make steps towards developing a new wet-oxidation model of silicon based on electron-stimulated dissociation of H2O molecules. The need for a new model arises from the fact that existing physical models are inadequate to describe the thin-oxide regime. Two regimes of silicon oxidati

  2. Development of a Catalytic Wet Air Oxidation Method to Produce Feedstock Gases from Waste Polymers

    Science.gov (United States)

    Kulis, Michael J.; Guerrero-Medina, Karen J.; Hepp, Aloysius F.

    2012-01-01

    Given the high cost of space launch, the repurposing of biological and plastic wastes to reduce the need for logistical support during long distance and long duration space missions has long been recognized as a high priority. Described in this paper are the preliminary efforts to develop a wet air oxidation system in order to produce fuels from waste polymers. Preliminary results of partial oxidation in near supercritical water conditions are presented. Inherent corrosion and salt precipitation are discussed as system design issues for a thorough assessment of a second generation wet air oxidation system. This work is currently being supported by the In-Situ Resource Utilization Project.

  3. Kinetics of wet air oxidation of glyoxalic acid and oxalic acid

    Energy Technology Data Exchange (ETDEWEB)

    Shende, R.V.; Mahajani, V.V. (Univ. of Bombay (India). Dept. of Chemical Technology)

    1994-12-01

    Oxidation of lower molecular weight monobasic and dibasic acids such as formic acid, acetic acid, glyoxalic acid, and oxalic acid is often the rate-controlling step during wet air oxidation (WAO) of an aqueous waste stream exhibiting very high chemical oxygen demand (COD). The kinetics of WAO of glyoxalic acid and oxalic acid was studied in absence and presence of a cupric sulfate catalyst in the temperature range of 120--245 C and oxygen partial pressure of 0.345--1.380 MPa. The wet oxidation of oxalic acid was found to require more severe conditions as compared to glyoxalic acid. The reaction mechanism and kinetic model have been discussed.

  4. Oxidation mechanism of Fe–16Cr alloy as SOFC interconnect in dry/wet air

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Zhi-Yuan [School of Metallurgical and Ecological Engineering, University of Science and Technology Beijing, Beijing 100083 (China); Wang, Li-Jun, E-mail: lijunwang@ustb.edu.cn [School of Metallurgical and Ecological Engineering, University of Science and Technology Beijing, Beijing 100083 (China); Li, Fu-Shen [School of Material Science Engineering, University of Science and Technology Beijing, Beijing 100083 (China); Chou, Kuo-Chih [School of Metallurgical and Ecological Engineering, University of Science and Technology Beijing, Beijing 100083 (China)

    2013-10-15

    Highlights: •A special thermodynamic description corresponding to the kinetics was applied. •We reported the relationships of degradation time with temperature and moisture. •”Turning time” in the Fe–16Cr alloy oxidation kinetic model was given. •The oxidation mechanism of Fe–16Cr alloy in the wet air was discussed. -- Abstract: Experimental study on the oxidation corrosions of Fe–16Cr alloy was carried out at 800–1100 °C under dry/wet air conditions. Faster oxidation rate was observed at higher temperature and water vapor content. The degradation time t{sub d} between two stages in oxidation process showed an exponential relationship with elevating corrosion temperature in dry air, and a linear relationship with the water content in the case of water vapor introduced to the system. The mechanism of oxidation corrosions of Fe–16Cr alloy was suggested by the Real Physical Picture (RPP) model. It was found that the break-away oxidation in stage II was controlled by diffusion at initial both in dry and wet air, then became linear with the exposure time, which implied that the oxidation rate was then controlled by chemical reaction of the interface between the metal and the oxidized scale. Moreover, the effect of water in the oxidation process is not only to supply more oxygen into system, but also to modify the structures of oxide scale due to the existence of hydrogen atom, which results in the accelerated corrosions.

  5. The Oxidation of AlN in Dry and Wet Oxygen

    Science.gov (United States)

    Opila, Elizabeth; Humphrey, Donald; Jacobson, Nathan; Yoshio, Tetsuo; Oda, Kohei

    1998-01-01

    The oxidation kinetics of AlN containing 3.5 wt% Y2O3 were studied by thermogravimetric analysis in dry oxygen and 10% H2O/balance oxygen at temperatures between 1000 and 1200 C for times between 48 and 100 h. The oxidation kinetics for AlN in dry oxygen were parabolic and of approximately the same magnitude and temperature dependence as other alumina forming materials. In this case, diffusion of oxygen and/or aluminum through the alumina scale is the rate limiting mechanism. The oxidation kinetics for AlN in wet oxygen were nearly linear and much more rapid than rates observed in dry oxygen. Numerous micropores were observed in the alumina formed on AIN in wet oxygen. These pores provide a fast path for oxygen transport. The linear kinetics observed in this case suggest that the interface reaction rate of AlN with wet oxygen is the oxidation rate limiting step.

  6. Ultrasmall PdmMn1-mOx binary alloyed nanoparticles on graphene catalysts for ethanol oxidation in alkaline media

    Science.gov (United States)

    Ahmed, Mohammad Shamsuddin; Park, Dongchul; Jeon, Seungwon

    2016-03-01

    A rare combination of graphene (G)-supported palladium and manganese in mixed-oxides binary alloyed catalysts (BACs) have been synthesized with the addition of Pd and Mn metals in various ratios (G/PdmMn1-mOx) through a facile wet-chemical method and employed as an efficient anode catalyst for ethanol oxidation reaction (EOR) in alkaline fuel cells. The as prepared G/PdmMn1-mOx BACs have been characterized by several instrumental techniques; the transmission electron microscopy images show that the ultrafine alloyed nanoparticles (NPs) are excellently monodispersed onto the G. The Pd and Mn in G/PdmMn1-mOx BACs have been alloyed homogeneously, and Mn presents in mixed-oxidized form that resulted by X-ray diffraction. The electrochemical performances, kinetics and stability of these catalysts toward EOR have been evaluated using cyclic voltammetry in 1 M KOH electrolyte. Among all G/PdmMn1-mOx BACs, the G/Pd0.5Mn0.5Ox catalyst has shown much superior mass activity and incredible stability than that of pure Pd catalysts (G/Pd1Mn0Ox, Pd/C and Pt/C). The well dispersion, ultrafine size of NPs and higher degree of alloying are the key factor for enhanced and stable EOR electrocatalysis on G/Pd0.5Mn0.5Ox.

  7. Kinetics of wet oxidation of propionic and 3-hydroxypropionic acids

    Energy Technology Data Exchange (ETDEWEB)

    Shende, R.V.; Levec, J. [National Inst. of Chemistry, Ljubljana (Slovenia). Lab. for Catalysis and Chemical Reaction Engineering]|[Univ. of Ljubljana (Slovenia). Dept. of Chemical Engineering

    1999-07-01

    Oxidation of aqueous solutions of 3-hydroxypropionic (3-HPA) and propionic acids (PA) was studied in a titanium high-pressure reactor at 280--310 C using oxygen partial pressures between 10 and 45 bar. Oxidation of both acids was found to obey first-order kinetic with respect to their concentrations as well as to their lumped TOC concentrations. Oxidation rate revealed a half order dependence with respect to oxygen for oxidation of both acids. In the case of 3-HPA oxidation, the activation energy was found to be 135 kJ/mol, and it was 140 kJ/mol when lumped concentration TOC was used. The activation energy for PA oxidation is 150 kJ/mol, and it is slightly higher, 158 kJ/mol, for TOC reduction. Almost complete conversion of 3-HPA was achieved at 300 C after 1 h, whereas 95% conversion of PA acid was obtained at 310 C after 3 h. During oxidation of 3-HPA, 3-oxopropionic and acetic acids were identified as intermediate products. Oxidation of PA yielded acetic and formic acids as intermediates; at oxygen partial pressures above 25 bar and 310 C, the formation of acetic acid was appreciably reduced. In both cases, however, direct oxidation to carbon dioxide and water was found to be the main reaction route.

  8. Reactive dye house wastewater treatment. Use of hybrid technology: Membrane, sonication followed by wet oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Dhale, A.D.; Mahajani, V.V. [Univ. of Mumbai (India)

    1999-05-01

    To address problems associated with treatment of an aqueous waste stream from a reactive dye house, a model dye, turquoise blue CI25, was studied. A hybrid technology, membrane separation followed by sonication and wet oxidation, has been demonstrated to treat the wastewater for reuse and discharge. Experiments were first performed with the reactive dye solution in water. A nanofiltration membrane (MPT 30) was found to be suitable to concentrate the dye. The concentrate was then treated with a wet oxidation process. Kinetics studies were performed with and without catalyst, in the temperature range of 170--215 C. The color destruction achieved was > 99%. After process parameters were fixed, studies were conducted with the actual dye waste stream. The actual waste stream was found to be refractory for wet oxidation under the above conditions. Sonication of the concentrate obtained after membrane filtration, in the presence of CuSO{sub 4}, made the waste stream amenable to wet oxidation. Sonication followed by wet oxidation was found to be more effective at near neutral conditions as compared to basic conditions.

  9. Alkaline earth oxide nanoparticles as destructive absorbents for environmental toxins

    Energy Technology Data Exchange (ETDEWEB)

    Moscovici, J.; Latreche, K. [Univ. Paris XII, Groupe de Physique des Milieux Denses, Creteil (France); Michalowicz, A. [Univ. Paris Sud, LURE, Orsay (France); Decker, S.; Lagadic, I.; Klabunde, K. [Kansas State Univ., Chemistry Dept., Manhattan, Kansas (United States)

    1999-11-01

    Sr and Ca oxide nanoparticles are very reactive materials used to mitigate atmospheric pollution and to sequester polluting molecules. We have studied the structure of SrO nanoparticles, using Sr K-edge and Fe K-edge XAFS, that were prepared with various reactivities, with or without a Fe{sub 2}O{sub 3} coating, and before and after reaction with CCl{sub 4} or SO2. For CCl4, the polluting fraction of the reagent is totally absorbed in the bulk particle. For SO{sub 2}, the results show a total reaction for the Aerogel Preparation (AP) compound. For the coated particles before reaction, the iron oxide has a very disordered structure, and it is mixed with small metallic iron clusters for Conventional Preparation (CP) compounds. (au) 4 refs.

  10. Oxidation and mineralisation of substituted phenols by Fenton's reagent and catalytic wet oxidation.

    Science.gov (United States)

    Santos, A; Rodriguez, S; Garcia-Ochoa, F; Yustos, P

    2007-01-01

    Catalytic abatement of solutions of 1,000 mg/L in phenol, ortho and para nitrophenol and ortho and para cresols was acomplished by using two catalytic systems. Fenton's reagent was used at 50 degrees C by adding 10 mg/L of ferrous cation and different dosages of H2O2. The mixture was reacting isothermically in a batch way during 3 hours. Catalytic wet oxidation (CWO) was carried out by using a commercial Activated Carbon, Industrial React FE01606A, CWO runs were carried out in a fixed bed reactor (FBR) with concurrent upflow. Temperature and oxygen pressure of the reactor were set to 160 degrees C and 16 bar, respectively. While phenols are quicky oxidised by the Fenton reagent higher mineralisation was obtained in the CWO process.

  11. Activity of Cu-activated carbon fiber catalyst in wet oxidation of ammonia solution.

    Science.gov (United States)

    Hung, Chang-Mao

    2009-07-30

    Aqueous solutions of 200-1000 mg/L of ammonia were oxidized in a trickle-bed reactor using Cu-activated carbon fiber (ACF) catalysts, which were prepared by incipient wet impregnation with aqueous solutions of copper nitrate that was deposited on ACF substrates. The results reveal that the conversion of ammonia by wet oxidation in the presence of Cu-ACF catalysts was a function of the metal loading weight ratio of the catalyst. The total conversion efficiency of ammonia was 95% during wet oxidation over the catalyst at 463 K at an oxygen partial pressure of 3.0 MPa. Moreover, the effect of the initial concentration of ammonia and the reaction temperature on the removal of ammonia from the effluent streams was also studied at a liquid space velocity of less than 3.0 h(-1).

  12. Wet Oxidation Pre-Treatment – the Way To Improve Economics of Energy Production From Manure?

    DEFF Research Database (Denmark)

    Uellendahl, Hinrich; Mladenovska, Zuzana; Langvad, Niels Bo

    2006-01-01

    and Wheatley, 1993). The combination of high temperature and pressure, together with the addition of oxygen in the wet oxidation process, has shown a superior potential for increasing the hydrolysis of lignocellulosic biomass with subsequent ethanol fermentation. In the present study the wet oxidation process...... was tested as pretreatment for increasing the biogas yield of the fiber fraction of manure. The wet oxidation pretreatment in combination with solid liquid separation of manure by using either chemical precipitation or decanter centrifuge (Møller et al., 2004) could be a promising option for a significant......Throughout recent years, several physical, chemical and biological pretreatment methods have been tested with limited success in order to increase hydrolysis of the lignocellulose structure of manure fibers (Fan et al., 1982; Gharpuray et al., 1983; Grethlein, 1984; Hartmann et. al. 2000; Hobson...

  13. Wet Etching of Heat Treated Atomic Layer Chemical Vapor Deposited Zirconium Oxide in HF Based Solutions

    Science.gov (United States)

    Balasubramanian, Sriram; Raghavan, Srini

    2008-06-01

    Alternative materials are being considered to replace silicon dioxide as gate dielectric material. Of these, the oxides of hafnium and zirconium show the most promise. However, integrating these new high-k materials into the existing complementary metal-oxide-semiconductor (CMOS) process remains a challenge. One particular area of concern is the wet etching of heat treated high-k dielectrics. In this paper, work done on the wet etching of heat treated atomic layer chemical vapor deposited (ALCVD) zirconium oxide in HF based solutions is presented. It was found that heat treated material, while refractory to wet etching at room temperature, is more amenable to etching at higher temperatures when methane sulfonic acid is added to dilute HF solutions. Selectivity over SiO2 is still a concern.

  14. A novel oxidation-based wet etching method for AlGaN/GaN heterostructures

    Institute of Scientific and Technical Information of China (English)

    Cai Jinbao; Wang Jinyan; Liu Yang; Xu Zhe; Wang Maojun; Yu Min; Xie Bing

    2013-01-01

    A novel wet etching method for AlGaN/GaN heterojunction structures is proposed using thermal oxidation followed by wet etching in KOH solution.It is found that an AlGaN/GaN heterostructure after high temperature oxidation above 700 ℃ could be etched off in a homothermal (70 ℃) KOH solution while the KOH solution had no etching effects on the region of the A1GaN/GaN heterostructure protected by a SiO2 layer during the oxidation process.A groove structure with 150 nm step depth on an AlGaN/GaN heterostructure was formed after 8 h thermal oxidation at 900 ℃ followed by 30 min treatment in 70 ℃ KOH solution.As the oxidation time increases,the etching depth approaches saturation and the roughness of the etched surface becomes much better.The physical mechanism of this phenomenon is also discussed.

  15. Formation and degradation of valuable intermediate products during wet oxidation of municipal sludge.

    Science.gov (United States)

    Baroutian, Saeid; Gapes, Daniel J; Sarmah, Ajit K; Farid, Mohammed M; Young, Brent R

    2016-04-01

    The current study investigated the formation of organic acids and alcohols as major intermediate products of wet oxidation of municipal sludge. Municipal sludge was subjected to 60-min wet oxidation at temperatures ranging from 220 to 240°C, with 20bar oxygen partial pressure. Acetic acid was the main intermediate compound produced in this study, followed by propionic, n-butyric, iso-butyric and pentanoic acids and methanol. It was found that the process severity has a significant influence on the formation and degradation of these intermediate products.

  16. Catalytic wet air oxidation of aniline with nanocasted Mn-Ce-oxide catalyst.

    Science.gov (United States)

    Levi, R; Milman, M; Landau, M V; Brenner, A; Herskowitz, M

    2008-07-15

    The catalytic wet air oxidation of aqueous solution containing 1000 ppm aniline was conducted in a trickle-bed reactor packed with a novel nanocasted Mn-Ce-oxide catalyst (surface area of 300 m2/g) prepared using SBA-15 silica as a hard template. A range of liquid hourly space velocities (5-20 h(-1)) and temperatures (110-140 degrees C) at 10 bar of oxygen were tested. The experiments were conducted to provide the intrinsic performance of the catalysts. Complete aniline conversion, 90% TOC conversion, and 80% nitrogen mineralization were achieved at 140 degrees C and 5 h(-1). Blank experiments yielded relatively low homogeneous aniline (<35%) and negligible TOC conversions. Fast deactivation of the catalysts was experienced due to leaching caused by complexation with aniline. Acidification of the solution with HCI (molar HCI to aniline ratio of 1.2) was necessary to avoid colloidization and leaching of the nanoparticulate catalyst components. The catalyst displayed stable performance for over 200 h on stream.

  17. Preparation of rare-earth metal complex oxide catalysts for catalytic wet air oxidation

    Institute of Scientific and Technical Information of China (English)

    LI Ning; LI Guangming; YAO Zhenya; ZHAO Jianfu

    2007-01-01

    Catalytic wet air oxidation(CWAO)is one of the most promising technologies for pollution abatement.Developing catalysts with high activity and stability is crucial for the application of the CWAO process.The Mn/Ce complex oxide catalyrsts for CWAO of high concentration phenol containing wastewater were prepared by coprecipitation.The catalyst preparation conditions were optimized by using an orthogonal layout method and single-factor experimental analysis.The Mn/Ce serial catalysts were characterized by Brunauer-Emmett-Teller(BET)analysis and the metal cation leaching was measured by inductively coupled plasma torch-atomic emission spectrometry(ICP-AES).The results show that the catalysts have high catalytic activities even at a low temperature(80℃)and low oxygen partial pressure(0.5 MPa)in a batch reactor.The metallic ion leaching is comparatively low(Mn<6.577 mg/L and Ce<0.6910 mg/L,respectively)in the CWAO process.The phenol,CODCD and TOC removal efficiencies in the solution exceed 98.5% using the optimal catalyst(named CSP).The new catalyst would have a promising application in CWAO treatment of high concentration organic wastewater.

  18. Fabricating nanostructures through a combination of nano-oxidation and wet etching on silicon wafers with different surface conditions.

    Science.gov (United States)

    Huang, Jen-Ching

    2012-01-01

    This study investigates the surface conditions of silicon wafers with native oxide layers (NOL) or hydrogen passivated layers (HPL) and how they influence the processes of nano-oxidation and wet etching. We also explore the combination of nano-oxidation and wet etching processes to produce nanostructures. Experimental results reveal that the surface conditions of silicon wafers have a considerable impact on the results of nano-oxidation when combined with wet etching. The height and width of oxides on NOL samples exceeded the dimensions of oxides on HPL samples, and this difference became increasingly evident with an increase in applied bias voltage. The height of oxidized nanolines on the HPL sample increased after wet etching; however, the width of the lines increased only marginally. After wet etching, the height and width of oxides on the NOL were more than two times greater than those on the HPL. Increasing the applied bias voltage during nano-oxidation on NOL samples increased both the height and width of the oxides. After wet etching however, the increase in bias voltage appeared to have little effect on the height of oxidized nanolines, but the width of oxidized lines increased. This study also discovered that the use of higher applied bias voltages on NOL samples followed by wet etching results in nanostructures with a section profile closely resembling a curved surface. The use of this technique enabled researchers to create molds in the shape of a silicon nanolens array and an elegantly shaped nanoscale complex structures mold.

  19. A facile chemical route for recovery of high quality zinc oxide nanoparticles from spent alkaline batteries.

    Science.gov (United States)

    Deep, Akash; Sharma, Amit L; Mohanta, Girish C; Kumar, Parveen; Kim, Ki-Hyun

    2016-05-01

    Recycling of spent domestic batteries has gained a great environmental significance. In the present research, we propose a new and simple technique for the recovery of high-purity zinc oxide nanoparticles from the electrode waste of spent alkaline Zn-MnO2 batteries. The electrode material was collected by the manual dismantling and mixed with 5M HCl for reaction with a phosphine oxide reagent Cyanex 923® at 250°C for 30min. The desired ZnO nanoparticles were restored from the Zn-Cyanex 923 complex through an ethanolic precipitation step. The recovered particle product with about 5nm diameter exhibited fluorescent properties (emission peak at 400nm) when excited by UV radiation (excitation energy of 300nm). Thus, the proposed technique offered a simple and efficient route for recovering high purity ZnO nanoparticles from spent alkaline batteries.

  20. Electrocatalytic Oxidation of Cellulose to Gluconate on Carbon Aerogel Supported Gold Nanoparticles Anode in Alkaline Medium

    OpenAIRE

    Hanshuang Xiao; Meifen Wu; Guohua Zhao

    2015-01-01

    The development of high efficient and low energy consumption approaches for the transformation of cellulose is of high significance for a sustainable production of high value-added feedstocks. Herein, electrocatalytic oxidation technique was employed for the selective conversion of cellulose to gluconate in alkaline medium by using concentrated HNO3 pretreated carbon aerogel (CA) supported Au nanoparticles as anode. Results show that a high gluconate yield of 67.8% and sum salts yield of 88.9...

  1. Occurrence and activity of iron- and sulfur-oxidizing microorganisms in alkaline coal strip mine spoils.

    Science.gov (United States)

    Olson, G J; McFeters, G A; Temple, K L

    1981-03-01

    Spoils samples collected from a coal strip mine in southeastern Montana were examined for populations and activities of iron- and sulfur-oxidizing bacteria. Spoils examined were of three types: (a) acidic pyrite-rich waste coal, (b) oxidation halo material, and (c) alkaline material, which was the most widespread type. Bacterial numbers, sulfur oxidation, and(14)CO2 uptake activity declined to low levels in the summer when spoils were dry. Even in wetter spring months pyritic spoils contained relatively low numbers of acidophilic iron- and sulfur-oxidizing bacteria, probably indicative of water stress since the same spoils incubated with excess water or dilute mineral salts showed considerably greater bacterial numbers and activity. Certain wells in coal and spoils aquifers contained substantial populations of iron-oxidizing acidophilic bacteria. However, these wells were always of alkaline or neutral pH, indicating that bacterial pyrite oxidation occurred where groundwaters contacted either replaced spoils or coal that contained pyrite or other metal sulfides. Bacterial activity may contribute to trace metal and sulfate leaching in the area.

  2. Study on rare earth/alkaline earth oxide-doped CeO2 solid electrolyte

    Institute of Scientific and Technical Information of China (English)

    YAN Kai; ZHEN Qiang; Song Xiwen

    2007-01-01

    Five types of rare earth/alkaline earth oxide-doped CeO2 superfine-powders were synthesized by a low-temperature combustion technique. The relevant solid electrolyte materials were also sintered by pressureless sintering at different temperatures. The results of X-ray diffraction and transmission electron microscopy showed that the grain size of the powders was approximately 20-30 nm, and rare earth/alkaline earth oxides were completely dissolved into ceria-based solid solution with fluorite structure. The electrical conductivities of the Sm2O3-CeO2 system were measured by the ac impedance technique in air at temperatures ranging from 513-900℃. The results indicated that the ionic conductivities of Sm0.20Ce0.8O1.875 solid electrolyte increase with increasing sintering temperature, and the relationship between the conductivities and measuring temperature obeys the Arrhenius equation. Then the Sm2O3-CeO2 material was further doped with other rare earth/alkaline earth oxide, and the conductivities improve with the effective index.

  3. Alkaline earth metal doped tin oxide as a novel oxygen storage material

    Energy Technology Data Exchange (ETDEWEB)

    Dong, Qiang, E-mail: dong@tagen.tohoku.ac.jp [Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, 2-1-1 Katahira, Aoba-ku Sendai 980-8577 (Japan); Yin, Shu; Yoshida, Mizuki; Wu, Xiaoyong; Liu, Bin [Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, 2-1-1 Katahira, Aoba-ku Sendai 980-8577 (Japan); Miura, Akira; Takei, Takahiro; Kumada, Nobuhiro [Department of Research Interdisciplinary Graduate School of Medicine and Engineering, University of Yamanashi, Miyamae cho-7, Kofu 400-8511 (Japan); Sato, Tsugio [Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, 2-1-1 Katahira, Aoba-ku Sendai 980-8577 (Japan)

    2015-09-15

    Alkaline earth metal doped tin oxide (SnO{sub 2}) hollow nanospheres with a diameter of 50 nm have been synthesized successfully via a facial solvothermal route in a very simple system composed of only ethanol, acetic acid, SnCl{sub 4}·5H{sub 2}O and A(NO{sub 3}){sub 2}·xH{sub 2}O (A = Mg, Ca, Sr, Ba). The synthesized undoped SnO{sub 2} and A-doped SnO{sub 2} hollow nanospheres were characterized by the oxygen storage capacity (OSC), X-ray diffraction, transmission electron microscopy and the Brunauer–Emmet–Teller (BET) technique. The OSC values of all samples were measured using thermogravimetric-differential thermal analysis. The incorporation of alkaline earth metal ion into tin oxide greatly enhanced the thermal stability and OSC. Especially, Ba-doped SnO{sub 2} hollow nanospheres calcined at 1000 °C for 20 h with a BET surface area of 61 m{sup 2} g{sup −1} exhibited the considerably high OSC of 457 μmol-O g{sup −1} and good thermal stability. Alkaline earth metal doped tin oxide has the potential to be a novel oxygen storage material.

  4. Design, fabrication and testing of a wet oxidation waste processing system. [for manned space flight

    Science.gov (United States)

    1975-01-01

    The wet oxidation of sewage sludge during space flight was studied for water and gas recovery, and the elimination of overboard venting. The components of the system are described. Slurry and oxygen supply modules were fabricated and tested. Recommendations for redesign of the equipment are included.

  5. Kinetics and Mechanism of Oxidation of L-Cystine by Hexacyanoferrate(III in Alkaline Medium

    Directory of Open Access Journals (Sweden)

    Annapurna Nowduri

    2009-01-01

    Full Text Available Kinetics of oxidation of L-cystine by hexacyanoferrate(III was studied in alkaline medium at 30 °C. The reaction was followed spectrophotometrically at λmax = 420 nm. The reaction was found to be first order dependence each on [HCF(III] and [cystine]. It was found that the rate of the reaction increases with increase in [OH-]. The oxidation product of the reaction was found to be cysteic acid. A plausible mechanism has been proposed to account for the experimental results.

  6. Pilot Testing of Mercury Oxidation Catalysts for Upstream of Wet FGD Systems

    Energy Technology Data Exchange (ETDEWEB)

    Gary Blythe; Conor Braman; Katherine Dombrowski; Tom Machalek

    2010-12-31

    This document is the final technical report for Cooperative Agreement DE-FC26-04NT41992, 'Pilot Testing of Mercury Oxidation Catalysts for Upstream of Wet FGD Systems,' which was conducted over the time-period January 1, 2004 through December 31, 2010. The objective of this project has been to demonstrate at pilot scale the use of solid catalysts and/or fixed-structure mercury sorbents to promote the removal of total mercury and oxidation of elemental mercury in flue gas from coal combustion, followed by wet flue gas desulfurization (FGD) to remove the oxidized mercury at high efficiency. The project was co-funded by the U.S. DOE National Energy Technology Laboratory (DOE-NETL), EPRI, Great River Energy (GRE), TXU Energy (now called Luminant), Southern Company, Salt River Project (SRP) and Duke Energy. URS Group was the prime contractor. The mercury control process under development uses fixed-structure sorbents and/or catalysts to promote the removal of total mercury and/or oxidation of elemental mercury in the flue gas from coal-fired power plants that have wet lime or limestone FGD systems. Oxidized mercury not adsorbed is removed in the wet FGD absorbers and leaves with the byproducts from the FGD system. The project has tested candidate materials at pilot scale and in a commercial form, to provide engineering data for future full-scale designs. Pilot-scale catalytic oxidation tests have been completed for periods of approximately 14 to19 months at three sites, with an additional round of pilot-scale fixed-structure sorbent tests being conducted at one of those sites. Additionally, pilot-scale wet FGD tests have been conducted downstream of mercury oxidation catalysts at a total of four sites. The sites include the two of three sites from this project and two sites where catalytic oxidation pilot testing was conducted as part of a previous DOE-NETL project. Pilot-scale wet FGD tests were also conducted at a fifth site, but with no catalyst or fixed

  7. Influence of substrate particle size and wet oxidation on physical surface structures and enzymatic hydrolysis of wheat straw.

    Science.gov (United States)

    Pedersen, Mads; Meyer, Anne S

    2009-01-01

    In the worldwide quest for producing biofuels from lignocellulosic biomass, the importance of the substrate pretreatment is becoming increasingly apparent. This work examined the effects of reducing the substrate particle sizes of wheat straw by grinding prior to wet oxidation and enzymatic hydrolysis. The yields of glucose and xylose were assessed after treatments with a benchmark cellulase system consisting of Celluclast 1.5 L (Trichoderma reesei) and Novozym 188 beta-glucosidase (Aspergillus niger). Both wet oxidized and not wet oxidized wheat straw particles gave increased glucose release with reduced particle size. After wet oxidation, the glucose release from the smallest particles (53-149 mum) reached 90% of the theoretical maximum after 24 h of enzyme treatment. The corresponding glucose release from the wet oxidized reference samples (2-4 cm) was approximately 65% of the theoretical maximum. The xylose release only increased (by up to 39%) with particle size decrease for the straw particles that had not been wet oxidized. Wet oxidation pretreatment increased the enzymatic xylose release by 5.4 times and the glucose release by 1.8 times across all particle sizes. Comparison of scanning electron microscopy images of the straw particles revealed edged, nonspherical, porous particles with variable surface structures as a result of the grinding. Wet oxidation pretreatment tore up the surface structures of the particles to retain vascular bundles of xylem and phloem. The enzymatic hydrolysis left behind a significant amount of solid, apparently porous structures within all particles size groups of both the not wet oxidized and wet oxidized particles.

  8. Catalytic wet oxidation of thiocyanate with homogeneous copper(II) sulphate catalyst.

    Science.gov (United States)

    Collado, Sergio; Laca, Adriana; Díaz, Mario

    2010-05-15

    The wet oxidation of thiocyanate has been investigated in a semi-batch reactor at temperatures between 423 and 473 K and pressures between 6.1 x 10(3) and 1.0 x 10(4)kPa in the presence of copper(II) sulphate as catalyst. The effects of copper concentration, initial thiocyanate concentration, pressure and temperature on the reaction rate were analyzed and the main products of reaction were identified. A kinetic model for the Cu-catalyzed reaction is here proposed, including temperature, oxygen concentration, and the reduction of Cu(2+) to Cu(+) that gives an accurate prediction of the oxidation process under the assayed conditions. A mechanistic model based on the formation of a transition complex between a copper cation and two thiocyanate anions has been proposed for the catalytic wet oxidation.

  9. Catalytic wet oxidation of thiocyanate with homogeneous copper(II) sulphate catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Collado, Sergio; Laca, Adriana [Department of Chemical Engineering and Environmental Technology, University of Oviedo, c/ Julian Claveria s/n, E-33071, Oviedo (Spain); Diaz, Mario, E-mail: mariodiaz@uniovi.es [Department of Chemical Engineering and Environmental Technology, University of Oviedo, c/ Julian Claveria s/n, E-33071, Oviedo (Spain)

    2010-05-15

    The wet oxidation of thiocyanate has been investigated in a semi-batch reactor at temperatures between 423 and 473 K and pressures between 6.1 x 10{sup 3} and 1.0 x 10{sup 4} kPa in the presence of copper(II) sulphate as catalyst. The effects of copper concentration, initial thiocyanate concentration, pressure and temperature on the reaction rate were analyzed and the main products of reaction were identified. A kinetic model for the Cu-catalyzed reaction is here proposed, including temperature, oxygen concentration, and the reduction of Cu{sup 2+} to Cu{sup +} that gives an accurate prediction of the oxidation process under the assayed conditions. A mechanistic model based on the formation of a transition complex between a copper cation and two thiocyanate anions has been proposed for the catalytic wet oxidation.

  10. Quantification of activated carbon contents in soils and sediments using chemothermal and wet oxidation methods.

    Science.gov (United States)

    Brändli, Rahel C; Bergsli, Anders; Ghosh, Upal; Hartnik, Thomas; Breedveld, Gijs D; Cornelissen, Gerard

    2009-12-01

    Activated carbon (AC) strongly sorbs organic pollutants and can be used for remediation of soils and sediments. A method for AC quantification is essential to monitor AC (re)distribution. Since AC is black carbon (BC), two methods for BC quantification were tested for AC mixed in different soils and sediments: i) chemothermal oxidation (CTO) at a range of temperatures and ii) wet-chemical oxidation with a potassium dichromate/sulfuric acid solution. For three soils, the amount of AC was accurately determined by CTO at 375 degrees C. For two sediments, however, much of the AC disappeared during combustion at 375 degrees C, which could probably be explained by catalytic effects by sediment constituents. CTO at lower temperatures (325-350 degrees C) was a feasible alternative for one of the sediments. Wet oxidation effectively functioned for AC quantification in sediments, with almost complete AC recovery (81-92%) and low remaining amounts of native organic carbon (5-16%).

  11. Ultra-high performance supercritical fluid chromatography of lignin-derived phenols from alkaline cupric oxide oxidation.

    Science.gov (United States)

    Sun, Mingzhe; Lidén, Gunnar; Sandahl, Margareta; Turner, Charlotta

    2016-08-01

    Traditional chromatographic methods for the analysis of lignin-derived phenolic compounds in environmental samples are generally time consuming. In this work, an ultra-high performance supercritical fluid chromatography method with a diode array detector for the analysis of major lignin-derived phenolic compounds produced by alkaline cupric oxide oxidation was developed. In an analysis of a collection of 11 representative monomeric lignin phenolic compounds, all compounds were clearly separated within 6 min with excellent peak shapes, with a limit of detection of 0.5-2.5 μM, a limit of quantification of 2.5-5.0 μM, and a dynamic range of 5.0-2.0 mM (R(2) > 0.997). The new ultra-high performance supercritical fluid chromatography method was also applied for the qualitative and quantitative analysis of lignin-derived phenolic compounds obtained upon alkaline cupric oxide oxidation of a commercial humic acid. Ten out of the previous eleven model compounds could be quantified in the oxidized humic acid sample. The high separation power and short analysis time obtained demonstrate for the first time that supercritical fluid chromatography is a fast and reliable technique for the analysis of lignin-derived phenols in complex environmental samples.

  12. Study of the electrochemical oxidation mechanism of formaldehyde on gold electrode in alkaline solution

    Institute of Scientific and Technical Information of China (English)

    Rui-Wen Yan; Bao-Kang Jin

    2013-01-01

    The oxidation of formaldehyde in alkaline solution was studied by in situ rapid-scan time-resolved IR spectroelectrochemistry (RS-TR-FTIRS) method.In the potential range between-0.7 V and 0.2 V,the gem-diol anions were oxidized (according to the 2765 cm-1 ofvH-o and 1034 cm-1 ofvco downward IR bands) and the formate ions appeared (according to the 1588,1357 cm-1 of the asymmetric and symmetricvoco and 1380 cm-1 ofδc-H upward IR bands) in aqueous solution.It was also confirmed that gem-diol anion was oxidized (according to the 2026,1034 cm-1 downward IR bands) to formate ions (according to the 1595,1357,1380 cm-1 upward IR bands) and water (according to the 3427 cm-1 ofvH-o upward IR band) in heavy water solution.The results illustrated that formaldehyde formed gem-diol anion in alkaline solution and was absorbed on the electrode surface; then gem-diol anion was oxidized to formate ions and water.

  13. Oxidation Kinetics of Chemically Vapor-Deposited Silicon Carbide in Wet Oxygen

    Science.gov (United States)

    Opila, Elizabeth J.

    1994-01-01

    The oxidation kinetics of chemically vapor-deposited SiC in dry oxygen and wet oxygen (P(sub H2O) = 0.1 atm) at temperatures between 1200 C and 1400 C were monitored using thermogravimetric analysis. It was found that in a clean environment, 10% water vapor enhanced the oxidation kinetics of SiC only very slightly compared to rates found in dry oxygen. Oxidation kinetics were examined in terms of the Deal and Grove model for oxidation of silicon. It was found that in an environment containing even small amounts of impurities, such as high-purity Al2O3 reaction tubes containing 200 ppm Na, water vapor enhanced the transport of these impurities to the oxidation sample. Oxidation rates increased under these conditions presumably because of the formation of less protective sodium alumino-silicate scales.

  14. Catalytic wet oxidation of ammonia solution: activity of the nanoscale platinum-palladium-rhodium composite oxide catalyst.

    Science.gov (United States)

    Hung, Chang-Mao

    2009-04-15

    Aqueous solutions of 400-1000 mg/L of ammonia were oxidized in a trickle-bed reactor (TBR) in this study of nanoscale platinum-palladium-rhodium composite oxide catalysts, which were prepared by the co-precipitation of H(2)PtCl(6), Pd(NO(3))(3) and Rh(NO(3))(3). Hardly any of the dissolved ammonia was removed by wet oxidation in the absence of any catalyst, whereas about 99% of the ammonia was reduced during wet oxidation over nanoscale platinum-palladium-rhodium composite oxide catalysts at 503 K in an oxygen partial pressure of 2.0 MPa. A synergistic effect exists in the nanoscale platinum-palladium-rhodium composite structure, which is the material with the highest ammonia reduction activity. The nanometer-sized particles were characterized by TEM, XRD and FTIR. The effect of the initial concentration and reaction temperature on the removal of ammonia from the effluent streams was also studied at a liquid hourly space velocity of under 9 h(-1) in the wet catalytic processes.

  15. Effect of Alloying Additions on the Oxidation of High Speed Steels under Dry and Wet Conditions

    Institute of Scientific and Technical Information of China (English)

    F.C. RIZZO; M.J.MONTEIRO; S.R.J.SAUNDERS

    2009-01-01

    An investigation has been carried out into the effects of chromium and vanadium content on the oxidation rate and on the adhesion of oxide scales grown on three different chemical compositions of high speed steels under dry and wet conditions. The oxidation tests were carried out in a thermobalance at 650 ℃ for up to 14.4 ks. The mass gain of the specimens increased with increasing contents of water vapour. Alloy composition had no effect on the oxidation rate in dry conditions. The "adhesion" of the oxide scale was determined using indentation with a Rockwell C diamond and the pull adhesion test to determine the interfacial toughness and the tensile strength of the oxide metal bond, respectively. Generally, the results of the investigation indicated that oxide adhesion was lowest for the specimens exposed to dry conditions, and that with increasing water vapour content, the scale was more adherent. Indentation test results showed that an increase in the Ⅴ concentration was deleterious to oxidc adhesion in both the dry and wet environments, whereas an increase in the Cr-content had little effect on adhesion.

  16. Phytoxicity study of the products of wet oxidation of a representative biomass (lettuce)

    Science.gov (United States)

    Onisko, B. L.; Wydeven, T.

    1983-01-01

    In an attempt to verify the results reported previously concerning the phytotoxicity of wet-oxidation (wet-ox) products, lettuce solids were suspended in water and then heated to 548 K for 3.6 ksec (1 hr) under 4.1x10 to the -7 Pa (400 psig at 294 K) oxygen pressure and 1.52x10 to the 8th (1500 psig at 548 K) total pressure. Such treatment resulted in oxidation of 80% of the initial organic carbon to carbon dioxide. Thirty-three percent of the remaining organic carbon was present in acetic acid. Organic nitrogen in the feed was decreased 90% by the wet-ox treatment. Ammonia and nitrogen gas were the main nitrogen products. Analysis of the liquid product of wet-ox indicated that most of the minerals essential for plant growth were present. However, when tested using a lettuce-root growth-rate assay, the solution was toxic. This toxicity was not due to excessive salt or ammonia or to an improper pH. Analysis of the wet-ox solution revealed the presence of silver and chromium, thus implicating reactor corrosion as the cause of the phytotoxicity. Both cation and anion exchange resins removed the silver and the toxicity of the liquid effluent, indicating silver as the toxic component. Uptake of both silver and chromium by lettuce roots correlated with diminished root growth. Toxicity of the solution from wet-ox was not observed when precautions were taken to minimize contact of the liquid in the reactor with the metal reactor components.

  17. Valuable compounds from sewage sludge by thermal hydrolysis and wet oxidation. A review.

    Science.gov (United States)

    Suárez-Iglesias, Octavio; Urrea, José Luis; Oulego, Paula; Collado, Sergio; Díaz, Mario

    2017-04-15

    Sewage sludge is considered a costly waste, whose benefit has received a lot of attention for decades. In this sense, a variety of promising technologies, such as thermal hydrolysis and wet oxidation, are currently employed. Thermal hydrolysis is used as a pretreatment step ahead of anaerobic digestion processes and wet oxidation is intended for the solubilization and partial oxidation of the sludge. Such processes could be utilized for solubilizing polysaccharides, lipids, fragments of them and phosphorus (thermal hydrolysis) or for generating carboxylic acids (wet oxidation). This article compiles the available information on the production of valuable chemicals by these techniques and comments on their main features. Temperature, reaction duration times and sludge characteristics influence the experimental results significantly, but only the first two variables have been thoroughly studied. For thermal hydrolysis, a rise of temperature led to an increase in the solubilized biomolecules, but also to a greater decomposition of proteins and undesirable reactions of carbohydrates with themselves or with proteins. At constant temperature, the amounts of substances that can be recovered tend to become time independent after several minutes. Diluted and activated sludges seem to be more readily hydrolyzable than the thickened and primary ones. For wet oxidation, the dependence of the production of carboxylic acids with temperature and time is not simple: their concentration can increase, decrease or go through a maximum. At high temperatures, acetic acid is the main carboxylic acid obtained. Concentrated, fermented and secondary sludge seem to be more suitable for yielding higher amounts of acid than diluted, undigested and primary ones.

  18. Differential response of ammonia-oxidizing archaea and bacteria to the wetting of salty arid soil.

    Science.gov (United States)

    Sher, Yonatan; Ronen, Zeev; Nejidat, Ali

    2016-08-01

    Ammonia-oxidizing archaea and bacteria (AOA, AOB) catalyze the first and rate-limiting step of nitrification. To examine their differential responses to the wetting of dry and salty arid soil, AOA and AOB amoA genes (encoding subunit A of the ammonia monooxygenase) and transcripts were enumerated in dry (summer) and wet (after the first rainfall) soil under the canopy of halophytic shrubs and between the shrubs. AOA and AOB were more abundant under shrub canopies than between shrubs in both the dry and wetted soil. Soil wetting caused a significant decrease in AOB abundance under the canopy and an increase of AOA between the shrubs. The abundance of the archaeal amoA gene transcript was similar for both the wet and dry soil, and the transcript-to-gene ratios were water content. In contrast, the bacterial amoA transcript-to-gene ratios were between 78 and 514. The lowest ratio was in dry soil under the canopy and the highest in the soil between the shrubs. The results suggest that the AOA are more resilient to stress conditions and maintain a basic activity in arid ecosystems, while the AOB are more responsive to changes in the biotic and abiotic conditions.

  19. Electrocatalytic Oxidation of Cellulose to Gluconate on Carbon Aerogel Supported Gold Nanoparticles Anode in Alkaline Medium

    Directory of Open Access Journals (Sweden)

    Hanshuang Xiao

    2015-12-01

    Full Text Available The development of high efficient and low energy consumption approaches for the transformation of cellulose is of high significance for a sustainable production of high value-added feedstocks. Herein, electrocatalytic oxidation technique was employed for the selective conversion of cellulose to gluconate in alkaline medium by using concentrated HNO3 pretreated carbon aerogel (CA supported Au nanoparticles as anode. Results show that a high gluconate yield of 67.8% and sum salts yield of 88.9% can be obtained after 18 h of electrolysis. The high conversion of cellulose and high selectivity to gluconate could be attributed to the good dissolution of cellulose in NaOH solution which promotes its hydrolysis, the surface oxidized CA support and Au nanoparticles catalyst which possesses high amount of active sites. Moreover, the bubbled air also plays important role in the enhancement of cellulose electrocatalytic conversion efficiency. Lastly, a probable mechanism for electrocatalytic oxidation of cellulose to gluconate in alkaline medium was also proposed.

  20. Kinetics and Mechanism of Oxidation of Some Diols by Dihydroxydiperiodatoargentate(Ⅲ) in Alkaline Medium

    Institute of Scientific and Technical Information of China (English)

    SHAN, Jin-Huan; LI, Sheng-Min; HUO, Shu-Ying; SHEN, Shi-Gang; SUN, Han-Wen

    2006-01-01

    The kinetics of oxidation of ethylene glycol and 1,3-butylene glycol by dihydroxydiperiodatoargentate(Ⅲ) in alkaline medium have been studied by spectrophotometry in the range of 298.2-318.2 K. It is shown that the reaction was first order with respect to each reductant and Ag(Ⅲ), and kobs increased with an increase of [OH-]. A plausible mechanism of reaction involving a pre-equilibrium of adduct formation between complex and reductants was proposed, which could be applied to explain all experimental phenomena, and the activation parameters of the ratedetermining step have been also calculated.

  1. Superconductivity at 31 K in Alkaline Metal-Doped Cobalt Oxides

    Institute of Scientific and Technical Information of China (English)

    闻海虎; 杨海朋; 鲁希锋; 闫静

    2003-01-01

    By using a simple solid reaction method, we have fabricated alkaline metal doped cobalt oxides Anx CoO2+δ(An = Na, K). The magnetic measurement shows a superconducting-like diamagnetic signal at 31 K based on a strong superparamagnetic signal. Below 31 K, the magnetization hysteresis loops contain a strong rough linear superparamagnetic background and a superconducting hysteresis. The typical magnetization hysteresis loops for a type-Ⅱ superconductor are found. Preliminary resistive data also show a fast dropping of resistance below Tc.These give indication of superconductivity below 31 K in Anx CoO2+δ (An = Na, K).

  2. Ultrasound assisted catalytic wet peroxide oxidation of phenol: kinetics and intraparticle diffusion effects.

    Science.gov (United States)

    Nikolopoulos, Apostolos N; Igglessi-Markopoulou, Olga; Papayannakos, Nikolaos

    2006-01-01

    The combination of ultrasound irradiation and catalytic wet peroxide oxidation was used as a means to degrade phenol. Direct and indirect irradiation were employed, while experiments in the absence of ultrasound were used as reference. A mixed (Al-Fe) pillared clay named FAZA, was used as a catalyst in the form of powder, extrudates and crushed extrudates. Ultrasound was found to clearly enhance the extrudates performance, increasing the conversion at 4h by more than 6 times under direct and almost 11 times under indirect irradiation. This observation is attributed to the reduction of diffusion resistance within the catalyst pores. The overall sonication-catalytic wet peroxide oxidation process appears very promising for environmental purposes.

  3. Uncatalysed wet oxidation of D-glucose with hydrogen peroxide and its combination with hydrothermal electrolysis.

    Science.gov (United States)

    Moreno, Teresa; Kouzaki, Goushi; Sasaki, Mitsuru; Goto, Motonobu; Cocero, María José

    2012-02-15

    An increasing interest in biomass as a renewable feedstock for the chemical industry has risen over the last decades, and glucose, the monomer unit of cellulose, has been widely studied as a source material to produce value-added products such as carboxylic acids, mainly gluconic and formic. In this work, the non-catalysed wet oxidation of glucose using hydrogen peroxide has been analysed, obtaining molar yields to gluconic and formic acids up to 15% and 64%, respectively. Glucose conversion was generally between 40 and 50%, reaching over 80% under the highest temperature (200°C). An appropriate choice of temperature can tune product distribution as well as reaction rates. The interaction of the wet oxidation with an electrolytic reaction was also analysed.

  4. Treatment of desizing wastewater from the textile industry by wet air oxidation

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    This paper describes the application of wet air oxidation to the treatment of desizing wastewater from two textile companies. A two-liter high temperature, high pressure autoclave reactor was used in the study. The range of operating temperatures examined was between 150 and 290℃, and the partial pressure of oxygen ranged from 0. 375 to 2.25 MPa. Variations in pH,CODCr and TOD content were monitored during each experiment and used to assess the extent of conversion of the process. The effects of temperature, pressure and reaction time were explored extensively. More than 90 % CODCr reduction and 80 % TOC removal have been obtained. The results have also been demonstrated that WAO is a suitable pre-treatment methods due to improvement of the BOD5/CODCr ratio of desizing wastewater. The reaction kinetics of wet air oxidation of desizing wastewater has been proved to be two steps, a fast reaction followed by a slow reaction stage.

  5. Pretreatment of Reed by Wet Oxidation and Subsequent Utilization of the Pretreated Fibers for Ethanol Production

    DEFF Research Database (Denmark)

    Szijarto, Nora; Kádár, Zsófia; Varga, Eniko

    2009-01-01

    lignocelluloses usually do. In the present study, wet oxidation was investigated as the pretreatment method to enhance the enzymatic digestibility of reed cellulose to soluble sugars and thus improve the convertibility of reed to ethanol. The most effective treatment increased the digestibility of reed cellulose...... by cellulases more than three times compared to the untreated control. During this wet oxidation, 51.7% of the hemicellulose and 58.3% of the lignin were solubilized, whereas 87.1% of the cellulose remained in the solids. After enzymatic hydrolysis of pretreated fibers from the same treatment, the conversion......Common reed (Phragmites australis) is often recognized as a promising source of renewable energy. However, it is among the least characterized crops from the bioethanol perspective. Although one third of reed dry matter is cellulose, without pretreatment, it resists enzymatic hydrolysis like...

  6. Preliminary Test of the Wet Oxidation of Organics in Basin F Wastewater at Rocky Mountain Arsenal

    Science.gov (United States)

    1978-04-01

    unless other costs such as heating and compression become prohibitive. It is particularly suitable for first-stage treatment of waste source containing...pressures lead to requirements for heavy walled vessels and high pressure pumps . j (2) Wet oxidation tends to produce oxygenated organic compounds of...From Table III, DIMP disappears during the first 10 or 20 percent of the COD reduction. Contrary to our experience with carbon adsorbtion , DIMP is not

  7. Kinetics of wet oxidation of phenol over an Fe/activated carbon catalyst

    NARCIS (Netherlands)

    Quintanilla, A.; Casas, J.A.; Rodriquez, J.J.; Kreutzer, M.T.; Kapteijn, F.; Moulijn, J.A.

    2007-01-01

    Wet oxidation of phenol over an Fe/activated carbon catalyst has been studied in a trickle-bed reactor in the following operational window: inlet C phenol=0.5 and 1 g/L, T=100-127 ºC, PT=3-8 atm, W=0-4.8 g, QL=0.125-2 mL/min and QO2=91.6 NmL/min. The experiments were carried out in the absence of ma

  8. Glycerol-based carbon materials for the catalytic wet peroxide oxidation process

    OpenAIRE

    Ribeiro, Rui S.; Silva, Adrián; Pinho, Maria; Figueiredo,José; Faria, Joaquim; Gomes, Helder

    2013-01-01

    It is known that metal-free carbon materials can act as catalysts for the catalytic wet peroxide oxidation (CWPO) process to treat organic pollutants in aqueous solutions [I]. On the other hand, crude glycerol, such as resulting from biodiesel production, is being offered as an abundant and low cost feedstock [2]. In the present work, glycerol-based carbon materials (OBCMs) with distinct properties were produced and tested as catalysts for CWPO, using 2-nitrophenol (2-NP) as a ...

  9. The degradation of Isophorone by catalytic wet air oxidation on Ru/TiZrO4.

    Science.gov (United States)

    Wei, Huangzhao; Yan, Xiaomiao; Li, Xianru; He, Songbo; Sun, Chenglin

    2013-01-15

    The catalyst Ru/TiZrO(4) was applied in the degradation of Isophorone by catalytic wet air oxidation. Mathematical models for the effects of reaction conditions on the Isophorone degradation by catalytic wet air oxidation were developed using a response surface methodology. A model was obtained for each response with multiple regression analysis and then was refined. Analysis of variance revealed that the models developed were adequate. The validity of the models was also verified by experimental data. Analysis of response surface showed that total organic carbon removal and Isophorone conversion were significantly affected (P≤0.01) by reaction time, temperature and their interactions, and affected (P≤0.05) by the square of reaction time. The point of zero charge of Ru/TiZrO(4) catalyst was about 1.72. The total organic carbon removal and Isophorone conversion had a great association with the zeta potential of Ru/TiZrO(4) catalyst. Finally, the degradation pathway of Isophorone in catalytic wet air oxidation was proposed. Within 410 h, the total organic carbon removal remained above 95%, indicating that the Ru/TiZrO(4) catalyst had a good stability.

  10. Development and testing of a wet oxidation waste processing system. [for waste treatment aboard manned spacecraft

    Science.gov (United States)

    Weitzmann, A. L.

    1977-01-01

    The wet oxidation process is considered as a potential treatment method for wastes aboard manned spacecraft for these reasons: (1) Fecal and urine wastes are processed to sterile water and CO2 gas. However, the water requires post-treatment to remove salts and odor; (2) the residual ash is negligible in quantity, sterile and easily collected; and (3) the product CO2 gas can be processed through a reduction step to aid in material balance if needed. Reaction of waste materials with oxygen at elevated temperature and pressure also produces some nitrous oxide, as well as trace amounts of a few other gases.

  11. Integration of advanced oxidation processes at mild conditions in wet scrubbers for odourous sulphur compounds treatment.

    Science.gov (United States)

    Vega, Esther; Martin, Maria J; Gonzalez-Olmos, Rafael

    2014-08-01

    The effectiveness of different advanced oxidation processes on the treatment of a multicomponent aqueous solution containing ethyl mercaptan, dimethyl sulphide and dimethyl disulphide (0.5 mg L(-1) of each sulphur compound) was investigated with the objective to assess which one is the most suitable treatment to be coupled in wet scrubbers used in odour treatment facilities. UV/H2O2, Fenton, photo-Fenton and ozone treatments were tested at mild conditions and the oxidation efficiency obtained was compared. The oxidation tests were carried out in magnetically stirred cylindrical quartz reactors using the same molar concentration of oxidants (hydrogen peroxide or ozone). The results show that ozone and photo-Fenton are the most efficient treatments, achieving up to 95% of sulphur compounds oxidation and a mineralisation degree around 70% in 10 min. Furthermore, the total costs of the treatments taking into account the capital and operational costs were also estimated for a comparative purpose. The economic analysis revealed that the Fenton treatment is the most economical option to be integrated in a wet scrubber to remove volatile organic sulphur compounds, as long as there are no space constraints to install the required reactor volume. In the case of reactor volume limitation or retrofitting complexities, the ozone and photo-Fenton treatments should be considered as viable alternatives.

  12. Heterogeneous catalytic wet air oxidation of refractory organic pollutants in industrial wastewaters: a review.

    Science.gov (United States)

    Kim, Kyoung-Hun; Ihm, Son-Ki

    2011-02-15

    Catalytic wet air oxidation (CWAO) is one of the most economical and environmental-friendly advanced oxidation process. It makes a promising technology for the treatment of refractory organic pollutants in industrial wastewaters. Various heterogeneous catalysts including noble metals and metal oxides have been extensively studied to enhance the efficiency of CWAO. The present review is concerned about the literatures published in this regard. Phenolics, carboxylic acids, and nitrogen-containing compounds were taken as model pollutants in most cases, and noble metals such as Ru, Rh, Pd, Ir, and Pt as well as oxides of Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, and Ce were applied as heterogeneous catalysts. Reports on their characterization and catalytic performances for the CWAO of aqueous pollutants are reviewed. Discussions are also made on the reaction mechanisms and kinetics proposed for heterogeneous CWAO and also on the typical catalyst deactivations in heterogeneous CWAO, i.e. carbonaceous deposits and metal leaching.

  13. Wet Chemical Synthesis and Screening of Thick Porous Oxide Films for Resistive Gas Sensing Applications

    Directory of Open Access Journals (Sweden)

    Wilhelm F. Maier

    2006-11-01

    Full Text Available A method of wet chemical synthesis suitable for high throughput and combinatorial applications has been developed for the synthesis of porous resistive thick-film gas sensors. This method is based on the robot-controlled application of unstable metal oxide suspensions on an array of 64 inter-digital electrodes positioned on an Al2O3 substrate. SnO2, WO3, ZrO2, TiO2, CeO2, In2O3 and Bi2O3 were chosen as base oxides, and were optimised by doping or mixed oxide formation. The parallel synthesis of mixed oxide sensors is illustrated by representative examples. The electrical characteristics and the sensor performance of the films were measured by high-throughput impedance spectroscopy while supplying various test gases (H2, CO, NO, NO2, propene. Data collection, data mining techniques applied and the best potential sensor materials discovered are presented.

  14. Highly Dispersed Palladium Nanoparticles on Functional MWNT Surfaces for Methanol Oxidation in Alkaline Solutions

    Institute of Scientific and Technical Information of China (English)

    WANG zhe; ZHU Zan-Zan; LI You-Xiang; LI Hu-Lin

    2008-01-01

    Palladium nanoparticles were crystallized on 4-aminobenzoic acid monolayer-grafted multi-walled carbon nanotubes (MWNT) by diazotization. The structure and nature of the resulting Pd/MWNT composite were characterized by transmission electron microscopy and X-ray diffraction, the results show that the chemically synthesized Pd nanoparticles were homogeneously dispersed and well-separated from one another on the modified MWNT surfaces. Cyclic voltammogram showed that the Pd-MWNT composite materials performed higher electrocatalytic activity and better long-term stability toward methanol oxidation in alkaline solution than Pd-C. The results imply that the Pd-MWNT composite materials as a promising support material improve the excellent electrocatalytic activity for methanol oxidation greatly. So the Pd/MWNT composites have a good application potential to fuel cells.

  15. PILOT TESTING OF MERCURY OXIDATION CATALYSTS FOR UPSTREAM OF WET FGD SYSTEMS

    Energy Technology Data Exchange (ETDEWEB)

    Gary M. Blythe

    2003-01-21

    This document summarizes progress on Cooperative Agreement DE-FC26-01NT41185, Pilot Testing of Mercury Oxidation Catalysts for Upstream of Wet FGD Systems, during the time period October 1, 2002 through December 31, 2002. The objective of this project is to demonstrate at pilot scale the use of solid honeycomb catalysts to promote the oxidation of elemental mercury in the flue gas from coal combustion. The project is being funded by the U.S. DOE National Energy Technology Laboratory under Cooperative Agreement DE-FC26-01NT41185. EPRI, Great River Energy (GRE), and City Public Service (CPS) of San Antonio are project co-funders. URS Group is the prime contractor. The mercury catalytic oxidation process under development uses catalyst materials applied to honeycomb substrates to promote the oxidation of elemental mercury in the flue gas from coal-fired power plants that have wet lime or limestone flue gas desulfurization (FGD) systems. Oxidized mercury is removed in the wet FGD absorbers and co-precipitates with the byproducts from the FGD system. The co-precipitated mercury does not appear to adversely affect the disposal or reuse properties of the FGD byproduct. The current project testing previously identified, effective catalyst materials at a larger, pilot scale and in a commercial form, to provide engineering data for future fullscale designs. The pilot-scale tests will continue for up to 14 months at each of two sites to provide longer-term catalyst life data. This is the fifth full reporting period for the subject Cooperative Agreement. During this period, project efforts included starting up the pilot unit with three catalysts at the first site, conducting catalyst activity measurements, completing comprehensive flue gas sampling and analyses, and procuring additional catalysts for the pilot unit. This technical progress report provides an update on these efforts.

  16. Green synthesis of core-shell gold-palladium@palladium nanocrystals dispersed on graphene with enhanced catalytic activity toward oxygen reduction and methanol oxidation in alkaline media

    Science.gov (United States)

    Zheng, Jie-Ning; Li, Shan-Shan; Ma, Xiaohong; Chen, Fang-Yi; Wang, Ai-Jun; Chen, Jian-Rong; Feng, Jiu-Ju

    2014-09-01

    Well-defined core-shell gold-palladium@palladium nanocrystals (AuPd@Pd) are facilely prepared by a simple and green wet-chemical method at 25 °C. A Good's buffer, 2-[4-(2-hydroxyethyl)-1-piperazinyl] ethanesulfonic acid (HEPES), is used as a reducing agent and a shape-directing agent, while there is no template, seed, organic solvent, or surfactant involved. The AuPd@Pd nanocrystals are uniformly dispersed on graphene nanosheets by ultrasonication, resulting in the formation of graphene supported AuPd@Pd (G-AuPd@Pd). The as-prepared nanocomposites exhibit the improved catalytic activity, good tolerance, and better stability for oxygen reduction reaction (ORR) and methanol oxidation reaction (MOR) in alkaline media, compared with the G-Pd and commercial Pd black catalysts. The as-developed method may provide a promising pathway for large-scale fabrication of AuPd-based catalysts.

  17. Influence of Substrate Particle Size and Wet Oxidation on Physical Surface Structures and Enzymatic Hydrolysis of Wheat Straw

    DEFF Research Database (Denmark)

    Pedersen, Mads; Meyer, Anne S.

    2009-01-01

    In the worldwide quest for producing biofuels from lignocellulosic biomass, the importance of the substrate pretreatment is becoming increasingly apparent. This work examined the effects of reducing the substrate particle sizes of wheat straw by grinding prior to wet oxidation and enzymatic...... release only increased (by up to 39%) with particle size decrease for the straw particles that had not been wet oxidized. Wet oxidation pretreatment increased the enzymatic xylose release by 5.4 times and the glucose release by 1.8 times across all particle sizes. Comparison of scanning electron...... microscopy images of the straw particles revealed edged, nonspherical, porous particles with variable surface structures as a result of the grinding. Wet oxidation pretreatment tore up the surface structures of the particles to retain vascular bundles of xylem and phloem. The enzymatic hydrolysis left behind...

  18. Catalytic wet peroxide oxidation of p-nitrophenol by Fe (III) supported on resin.

    Science.gov (United States)

    Liou, Rey-May; Chen, Shih-Hsiung; Huang, Cheng-Hsien; Lai, Cheng-Lee; Shih, C Y; Chang, Jing-Song; Hung, Mu-Ya

    2010-01-01

    Fe(III) supported on resin (Fe(III)-resin) as an effective catalyst for peroxide oxidation was prepared and applied for the degradation of p-nitrophenol (PNP). Catalytic wet peroxide oxidation (CWPO) experiments with hydrogen peroxide as oxidant were performed in a batch rector with p-nitrophenol as the model pollutant. Under given conditions (PNP concentration 500 mg/L, H(2)O(2) 0.1 M, 80°C, resin dosage 0.6% g/mL), p-nitrophenol was almost completely removed, corresponding to an 84% of COD removal. It was found that the reaction temperature, oxidant concentration. and initial pH of solution significantly affected both p-nitrophenol conversion and COD removal by oxidation. It can be inferred from the experiments that Fe(III) supported on resin was an effective catalyst in the mineralization of p-nitrophenol. In an acidic environment of oxidation, the leaching test showed that there was only a slight leaching effect on the activity of catalytic oxidation. It was also confirmed by the aging test of catalysts in the oxidation.

  19. Study on dynamics characteristics of wet air oxidation of non-ionic surfactants

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    Wet air oxidation is an effective method to deal with highly concentrated nondegradable emulsification wastewater which contains non-ionic surfactants. This article illustrates our investigation on dynamic characteristics of wet air oxidation of typical non-ionic surfactants like polyether, phenol ether and widely used alcohol ether. The experimental results indicated that the oxidation rate of polyether, phenol ether and alcohol ether obviously ascended as the temperature rose. A good oxidation effect was available at 240℃. The TOC removal rate could reach 88.0%, 94% and 91.5%, after 125 min reaction. Alcohol ether was prone to an easier oxidation compared with polyether and phenol ether when the temperature was 220℃ or below. The oxidation rate of alcohol ether was higher than that of polyether at 160℃, while the oxidation rate of polyether was higher than that of phenol ether between 180℃ and 220℃. During the later period of the reaction at 240℃, the rate of phenol ether was higher than that of alcohol ether, which was still higher than that of polyether. Partitioned first order kinetics model analy-sis showed that the apparent activation energy of alcohol ether was lower than that of both polyether and phenol ether in the leading stage and lagging stage, and it was easy to acquire a higher oxidation rate for alcohol ether at low temperature. Three parameter general dynamics model analyses showed that the reason why the oxidation rate of polyether was lower than that of alcohol ether was that the oxidation of polyether was more apt to be converted to intermediate production than that of alcohol ether, whereas between 200℃ and 220℃, the direct oxidation rate of polyether and the oxidation rate of intermediate product were obviously lower than that of alcohol ether. The apparent activation energy of direct and indirect oxidation of polyether was 43.37 and 60.45 kJ?mol?1, respectively, while the corre-sponding apparent activation energy of alcohol

  20. Study on dynamics characteristics of wet air oxidation of non-ionic surfactants

    Institute of Scientific and Technical Information of China (English)

    ZENG XinPing; TANG WenWei; ZHAO JianFu; GU GuoWei

    2008-01-01

    Wet air oxidation is an effective method to deal with highly concentrated nondegradable emulsification wastewater which contains non-ionic surfactants. This article illustrates our investigation on dynamic characteristics of wet air oxidation of typical non-ionic surfactants like polyether, phenol ether and widely used alcohol ether. The experimental results indicated that the oxidation rate of polyether, phenol ether and alcohol ether obviously ascended as the temperature rose. A good oxidation effect was available at 240℃. The TOC removal rate could reach 88.0%, 94% and 91.5%, after 125 min reaction. Alcohol ether was prone to an easier oxidation compared with polyether and phenol ether when the temperature was 220℃ or below. The oxidation rate of alcohol ether was higher than that of polyether at 160℃, while the oxidation rate of polyether was higher than that of phenol ether between 180℃ and 220℃. During the later period of the reaction at 240℃, the rate of phenol ether was higher than that of alcohol ether, which was still higher than that of polyether. Partitioned first order kinetics model analysis showed that the apparent activation energy of alcohol ether was lower than that of both polyether and phenol ether in the leading stage and lagging stage, and it was easy to acquire a higher oxidation rate for alcohol ether at low temperature. Three parameter general dynamics model analyses showed that the reason why the oxidation rate of polyether was lower than that of alcohol ether was that the oxidation of polyether was more apt to be converted to intermediate production than that of alcohol ether, whereas between 200℃ and 220℃, the direct oxidation rate of polyether and the oxidation rate of intermediate product were obviously lower than that of alcohol ether. The apparent activation energy of direct and indirect oxidation of polyether was 43.37 and 60.45 kJ·mol-1, respectively, while the corresponding apparent activation energy of alcohol

  1. Treatment of refractory organic pollutants in industrial wastewater by wet air oxidation

    Directory of Open Access Journals (Sweden)

    Mingming Luan

    2017-02-01

    Full Text Available Wet air oxidation (WAO is one of the most economical and environmentally-friendly advanced oxidation processes. It makes a promising technology for the treatment of refractory organic pollutants in industrial wastewaters. In wet air oxidation aqueous waste is oxidized in the liquid phase at high temperatures (125–320 °C and pressures (0.5–20 MPa in the presence of an oxygen-containing gas (usually air. The advantages of the process include low operating costs and minimal air pollution discharges. The present review is concerned about the literature published in the treatment of refractory organic pollutants in industrial wastewaters, such as dyes. Phenolics were taken as model pollutants in most cases. Reports on effect of treatment for the WAO of refractory organic pollutants in industrial wastewaters are reviewed, such as emulsified wastewater, TNT red water, etc. Discussions are also made on the mechanism and kinetics of WAO and main technical parameters influencing WAO. Finally, development direction of WAO is summed up.

  2. PILOT TESTING OF MERCURY OXIDATION CATALYSTS FOR UPSTREAM OF WET FGD SYSTEMS

    Energy Technology Data Exchange (ETDEWEB)

    Gary M. Blythe

    2003-05-01

    This document summarizes progress on Cooperative Agreement DE-FC26-01NT41185, ''Pilot Testing of Mercury Oxidation Catalysts for Upstream of Wet FGD Systems,'' during the time period January 1, 2003 through March 31, 2003. The objective of this project is to demonstrate at pilot scale the use of solid honeycomb catalysts to promote the oxidation of elemental mercury in the flue gas from coal combustion. The project is being funded by the U.S. DOE National Energy Technology Laboratory under Cooperative Agreement DE-FC26-01NT41185. EPRI, Great River Energy (GRE), and City Public Service (CPS) of San Antonio are project cofunders. URS Group is the prime contractor. The mercury control process under development uses catalyst materials applied to honeycomb substrates to promote the oxidation of elemental mercury in the flue gas from coal-fired power plants that have wet lime or limestone flue gas desulfurization (FGD) systems. Oxidized mercury is removed in the wet FGD absorbers and co-precipitates with the byproducts from the FGD system. The current project is testing previously identified, effective catalyst materials at a larger, pilot scale and in a commercial form, to provide engineering data for future full-scale designs. The pilot-scale tests will continue for up to 14 months at each of two sites to provide longer-term catalyst life data. This is the sixth full reporting period for the subject Cooperative Agreement. During this period, project efforts included continued operation of the pilot unit with three catalysts, conducting catalyst activity measurements, and procuring the fourth catalyst, all for the GRE Coal Creek pilot unit site. Laboratory efforts were also conducted to support catalyst selection for the second pilot unit site, at CPS' Spruce Plant. This technical progress report provides an update on these efforts.

  3. Catalytic wet peroxide oxidation of phenol solutions over CuO/CeO2 systems.

    Science.gov (United States)

    Massa, Paola; Ivorra, Fernando; Haure, Patricia; Fenoglio, Rosa

    2011-06-15

    Three 5% CuO/CeO(2) catalysts were synthesized by sol-gel, precipitation and combustion methods, followed by incipient wetness impregnation with copper nitrate. The samples were characterized by XRD, TPR, BET and tested for the catalytic wet peroxide oxidation of a phenol solution (5 g/L). The reaction took place in a batch reactor at atmospheric pressure, in a temperature range of 60-80°C, during 4h. Phenol conversion, H(2)O(2) consumption, pH and chemical oxygen demand were determined. The reaction temperature and the catalyst loading did improve the phenol and the H(2)O(2) conversions. The effect on the selectivity towards complete mineralization was less marked, with levels among 60-70%. Stepwise addition of H(2)O(2) was also tested.

  4. Catalytic wet peroxide oxidation of phenol solutions over CuO/CeO{sub 2} systems

    Energy Technology Data Exchange (ETDEWEB)

    Massa, Paola, E-mail: pamassa@fi.mdp.edu.ar [Division Catalizadores y Superficies, INTEMA, Universidad Nacional de Mar del Plata/CONICET, Juan B. Justo 4302, 7600 Mar del Plata, Buenos Aires (Argentina); Ivorra, Fernando; Haure, Patricia; Fenoglio, Rosa [Division Catalizadores y Superficies, INTEMA, Universidad Nacional de Mar del Plata/CONICET, Juan B. Justo 4302, 7600 Mar del Plata, Buenos Aires (Argentina)

    2011-06-15

    Three 5% CuO/CeO{sub 2} catalysts were synthesized by sol-gel, precipitation and combustion methods, followed by incipient wetness impregnation with copper nitrate. The samples were characterized by XRD, TPR, BET and tested for the catalytic wet peroxide oxidation of a phenol solution (5 g/L). The reaction took place in a batch reactor at atmospheric pressure, in a temperature range of 60-80{sup Degree-Sign }C , during 4 h. Phenol conversion, H{sub 2}O{sub 2} consumption, pH and chemical oxygen demand were determined. The reaction temperature and the catalyst loading did improve the phenol and the H{sub 2}O{sub 2} conversions. The effect on the selectivity towards complete mineralization was less marked, with levels among 60-70%. Stepwise addition of H{sub 2}O{sub 2} was also tested.

  5. Catalytic wet-oxidation of a mixed liquid waste: COD and AOX abatement.

    Science.gov (United States)

    Goi, D; de Leitenburg, C; Trovarelli, A; Dolcetti, G

    2004-12-01

    A series of catalytic wet oxidation (CWO) reactions, at temperatures of 430-500 K and in a batch bench-top pressure vessel were carried out utilizing a strong wastewater composed of landfill leachate and heavily organic halogen polluted industrial wastewater. A CeO2-SiO2 mixed oxide catalyst with large surface area to assure optimal oxidation performance was prepared. The catalytic process was examined during batch reactions controlling Chemical Oxygen Demand (COD) and Adsorbable Organic Halogen (AOX) parameters, resulting AOX abatement to achieve better effect. Color and pH were also controlled during batch tests. A simple first order-two stage reaction behavior was supposed and verified with the considered parameters. Finally an OUR test was carried out to evaluate biodegradability changes of wastewater as a result of the catalytic reaction.

  6. Chloride interference in the analysis of dissolved organic carbon by the wet oxidation method

    Science.gov (United States)

    Aiken, G.R.

    1992-01-01

    The presence of Cl- in concentrations greater than 0.02 M is shown to interfere with the analysis of aqueous DOC concentrations by the wet oxidation method of analysis when a reaction time of 5 min is employed. Chloride competes with DOC for S2O82-, lowering the overall oxidation efficiency. The resulting HOCl from the oxidation of Cl- reacts with DOC, producing significant amounts of chlorinated intermediate compounds in addition to CO2. These compounds were found in the waste effluent from the reaction chamber and in the gas stream transporting CO2 to the detector. While a possible Cl- effect has been noted for DOC measurements in the past, it has not previously been demonstrated to be a source of error at the concentrations reported in this paper. The interference can be overcome either by increasing the digestion time or by diluting samples to contain less than 0.02 M Cl-.

  7. Spectroscopic and mechanistic investigations into oxidation of aspartame by diperiodatocuprate(III in aqueous alkaline medium

    Directory of Open Access Journals (Sweden)

    Jayant I. Gowda

    2015-12-01

    Full Text Available The oxidation of aspartame (ASP by diperiodatocuprate(III (DPC in aqueous alkaline medium at 298 K and a constant ionic strength of 0.30 mol dm−3 was studied spectrophotometrically. The reaction between aspartame and diperiodatocuprate(III in alkaline medium exhibits 1:6 stoichiometry in the reaction. The order of the reaction with respect to [diperiodatocuprate(III] was unity, while the apparent order with respect to [aspartame] was less than unity over the concentration range studied. The rate of the reaction increased with increase in [OH−] whereas the rate decreased with increase in [$ {\\text{IO}}^-_4 $]. Increasing the ionic strength of the medium increased the rate. The main products were identified by FT-IR, NMR, and LC-MS spectral studies. The probable mechanism was proposed. The activation parameters with respect to slow step of the mechanism were computed and discussed. Thermodynamic quantities were also calculated. Kinetic studies suggest that [Cu(H2IO6(H2O2] is the reactive species of Cu(III.

  8. Alkaline deoxygenated graphene oxide as adsorbent for cadmium ions removal from aqueous solutions.

    Science.gov (United States)

    Liu, Jun; Du, Hongyan; Yuan, Shaowei; He, Wanxia; Yan, Pengju; Liu, Zhanhong

    2015-01-01

    Alkaline deoxygenated graphene oxide (aGO) was prepared through alkaline hydrothermal treatment and used as adsorbent to remove Cd(II) ions from aqueous solutions for the first time. The characterization results of transmission electron microscopy, X-ray diffraction, Raman spectroscopy, and Fourier transform infrared (FT-IR) spectra indicate that aGO was successfully synthesized. The batch adsorption experiments showed that the adsorption kinetics could be described by the pseudo-second-order kinetic model, and the isotherms equilibrium data were well fitted with the Langmuir model. The maximum adsorption capacity of Cd(II) on aGO was 156 mg/g at pH 5 and T=293 K. The adsorption thermodynamic parameters indicated that the adsorption process was a spontaneous and endothermic reaction. The mainly adsorption mechanism speculated from FT-IR results may be attributed to the electrostatic attraction between Cd2+ and negatively charged groups (-CO-) of aGO and cation-π interaction between Cd2+ and the graphene planes. The findings of this study demonstrate the potential utility of the nanomaterial aGO as an effective adsorbent for Cd(II) removal from aqueous solutions.

  9. Full-Scale Testing of a Mercury Oxidation Catalyst Upstream of a Wet FGD System

    Energy Technology Data Exchange (ETDEWEB)

    Gary Blythe; Jennifer Paradis

    2010-06-30

    This document presents and discusses results from Cooperative Agreement DE-FC26-06NT42778, 'Full-scale Testing of a Mercury Oxidation Catalyst Upstream of a Wet FGD System,' which was conducted over the time-period July 24, 2006 through June 30, 2010. The objective of the project was to demonstrate at full scale the use of solid honeycomb catalysts to promote the oxidation of elemental mercury in pulverized-coal-fired flue gas. Oxidized mercury is removed downstream in wet flue gas desulfurization (FGD) absorbers and collected with the byproducts from the FGD system. The project was co-funded by EPRI, the Lower Colorado River Authority (LCRA), who also provided the host site, Great River Energy, Johnson Matthey, Southern Company, Salt River Project (SRP), the Tennessee Valley Authority (TVA), NRG Energy, Ontario Power and Westar. URS Group was the prime contractor and also provided cofunding. The scope of this project included installing and testing a gold-based catalyst upstream of one full-scale wet FGD absorber module (about 200-MW scale) at LCRA's Fayette Power Project (FPP) Unit 3, which fires Powder River Basin coal. Installation of the catalyst involved modifying the ductwork upstream of one of three wet FGD absorbers on Unit 3, Absorber C. The FGD system uses limestone reagent, operates with forced sulfite oxidation, and normally runs with two FGD modules in service and one spare. The full-scale catalyst test was planned for 24 months to provide catalyst life data. Over the test period, data were collected on catalyst pressure drop, elemental mercury oxidation across the catalyst module, and mercury capture by the downstream wet FGD absorber. The demonstration period began on May 6, 2008 with plans for the catalyst to remain in service until May 5, 2010. However, because of continual increases in pressure drop across the catalyst and concerns that further increases would adversely affect Unit 3 operations, LCRA decided to end the

  10. Conversion of the refractory ammonia and acetic acid in catalytic wet air oxidation of animal byproducts.

    Science.gov (United States)

    Fontanier, Virginie; Zalouk, Sofiane; Barbati, Stéphane

    2011-01-01

    Wet air oxidation (WAO) and catalytic wet air oxidation (CWAO) of slaughtered animal byproducts (ABPs) were investigated. Two step experiment was carried out consisting of a non-catalysed WAO run followed by a CWAO run at 170-275 degrees C, 20 MPa, and reaction time 180 min. The WAO (1st step) of sample (5 g/L total organic carbon (TOC)) yielded (82.0 +/- 4)% TOC removal and (78.4 +/- 13.2)% conversion of the initial organic-N into NH4(+)-N. Four metal catalysts (Pd, Pt, Rh, Ru) supported over alumina have been tested in catalytic WAO (2nd step) at elevated pH to enhance ammonia conversion and organic matter removal, particularly acetic acid. It was found that the catalysts Ru, Pt, and Rh had significant effects on the TOC removal (95.1%, 99.5% and 96.7%, respectively) and on the abatement of ammonia (93.4%, 96.7% and 96.3%, respectively) with high nitrogen selectivity. The catalyst Pd was found to have the less activity while Pt had the best performance. The X-Ray diffraction analysis showed that the support of catalyst was not stable under the experimental conditions since it reacted with phosphate present in solution. Nitrite and nitrate ions were monitored during the oxidation reaction and it was concluded that CWAO of ammonia in real waste treatment framework was in good agreement with the results obtained from the literature for ideal solutions of ammonia.

  11. Application of Catalytic Wet Air Oxidation to Treatment of Landfill Leachate on Co/Bi Catalyst

    Institute of Scientific and Technical Information of China (English)

    LI Hai-sheng; LIU Liang; ZHANG Rong; DONG De-ming; LIU Hong-liang; LI Yu

    2004-01-01

    Catalytic wet air oxidation(CWAO) was employed to reduce the organic compounds in landfill leachate and the effects of temperature, oxygen pressure, catalyst dosage, and concentration of the organic compounds on the TOC and CODCr removal rates were studied. The degradation kinetics of landfill leachate was also investigated and an exponential experiential model consisting of four influential factors was established to describe the reduction of the organic compounds in the landfill leachate. Meanwhile, the GC-MS technique was used to detect the components of the organic intermediates for the inference of the decomposition mechanisms of the organic compounds in landfill leachate. The results reveal that the reaction temperature and the catalyst dosage are the most important factors affecting the degradation reaction of the organic compounds and that the principal intermediates confirmed by GC-MS are organic acids at a percentage of more than 88% with no aldehydes or alcohols detected. The decomposition mechanisms of the organic compounds in landfill leachate were inferred based on the GC-MS information as follows: the activated gas phase O2 captured the hydrogen of the organic pollutants to produce free radicals, which then initiated the catalytic reaction. So most of the organic compounds were oxidized into CO2 and H2O ultimately. In general, catalytic wet air oxidation over catalyst Co3O4/Bi2O3 was a very promising technique for the treatment of landfill leachate.

  12. An analytical method for 14C in environmental water based on a wet-oxidation process.

    Science.gov (United States)

    Huang, Yan-Jun; Guo, Gui-Yin; Wu, Lian-Sheng; Zhang, Bing; Chen, Chao-Feng; Zhang, Hai-Ying; Qin, Hong-Juan; Shang-Guan, Zhi-Hong

    2015-04-01

    An analytical method for (14)C in environmental water based on a wet-oxidation process was developed. The method can be used to determine the activity concentrations of organic and inorganic (14)C in environmental water, or total (14)C, including in drinking water, surface water, rainwater and seawater. The wet-oxidation of the organic component allows the conversion of organic carbon to an inorganic form, and the extraction of the inorganic (14)C can be achieved by acidification and nitrogen purging. Environmental water with a volume of 20 L can be used for the wet-oxidation and extraction, and a detection limit of about 0.02 Bq/g(C) can be achieved for water with carbon content above 15 mg(C)/L, obviously lower than the natural level of (14)C in the environment. The collected carbon is sufficient for measurement with a low level liquid scintillation counter (LSC) for typical samples. Extraction or recovery experiments for inorganic carbon and organic carbon from typical materials, including analytical reagents of organic benzoquinone, sucrose, glutamic acid, nicotinic acid, humic acid, ethane diol, et cetera., were conducted with excellent results based on measurement on a total organic carbon analyzer and LSC. The recovery rate for inorganic carbon ranged tween 98.7%-99.0% with a mean of 98.9(± 0.1)%, for organic carbon recovery ranged between 93.8% and 100.0% with a mean of 97.1(± 2.6)%. Verification and an uncertainty budget of the method are also presented for a representative environmental water. The method is appropriate for (14)C analysis in environmental water, and can be applied also to the analysis of liquid effluent from nuclear facilities.

  13. Wild soybean roots depend on specific transcription factors and oxidation reduction related genesin response to alkaline stress.

    Science.gov (United States)

    DuanMu, Huizi; Wang, Yang; Bai, Xi; Cheng, Shufei; Deyholos, Michael K; Wong, Gane Ka-Shu; Li, Dan; Zhu, Dan; Li, Ran; Yu, Yang; Cao, Lei; Chen, Chao; Zhu, Yanming

    2015-11-01

    Soil alkalinity is an important environmental problem limiting agricultural productivity. Wild soybean (Glycine soja) shows strong alkaline stress tolerance, so it is an ideal plant candidate for studying the molecular mechanisms of alkaline tolerance and identifying alkaline stress-responsive genes. However, limited information is available about G. soja responses to alkaline stress on a genomic scale. Therefore, in the present study, we used RNA sequencing to compare transcript profiles of G. soja root responses to sodium bicarbonate (NaHCO3) at six time points, and a total of 68,138,478 pairs of clean reads were obtained using the Illumina GAIIX. Expression patterns of 46,404 G. soja genes were profiled in all six samples based on RNA-seq data using Cufflinks software. Then, t12 transcription factors from MYB, WRKY, NAC, bZIP, C2H2, HB, and TIFY families and 12 oxidation reduction related genes were chosen and verified to be induced in response to alkaline stress by using quantitative real-time polymerase chain reaction (qRT-PCR). The GO functional annotation analysis showed that besides "transcriptional regulation" and "oxidation reduction," these genes were involved in a variety of processes, such as "binding" and "response to stress." This is the first comprehensive transcriptome profiling analysis of wild soybean root under alkaline stress by RNA sequencing. Our results highlight changes in the gene expression patterns and identify a set of genes induced by NaHCO3 stress. These findings provide a base for the global analyses of G. soja alkaline stress tolerance mechanisms.

  14. Selective oxidation of methanol to hydrogen over gold catalysts promoted by alkaline-earth-metal and lanthanum oxides.

    Science.gov (United States)

    Hereijgers, Bart P C; Weckhuysen, Bert M

    2009-01-01

    A series of alumina-supported gold catalysts was investigated for the CO-free production of hydrogen by partial oxidation of methanol. The addition of alkaline-earth metal oxide promoters resulted in a significant improvement of the catalytic performance. The methanol conversion was ca. 85 % with all studied catalyst materials, however, the selectivity for hydrogen increased from 15 % to 51 % when going from the unpromoted to a BaO-promoted catalyst. The formation of the undesired byproducts CO, methane, and dimethyl ether was considerably reduced as well. The observed trend in catalyst performance follows the trend in increasing basicity of the studied promoter elements, indicating a chemical effect of the promoter material. Superior catalytic performance, in terms of H(2) and CO selectivity, was obtained with a Au/La(2)O(3) catalyst. At 300 degrees C the hydrogen selectivity reached 80 % with only 2 % CO formation, and the catalyst displayed a stable performance over at least 24 h on-stream. Furthermore, the formation of CO was found to be independent of the oxygen concentration in the feed. The commercial lanthanum oxide used in this study had a low specific surface area, which led to the formation of relative large gold particles. Therefore, the catalytic activity could be enhanced by decreasing the gold particle size through deposition on lanthanum oxide supported on high-surface-area alumina.

  15. Comparative kinetic analysis of silent and ultrasound-assisted catalytic wet peroxide oxidation of phenol.

    Science.gov (United States)

    Rokhina, Ekaterina V; Repo, Eveliina; Virkutyte, Jurate

    2010-03-01

    The kinetic study of silent and ultrasound-assisted catalytic wet peroxide oxidation of phenol in water was performed to qualitatively assess the effect of ultrasound on the process kinetics. Various kinetic parameters such as the apparent kinetic rate constants, the surface utilization coefficient and activation energy of phenol oxidation over RuI(3) catalyst were investigated. Comparative analysis revealed that the use of ultrasound irradiation reduced the energy barrier of the reaction but had no impact on the reaction pathway. The activation energy for the oxidation of phenol over RuI(3) catalyst in the presence of ultrasound was found to be 13kJmol(-1), which was four times smaller in comparison to the silent oxidation process (57kJmol(-1)). Finally, 'figures-of-merit' was utilized to assess different experimental strategies such as sonolysis alone, H(2)O(2)-enhanced sonolysis and sono-catalytic oxidation of phenol in order to estimate the electric energy consumption based on the kinetic rate constants of the oxidation process.

  16. Chloride ions promoted the catalytic wet peroxide oxidation of phenol over clay-based catalysts.

    Science.gov (United States)

    Zhou, Shiwei; Zhang, Changbo; Xu, Rui; Gu, Chuantao; Song, Zhengguo; Xu, Minggang

    2016-01-01

    Catalytic wet peroxide oxidation (CWPO) of phenol over clay-based catalysts in the presence and absence of NaCl was investigated. Changes in the H2O2, Cl(-), and dissolved metal ion concentration, as well as solution pH during phenol oxidation, were also studied. Additionally, the intermediates formed during phenol oxidation were detected by liquid chromatography-mass spectroscopy and the chemical bonding information of the catalyst surfaces was analyzed by X-ray photoelectron spectroscopy (XPS). The results showed that the presence of Cl(-) increased the oxidation rate of phenol to 155%, and this phenomenon was ubiquitous during the oxidation of phenolic compounds by H2O2 over clay-based catalysts. Cl(-)-assisted oxidation of phenol was evidenced by several analytical techniques such as mass spectroscopy (MS) and XPS, and it was hypothesized that the rate-limiting step was accelerated in the presence of Cl(-). Based on the results of this study, the CWPO technology appears to be promising for applications in actual saline phenolic wastewater treatment.

  17. Pretreatment of corn stover using wet oxidation to enhance enzymatic digestibility

    DEFF Research Database (Denmark)

    Varga, E.; Schmidt, A.S.; Reczey, K.

    2003-01-01

    Corn stover is an abundant, promising raw material for fuel ethanol production. Although it has a high cellulose content, without pretreatment it resists enzymatic hydrolysis, like most lignocellulosic materials. Wet oxidation (water, oxygen, mild alkali or acid, elevated temperature and pressure......) was investigated to enhance the enzymatic digestibility of corn stover. Six different combinations of reaction temperature, time, and pH were applied. The best conditions (60 g/L of corn stover, 195degreesC, 15 min, 12 bar O-2, 2 g/L of Na2CO) increased the enzymatic conversion of corn stover four times, compared...

  18. Wet Oxidation Pretreatment of Tobacco Stalks and Orange Waste for Bioethanol Production. Preliminary results

    DEFF Research Database (Denmark)

    Martin, Carlos; Fernandez, Teresa; Garcia, Ariel

    2009-01-01

    Wet oxidation (WO) was used as a pretreatment method prior to enzymatic hydrolysis of tobacco stalks and orange waste. The pretreatment, performed at 195 degrees C and an oxygen pressure of 1.2 MPa, for 15 min, in the presence of Na2CO3, increased the cellulose content of the materials and gave...... cellulose recoveries of approximately 90%. The pretreatment enhanced the susceptibility of cellulose to enzymatic hydrolysis. The highest enzymatic convertibility, that of 64.9%, was achieved for pretreated tobacco stalks. The ethanolic fermentation of the WO filtrates, using Saccharomyces cerevisiae...

  19. Kinetics and Mechanism of Oxidation of Lactic Acid by Dihydroxyditelluratoargentate(Ⅲ) in Alkaline Medium

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    The kinetics of the oxidation of lactic acid(Lac) by dihydroxyditelluratoargentate(Ⅲ)[abbreviated as DDA of Ag(Ⅲ)] anions was studied in an aqueous alkaline medium by conventional spectrophotometry in a temperature range of 25—40 ℃. The order of the redox reaction of lactic acid and DDA was found to be first-order. The rates increased with the increase in [OH-] and decreased with the increase in [tellurate]. No free radical was detected. In the view of this the dihydroxymonotelluratoargentate(Ⅲ) species(DMA) is assumed to be the active species. A plausible mechanism involving a two-electron transfer is proposed, and the rate equation derived from the mechanism can be used to explain all the experimental results. The activation parameters(25 ℃) and the rate constants of the rate-determining step along with the preequilibrium constants at different temperatures were evaluated.

  20. Kinetics and Mechanism of Oxidation of Lactic Acid by Dihydroxyditelluratoargentate(Ⅲ)in Alkaline Medium

    Institute of Scientific and Technical Information of China (English)

    SHANJin-huan; WANGLi; LIUBao-sheng; SHENShi-gang

    2003-01-01

    The kinetics of the oxidation of lactic acid(Lac) by dihydroxyditelluratoargentate(Ⅲ)[abbreviated as DDA of Ag(Ⅲ)]anions was studied in an aqueous alkaline medium by conventional spectrophotometry in a temperature range of 25-40℃.The order of the redox reaction of lactic acid and DDA was found to be first-order.The rates increased with the increase in [OH-]and decreased with the increase in [tellurate].No free radical was detected.In the view of this the dihydroxymonotelluratoargentate(Ⅲ)species(DMA) is assumed to be the active species.A plausible mechanism involving a two-electron transfer is proposed,and the rate equation derived from the mechanism can be used to explain all the experimenttal results.The activation parameters(25℃)and the rate constants of the rate-determining step along with the preequilibrium constants at different temperatures were evaluated.

  1. Kinetic study of methanol oxidation on Pt2Ru3/C catalyst in the alkaline media

    Directory of Open Access Journals (Sweden)

    A. V. TRIPKOVIC

    2007-11-01

    Full Text Available The interaction of acridine orange (AO with double-stranded (ds The electrochemical oxidation of methanol in NaOH solution was examined on a thin film Pt2Ru3/C electrode. The XRD pattern revealed that the Pt2Ru3 alloy consisted of a solid solution of Ru in Pt and a small amount of Ru or a solid solution of Pt in Ru. It was shown that in alkaline solution, the difference in activity between Pt/C and Pt2Ru3/C is significantly smaller than in acid solution. It is proposed that the reaction follows a quasi bifunctional mechanism. The kinetic parameters indicated that the chemical reaction between adsorbed COad and OHad species could be the rate limiting step.

  2. Development of Pillared Clays for Wet Hydrogen Peroxide Oxidation of Phenol and Its Application in the Posttreatment of Coffee Wastewater

    Directory of Open Access Journals (Sweden)

    Nancy R. Sanabria

    2012-01-01

    Full Text Available This paper focuses on the use of pillared clays as catalysts for the Fenton-like advanced oxidation, specifically wet hydrogen peroxide catalytic oxidation (WHPCO. This paper discusses the limitations on the application of a homogeneous Fenton system, development of solid catalysts for the oxidation of phenol, advances in the synthesis of pillared clays, and their potential application as catalysts for phenol oxidation. Finally, it analyzes the use of pillared clays as heterogeneous Fenton-like catalysts for a real wastewater treatment, emphasizing the oxidation of phenolic compounds present in coffee wastewater. Typically, the wet hydrogen peroxide catalytic oxidation in a real effluent system is used as pretreatment, prior to biological treatment. In the specific case of coffee wet processing wastewater, catalytic oxidation with pillared bentonite with Al-Fe is performed to supplement the biological treatment, that is, as a posttreatment system. According to the results of catalytic activity of pillared bentonite with Al-Fe for oxidation of coffee processing wastewater (56% phenolic compounds conversion, 40% selectivity towards CO2, and high stability of active phase, catalytic wet hydrogen peroxide oxidation emerges as a viable alternative for management of this type of effluent.

  3. Catalytic and non-catalytic wet air oxidation of sodium dodecylbenzene sulfonate: kinetics and biodegradability enhancement.

    Science.gov (United States)

    Suárez-Ojeda, María Eugenia; Kim, Jungkwon; Carrera, Julián; Metcalfe, Ian S; Font, Josep

    2007-06-18

    Wet air oxidation (WAO) and catalytic wet air oxidation (CWAO) were investigated as suitable precursors for the biological treatment of industrial wastewater containing sodium dodecylbenzene sulfonate (DBS). Two hours WAO semi-batch experiments were conducted at 15 bar of oxygen partial pressure (P(O2)) and at 180, 200 and 220 degrees C. It was found that the highest temperature provides appreciable total organic carbon (TOC) and chemical oxygen demand (COD) abatement of about 42 and 47%, correspondingly. Based on the main identified intermediates (acetic acid and sulfobenzoic acid) a reaction pathway for DBS and a kinetic model in WAO were proposed. In the case of CWAO experiments, seventy-two hours tests were done in a fixed bed reactor in continuous trickle flow regime, using a commercial activated carbon (AC) as catalyst. The temperature and P(O2) were 140-160 degrees C and 2-9 bar, respectively. The influence of the operating conditions on the DBS oxidation, the occurrence of oxidative coupling reactions over the AC, and the catalytic activity (in terms of substrate removal) were established. The results show that the AC without any supported active metal behaves bi-functional as adsorbent and catalyst, giving TOC conversions up to 52% at 160 degrees C and 2 bar of P(O2), which were comparable to those obtained in WAO experiments. Respirometric tests were completed before and after CWAO and to the main intermediates identified through the WAO and CWAO oxidation route. Then, the readily biodegradable COD (COD(RB)) of the CWAO and WAO effluents were found. Taking into account these results it was possible to compare whether or not the CWAO or WAO effluents were suitable for a conventional activated sludge plant inoculated with non adapted culture.

  4. Mechanism of the development of a weakly alkaline barrier slurry without BTA and oxidizer

    Science.gov (United States)

    Xiaodong, Luan; Yuling, Liu; Xinhuan, Niu; Juan, Wang

    2015-07-01

    Controllable removal rate selectivity with various films (Cu, Ta, SiO2) is a challenging job in barrier CMP. H2O2 as an oxidizer and benzotriazole (BTA) as an inhibitor is considered to be an effective method in barrier CMP. Slurries that contain hydrogen peroxide have a very short shelf life because H2O2 is unstable and easily decomposed. BTA can cause post-CMP challenges, such as organic residue, toxicity and particle adhesion. We have been engaged in studying a weakly alkaline barrier slurry without oxidizer and benzotriazole. Based on these works, the objective of this paper is to discuss the mechanism of the development of the barrier slurry without oxidizer and benzotriazole by studying the effects of the different components (containing colloidal silica, FA/O complexing agent, pH of polishing solution and guanidine nitrate) on removal rate selectivity. The possible related polishing mechanism has also been proposed. Project supported by the Major National Science and Technology Special Projects (No. 2009ZX02308), the National Natural Science Foundation of Hebei Province, China (No. E2013202247), and the Department of Education-Funded Research Projects of Hebei Province, China (No. QN2014208).

  5. Spin-on metal oxide materials with high etch selectivity and wet strippability

    Science.gov (United States)

    Yao, Huirong; Mullen, Salem; Wolfer, Elizabeth; McKenzie, Douglas; Rahman, Dalil; Cho, JoonYeon; Padmanaban, Munirathna; Petermann, Claire; Hong, SungEun; Her, YoungJun

    2016-03-01

    Metal oxide or metal nitride films are used as hard mask materials in semiconductor industry for patterning purposes due to their excellent etch resistances against the plasma etches. Chemical vapor deposition (CVD) or atomic layer deposition (ALD) techniques are usually used to deposit the metal containing materials on substrates or underlying films, which uses specialized equipment and can lead to high cost-of-ownership and low throughput. We have reported novel spin-on coatings that provide simple and cost effective method to generate metal oxide films possessing good etch selectivity and can be removed by chemical agents. In this paper, new spin-on Al oxide and Zr oxide hard mask formulations are reported. The new metal oxide formulations provide higher metal content compared to previously reported material of specific metal oxides under similar processing conditions. These metal oxide films demonstrate ultra-high etch selectivity and good pattern transfer capability. The cured films can be removed by various chemical agents such as developer, solvents or wet etchants/strippers commonly used in the fab environment. With high metal MHM material as an underlayer, the pattern transfer process is simplified by reducing the number of layers in the stack and the size of the nano structure is minimized by replacement of a thicker film ACL. Therefore, these novel AZ® spinon metal oxide hard mask materials can potentially be used to replace any CVD or ALD metal, metal oxide, metal nitride or spin-on silicon-containing hard mask films in 193 nm or EUV process.

  6. Effect of SUS316L stainless steel surface conditions on the wetting of molten multi-component oxides ceramic

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Jin, E-mail: wangjinustb@gmail.com [Graduate School of Life Science and Systems Engineering, Kyushu Institute of Technology, Fukuoka, 808-0196 (Japan); Matsuda, Nozomu [Bar and Wire Product Unit, Nippon steel and Sumitomo Metal Corporation, Fukuoka, 802-8686 (Japan); Shinozaki, Nobuya [Graduate School of Life Science and Systems Engineering, Kyushu Institute of Technology, Fukuoka, 808-0196 (Japan); Miyoshi, Noriko [The Center for Instrumental Analysis, Kyushu Institute of Technology, Fukuoka, 804-8550 (Japan); Shiraishi, Takanobu [Graduate School of Biomedical Sciences, Nagasaki University, Nagasaki, 852-8588 (Japan)

    2015-02-01

    Highlights: • Multi-component oxides had a good wetting on stainless substrates with pretreatments. • Various substrates surface roughness caused the difference of final contact angles. • The wetting rate was slow on polished substrate due to the slow surface oxidation. - Abstract: A study on the effect of SUS316L stainless steel surface conditions on the wetting behavior of molten multi-component oxides ceramic was performed and aimed to contribute to the further understanding of the application of oxides ceramic in penetration treatment of stainless steel coatings and the deposition of stainless steel cermet coatings. The results show that at 1273 K, different surface pre-treatments (polishing and heating) had an important effect on the wetting behavior. The molten multi-component oxides showed good wettability on both stainless steel substrates, however, the wetting process on the polished substrate was significantly slower than that on the heated substrates. The mechanism of the interfacial reactions was discussed based on the microscopic and thermodynamic analysis, the substrates reacted with oxygen generated from the decomposition of the molten multi-component oxides and oxygen contained in the argon atmosphere, and the oxide film caused the molten multi-component oxides ceramic to spread on the substrates surfaces. For the polished substrate, more time was required for the surface oxidation to reach the surface composition of Heated-S, which resulted in relatively slow spreading and wetting rates. Moreover, the variance of the surface roughness drove the final contact angles to slightly different values following the sequence Polished-S > Heated-S.

  7. Preparation of glass carbon electrode modified with nanocrystalline nickel-decorated carbon nanotubes and electrocatalytic oxidation of methanol in alkaline solution

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    Nanocrystalline nickel with an average diameter of about 16 nm and a face-centered cubic (fcc)structure was uniformly attached to the surface of carbon nanotubes (CNT) by wet chemistry.The sample was characterized by X-ray powder diffraction and transmission electron microscopy (TEM).A glass carbon electrode modified with nickel-modified multi-wall carbon nanotubes (MWCNTs-Ni/GCE) was prepared.The electrochemical behavior of the MWCNTs-Ni/GCE and the electrocatalytic oxidation of methanol at the MWCNTsNi/GCE were investigated by cyclic voltammetry in 1.0 mol/L NaOH solution.The cyclic voltammograms showed that the electron transfer between β-Ni(OH)2 and β-NiOOH is mainly a diffusion-controlled quasireversible process,and that the electrode has high catalytic activity for the electrooxidation of methanol in alkaline medium,revealing its potential application in alkaline rechargeable batteries and fuel cells.

  8. Establishing the potential dependent equilibrium oxide coverage on platinum in alkaline solution and its influence on the oxygen reduction

    DEFF Research Database (Denmark)

    Wiberg, Gustav; Arenz, Matthias

    2012-01-01

    Publication year: 2012 Source:Journal of Power Sources, Volume 217 Gustav K.H. Wiberg, Matthias Arenz The oxidation process of polycrystalline platinum subjected to alkaline solution is re-examined using a combination of cyclic voltammetry and potential hold techniques in Ar, H2 and O2 purged 0.1 M...

  9. Wet Oxidation: A Promising Option for the Treatment of Pulp and Paper Mill Wastewater

    Science.gov (United States)

    Garg, A.

    2012-05-01

    Wet oxidation (WO) is used to degrade persistent organic or inorganic impurities present in industrial wastewater. The process utilizes severe oxidation conditions (i.e., high temperature and pressures) to achieve the efficient degradation of pollutants. To obtain high degradation at lower operation conditions, catalytic WO process is being suggested. The wastewater generated from a pulp and paper mill contains several recalcitrant compounds like lignin, hemi-cellulose, phenols, sulfides etc. Therefore, pulp and paper mill effluent have low biodegradability and are not amenable for conventional biological process. With the implementation of stringent regulations, pulp and paper mill operators need a cleaner disposal route for the wastewater. In this mini-review, the results obtained from the recently published studies on WO treatment for pulp and paper mill effluent are compiled and presented. Finally, the recommendations for the future work are also given.

  10. Wet etching of InSb surfaces in aqueous solutions: Controlled oxide formation

    Energy Technology Data Exchange (ETDEWEB)

    Aureau, D., E-mail: damien.aureau@chimie.uvsq.fr [Institut Lavoisier UVSQ-CNRS UMR 8180, 45 avenue des Etats Unis, Versailles, 78035 (France); Chaghi, R.; Gerard, I. [Institut Lavoisier UVSQ-CNRS UMR 8180, 45 avenue des Etats Unis, Versailles, 78035 (France); Sik, H.; Fleury, J. [Sagem Defense Sécurité, 72-74, rue de la tour Billy, 95101, Argenteuil Cedex (France); Etcheberry, A. [Institut Lavoisier UVSQ-CNRS UMR 8180, 45 avenue des Etats Unis, Versailles, 78035 (France)

    2013-07-01

    This paper investigates the wet etching of InSb surfaces by two different oxidant agents: Br{sub 2} and H{sub 2}O{sub 2} and the consecutive oxides generation onto the surfaces. The strong dependence between the chemical composition of the etching baths and the nature of the final surface chemistry of this low band-gap III–V semiconductor will be especially highlighted. One aqueous etching solution combined hydrobromic acid and Bromine (HBr–Br{sub 2}:H{sub 2}O) with adjusted concentrations. The other solution combines orthophosphoric and citric acids with hydrogen peroxide (H{sub 3}PO{sub 4}–H{sub 2}O{sub 2}:H{sub 2}O). Depending on its composition, each formulation gave rise to variable etching rate. The dosage of Indium traces in the etching solution by atomic absorption spectroscopy (AAS) gives the kinetic variation of the dissolution process. The variations on etching rates are associated to the properties and the nature of the formed oxides on InSb surfaces. Surface characterization is specifically performed by X-ray photoelectron spectroscopy (XPS). A clear evidence of the differences between the formed oxides is highlighted. Atomic force microscopy is used to monitor the surface morphology and pointed out that very different final morphologies can be reached. This paper presents new results on the strong variability of the InSb oxides in relation with the InSb reactivity toward environment interaction.

  11. pH Responsive and Oxidation Resistant Wet Adhesive based on Reversible Catechol-Boronate Complexation.

    Science.gov (United States)

    Narkar, Ameya R; Barker, Brett; Clisch, Matthew; Jiang, Jingfeng; Lee, Bruce P

    2016-08-09

    A smart adhesive capable of binding to a wetted surface was prepared by copolymerizing dopamine methacrylamide (DMA) and 3-acrylamido phenylboronic acid (AAPBA). pH was used to control the oxidation state and the adhesive property of the catechol side chain of DMA and to trigger the catechol-boronate complexation. FTIR spectroscopy confirmed the formation of the complex at pH 9, which was not present at pH 3. The formation of the catechol-boronate complex increased the cross-linking density of the adhesive network. Most notably, the loss modulus values of the adhesive were more than an order of magnitude higher for adhesive incubated at pH 9 when compared to those measured at pH 3. This drastic increase in the viscous dissipation property is attributed to the introduction of reversible complexation into the adhesive network. Based on the Johnson Kendall Roberts (JKR) contact mechanics test, adhesive containing both DMA and AAPBA demonstrated strong interfacial binding properties (work of adhesion (Wadh) = 2000 mJ/m(2)) to borosilicate glass wetted with an acidic solution (pH 3). When the pH was increased to 9, Wadh values (180 mJ/m(2)) decreased by more than an order of magnitude. During successive contact cycles, the adhesive demonstrated the capability to transition reversibly between its adhesive and nonadhesive states with changing pH. Adhesive containing only DMA responded slowly to repeated changes in pH and became progressively oxidized without the protection of boronic acid. Although adhesive containing only AAPBA also demonstrated strong wet adhesion (Wadh ∼ 500 mJ/m(2)), its adhesive properties were not pH responsive. Both DMA and AAPBA are required to fabricate a smart adhesive with tunable and reversible adhesive properties.

  12. Catalytic wet air oxidation of 2-chlorophenol over sewage sludge-derived carbon-based catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Tu, Yuting [Institut de recherches sur la catalyse et l’environnement de Lyon (IRCELYON), CNRS – Université Claude Bernard Lyon 1, 2 Avenue Albert Einstein, 69626 Villeurbanne Cedex (France); School of Environmental Science and Engineering, Sun Yat-Sen University, Guangzhou 510275 (China); Xiong, Ya; Tian, Shuanghong [School of Environmental Science and Engineering, Sun Yat-Sen University, Guangzhou 510275 (China); Guangdong Provincial Key Laboratory of Environmental Pollution Control and Remediation Technology, Guangzhou 510275 (China); Kong, Lingjun [School of Environmental Science and Engineering, Sun Yat-Sen University, Guangzhou 510275 (China); Descorme, Claude, E-mail: claude.descorme@ircelyon.univ-lyon1.fr [Institut de recherches sur la catalyse et l’environnement de Lyon (IRCELYON), CNRS – Université Claude Bernard Lyon 1, 2 Avenue Albert Einstein, 69626 Villeurbanne Cedex (France)

    2014-07-15

    Highlights: • A sewage sludge derived carbon-supported iron oxide catalyst (FeSC) was prepared. • FeSC exhibited high catalytic activity in the wet air oxidation of 2-chlorophenol. • A strong correlation was observed between the 2-CP conversion, the iron leaching and the pH. • Using an acetate buffer, the iron leaching was suppressed while keeping some catalytic activity. • A simplified reaction pathway was proposed for the CWAO of 2-CP over the FeSC catalyst. - Abstract: A sewage sludge derived carbon-supported iron oxide catalyst (FeSC) was prepared and used in the Catalytic Wet Air Oxidation (CWAO) of 2-chlorophenol (2-CP). The catalysts were characterized in terms of elemental composition, surface area, pH{sub PZC}, XRD and SEM. The performances of the FeSC catalyst in the CWAO of 2-CP was assessed in a batch reactor operated at 120 °C under 0.9 MPa oxygen partial pressure. Complete decomposition of 2-CP was achieved within 5 h and 90% Total Organic Carbon (TOC) was removed after 24 h of reaction. Quite a straight correlation was observed between the 2-CP conversion, the amount of iron leached in solution and the pH of the reaction mixture at a given reaction time, indicating a strong predominance of the homogeneous catalysis contribution. The iron leaching could be efficiently prevented when the pH of the solution was maintained at values higher than 4.5, while the catalytic activity was only slightly reduced. Upon four successive batch CWAO experiments, using the same FeSC catalyst recovered by filtration after pH adjustment, only a very minor catalyst deactivation was observed. Finally, based on all the identified intermediates, a simplified reaction pathway was proposed for the CWAO of 2-CP over the FeSC catalyst.

  13. Green chemicals from pulp production black liquor by partial wet oxidation.

    Science.gov (United States)

    Muddassar, Hassan Raja; Melin, Kristian; de Villalba Kokkonen, Daniela; Riera, Gerard Viader; Golam, Sarwar; Koskinen, Jukka

    2015-11-01

    To reduce greenhouse gas emissions, more sustainable sources of energy, fuel and chemicals are needed. Biomass side streams such as black liquor, which is a by-product of pulp production, has the potential to be used for this purpose. The aim of the study was the production of carboxylic acids, such as lactic acid, formic acid and acetic acid, from kraft and non-wood black liquor. The processes studied were partial wet oxidation (PWO) and catalytic partial wet oxidation (CPWO). The results show that the yield of carboxylic acid is higher when treated by PWO than the results from CPWO at temperatures of 170 °C and 230 °C. The results shows that the PWO process can increase the yield of carboxylic acids and hydroxy acids in black liquor, reduce lignin content and decrease pH, which makes further separation of the acids more favourable. The hydroxy acids are valuable raw materials for biopolymers, and acetic acid and formic acid are commonly used chemicals conventionally produced from fossil feedstock.

  14. Kinetics of Wet Air Oxidation of Wastewater from Natural Fiber Web Desizing

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    This work described the application of wet air oxidation (WAO) to the treatment of desizing wastewater from natural fiber processing. A two-liter autoclave batch reactor was used for the experiments. The range of operating temperature examined was between 150 and 290℃, and partial pressure of oxygen ranged from 0.375 to 2.25 MPa standardized at 25℃. Variations in Chemical Oxygen Demand(COD) and Total Organic Carbon(TOC) were monitored during each experiment and used to assess the performance of the process. Experimental results showed that WAO can be an efficient method for the treatment of desizing wnstewater. Furthermore, Catalytic Wet Air Oxidation (CWAO) was applied to reduce the reaction temperature and pressure in WAO process. A higher COD removal ratio was achieved under more mild reaction condition with the aid of CWAO. A mathematical model was also proposed to simulate the WAO process of desizing wastewater, in which three distinct kinetics steps were considered to describe the degradation of starch. The model simulations were in well agreement with the experimental data.

  15. Phosphorus recovery from sewage sludge with a hybrid process of low pressure wet oxidation and nanofiltration.

    Science.gov (United States)

    Blöcher, Christoph; Niewersch, Claudia; Melin, Thomas

    2012-04-15

    Phosphorus recovery from sewage sludge will become increasingly important within the next decades due to depletion of mineral phosphorus resources. In this work a new process concept was investigated, which aims at realising phosphorus recovery in a synergistic way with the overall sewage sludge treatment scheme. This process combines a low pressure wet oxidation for sewage sludge decomposition as well as phosphorus dissolution and a nanofiltration process to separate phosphorus from heavy metals and obtain a clean diluted phosphoric acid, from which phosphorus can be recovered as clean fertiliser. It was shown that this process concept is feasible for sewage sludge for wastewater treatment plants that apply enhanced biological removal or precipitation with alumina salts for phosphorus removal. The critical parameter for phosphorus dissolution in the low pressure wet oxidation process is the iron concentration, while in the nanofiltration multi-valent cations play a predominant role. In total, a phosphorus recovery of 54% was obtained for an exemplary wastewater treatment plant. Costs of the entire process are in the same range as conventional sewage sludge disposal, with the benefit being phosphorus recovery and reduced emission of greenhouse gases due to avoidance of sludge incineration.

  16. Effect of intermediate compounds and products on wet oxidation and biodegradation rates of pharmaceutical compounds.

    Science.gov (United States)

    Collado, Sergio; Laca, Adriana; Diaz, Mario

    2013-06-01

    Kinetics of pure compounds in batch agitated reactors are useful data to clarify the characteristics of a given reaction, but they frequently do not provide the required information to design industrial mixed continuous processes because in this case the final and intermediate products interact with the reaction of interest, due to backmixing effects. Simultaneously, the presence and transformations of other compounds, frequent in industrial wastewater treatments, adds more complexity to these types of interactions, whose effect can be different, favorable or unfavorable, for chemical or biological reactions. In this work, batch laboratory reactor data were obtained for the wet oxidation and biodegradation of four phenolic compounds present in a pharmaceutical wastewater and then compared with those collected from industrial continuous stirred tank reactors. For wet oxidation, batch laboratory degradation rates were significantly lower than those found in industrial continuous stirred operation. This behavior was explained by a different distribution of intermediate compounds in lab and industrial treatments, caused by the degree of backmixing and the synergistic effects between phenolic compounds (matrix effects). On the other hand, the specific utilization rates during aerobic biodegradation in the continuous industrial operation were lower than those measured in the laboratory, due to the simultaneous presence of the four pollutants in the industrial process (matrix effects) increasing the inhibitory effects of these compounds and its intermediates.

  17. Treatment of desizing wastewater from the textile industry by wet air oxidation

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    This paper describes the application of wet air oxidation to the treatment of desizing wastewater from two textile companies. A two-liter high temperature, high pressure autoclave reactor was used in the study. The range of operating temperatures examined was between 150 and 290℃, and the partial pressure of oxygen ranged from 0. 375 to 2.25 MPa. Variations in pH,CODCr and TOD content were monitored during each experiment and used to assess the extent of conversion of the process. The effects of temperature, pressure and reaction time were explored extensively. More than 90 % CODCr reduction and 80 % TOC removal have been obtained. The results have also been demonstrated that WAO is a suitable pre-treatment methods due to improvement of the BOD5/CODCr ratio of desizing wastewater. The reaction kinetics of wet air oxidation of desizing wastewater has been proved to be two steps, a fast reaction followed by a slow reaction stage.

  18. A preliminary study of the electro-oxidation of L-ascorbic acid on polycrystalline silver in alkaline solution

    Science.gov (United States)

    Majari Kasmaee, L.; Gobal, F.

    Electrochemical oxidation of L-ascorbic acid on polycrystalline silver in alkaline aqueous solutions is studied by cyclic voltammetry (CV), chronoamperometry (CA) and impedance spectroscopy (IS). The anodic electro-oxidation starts at -500 mV versus SCE and shows continued anodic oxidation in the cathodic half cycle in the CV regime signifying slowly oxidizing adsorbates. Diffusion coefficient of ascorbate ion measured under both voltammetric regimes is around 1.4 × 10 -5 cm 2 s -1. Impedance spectroscopy measures the capacitances associated with double layer and adsorption around 50 μF cm -2 and 4 mF cm -2 as well as the adsorption and decomposition resistances (rates).

  19. Deselenization and detellurization of precious-metal ore concentrates by swelling oxidizing roasting and successive alkaline leaching

    Science.gov (United States)

    Zhang, Fu-yuan; Zheng, Ya-jie; Peng, Guo-min

    2017-02-01

    A new technique of swelling oxidizing roasting and alkaline leaching was proposed for deselenization and detellurization of precious-metal ore concentrates. Alkali-metal and alkaline-earth-metal chlorides and carbonates were preliminarily selected as swelling agents. The roasting removal rate and alkaline leaching rate of selenium and tellurium were investigated, and NaCl was selected as an appropriate swelling agent. Furthermore, the effects of various factors on the selenium gasification rate and leaching rate of selenium and tellurium were investigated. The results show that the selenium gasification rate reaches 88.41% after swelling oxidizing roasting for 2 h at 510°C using an NaCl dosage coefficient of 100 and a sulfuric acid dosage coefficient of 1.3; the amorphous elemental tellurium is completely transformed into TiO2. The roasted product is subjected to alkaline leaching using a 100 g/L NaOH solution, which results in a selenium leaching rate of 10.51%, a total selenium removal rate of 98.92%, and a tellurium leaching rate of 97.64%. In the alkaline leaching residue, the contents of selenium, tellurium, gold, platinum, and palladium are 0.7825%, 5.492%, 8.333%, 0.2587%, and 1.113%, respectively; the precious metals are enriched approximately sixfold.

  20. Changes in methane oxidation activity and methanotrophic community composition in saline alkaline soils.

    Science.gov (United States)

    Serrano-Silva, Nancy; Valenzuela-Encinas, César; Marsch, Rodolfo; Dendooven, Luc; Alcántara-Hernández, Rocio J

    2014-05-01

    The soil of the former Lake Texcoco is a saline alkaline environment where anthropogenic drainage in some areas has reduced salt content and pH. Potential methane (CH4) consumption rates were measured in three soils of the former Lake Texcoco with different electrolytic conductivity (EC) and pH, i.e. Tex-S1 a >18 years drained soil (EC 0.7 dS m(-1), pH 8.5), Tex-S2 drained for ~10 years (EC 9.0 dS m(-1), pH 10.3) and the undrained Tex-S3 (EC 84.8 dS m(-1), pH 10.3). An arable soil from Alcholoya (EC 0.7 dS m(-1), pH 6.7), located nearby Lake Texcoco was used as control. Methane oxidation in the soil Tex-S1 (lowest EC and pH) was similar to that in the arable soil from Alcholoya (32.5 and 34.7 mg CH4 kg(-1) dry soil day(-1), respectively). Meanwhile, in soils Tex-S2 and Tex-S3, the potential CH4 oxidation rates were only 15.0 and 12.8 mg CH4 kg(-1) dry soil day(-1), respectively. Differences in CH4 oxidation were also related to changes in the methane-oxidizing communities in these soils. Sequence analysis of pmoA gene showed that soils differed in the identity and number of methanotrophic phylotypes. The Alcholoya soil and Tex-S1 contained phylotypes grouped within the upland soil cluster gamma and the Jasper Ridge, California JR-2 clade. In soil Tex-S3, a phylotype related to Methylomicrobium alcaliphilum was detected.

  1. Kinetics of oxidation of odorous sulfur compounds in aqueous alkaline solution with H2O2.

    Science.gov (United States)

    Feliers, C; Patria, L; Morvan, J; Laplanche, A

    2001-10-01

    Sulfur species oxidation is a crucial issue wastewater treatment. The production of sulfur compounds like H2S,CH3SH, C2H5SH, disulfides and dimethyle sulfide generates odorous nuisances for the neighborhood. The oxidation of these species by H2O2 in alkaline solution has been investigated. The results showed that thiols CH3SH and C2H5SH react with H202 only in their dissociated form RS- with rate constants respectively k = 8.81 +/- 0.48 M-1s-1 and 8.37 +/- 0.63 M-1.s-1. Mercaptans oxidation produces 100 % of dimethyldisulfide or diethyldisulfide. The oxidation of disulfides shows a difference of reactivity between H2O2 and HO2- towards sulfur species. Increasing the pH accelerates significantly the reactions in the case of CH3SSCH3. The oxidation rate can be described as: r = k[RSSR][H2O2][RSSR][H2O2] + k[RSSR][HO2-] [RSSR][HO2-] with k[RSSR][H2O2] = 1.2 x 10(-4) +/- 0.2 x 10(-4) M-1s-1 and k[RSSR][HO2-] = 3.4 x 10(-4) +/- 0.6 x 10(-4) M-1.s-1 for CH3SSCH3. Dimethyl sulfide presents a reactivity different from disulfides. The oxidation rate can also be described as: r = k[CH3SCH3][H2O21][CH3SCH3][H2O2] + k[CH3SCH3][HO-] [CH3SCH3][HO2-], however, oxidation rate decreases with pH increase. k[CH3SCH3][H2O2] = 12.8 x 10(-3) +/- 0.96 x 10(-3) M-1.s-1 and k[CH3SCH3][HO2-] = 4 x 10(-3) +/- 0.3 x 10(-3) M-1.s-1.

  2. Conversion and Estrogenicity of 17β-estradiol During Photolytic/Photocatalytic Oxidation and Catalytic Wet-air Oxidation.

    Science.gov (United States)

    Bistan, Mirjana; Tišler, Tatjana; Pintar, Albin

    2012-06-01

    Estrogen 17β-estradiol (E2), produced by human body and excreted into municipal wastewaters, belongs to the group of endocrine disrupting compounds that are resistant to biological degradation. The aim of this study was to assess the efficiency of E2 removal from aqueous solutions by means of catalytic wet-air oxidation (CWAO) and photolytic/photocatalytic oxidation. CWAO experiments were conducted in a trickle-bed reactor at temperatures up to 230 °C and oxygen partial pressure of 10 bar over TiO2 and Ru/TiO2 solids. Photolytic/photocatalytic oxidation was carried out in a batch slurry reactor employing a TiO2 P-25 (Degussa) catalyst under visible or UV light. HPLC analysis and yeast estrogen screen assay were used to evaluate the removal of E2 and estrogenicity of treated samples. The latter was completely removed during photolytic/photocatalytic oxidation under UV (365 nm) light and photocatalytic oxidation under visible light. In CWAO experiments, complete removal of both E2 and estrogenicity from the feed solution were noticed in the presence of TiO2 and Ru/TiO2 catalysts.

  3. Heterogeneous catalytic wet peroxide oxidation systems for the treatment of an industrial pharmaceutical wastewater.

    Science.gov (United States)

    Melero, J A; Martínez, F; Botas, J A; Molina, R; Pariente, M I

    2009-09-01

    The aim of this work was to assess the treatment of wastewater coming from a pharmaceutical plant through a continuous heterogeneous catalytic wet peroxide oxidation (CWPO) process using an Fe(2)O(3)/SBA-15 nanocomposite catalyst. This catalyst was preliminary tested in a batch stirred tank reactor (STR), to elucidate the influence of significant parameters on the oxidation system, such as temperature, initial oxidant concentration and initial pH of the reaction medium. In that case, a temperature of 80 degrees C using an initial oxidant concentration corresponding to twice the theoretical stoichiometric amount for complete carbon depletion and initial pH of ca. 3 allow TOC degradation of around 50% after 200 min of contact time. Thereafter, the powder catalyst was extruded with bentonite to prepare pellets that could be used in a fixed bed reactor (FBR). Results in the up-flow FBR indicate that the catalyst shows high activity in terms of TOC mineralization (ca. 60% under steady-state conditions), with an excellent use of the oxidant and high stability of the supported iron species. The activity of the catalyst is kept constant, at least, for 55h of reaction. Furthermore, the BOD(5)/COD ratio is increased from 0.20 to 0.30, whereas the average oxidation stage (AOS) changed from 0.70 to 2.35. These two parameters show a high oxidation degree of organic compounds in the outlet effluent, which enhances its biodegradability, and favours the possibility of a subsequent coupling with a conventional biological treatment.

  4. Effects of operational conditions on sludge degradation and organic acids formation in low-critical wet air oxidation.

    Science.gov (United States)

    Chung, Jinwook; Lee, Mikyung; Ahn, Jaehwan; Bae, Wookeun; Lee, Yong-Woo; Shim, Hojae

    2009-02-15

    Wet air oxidation processes are to treat highly concentrated organic compounds including refractory materials, sludge, and night soil, and usually operated at supercritical water conditions of high temperature and pressure. In this study, the effects of operational conditions including temperature, pressure, and oxidant dose on sludge degradation and conversion into subsequent intermediates such as organic acids were investigated at low critical wet oxidation conditions. The reaction time and temperature in the wet air oxidation process was shown an important factor affecting the liquefaction of volatile solids, with more significant effect on the thermal hydrolysis reaction rather than the oxidation reaction. The degradation efficiency of sludge and the formation of organic acids were improved with longer reaction time and higher reaction temperature. For the sludge reduction and the organic acids formation under the wet air oxidation, the optimal conditions for reaction temperature, time, pressure, and oxidant dose were shown approximately 240 degrees C, 30min, 60atm, and 2.0L/min, respectively.

  5. Catalytic wet air oxidation of phenol with functionalized carbon materials as catalysts: reaction mechanism and pathway.

    Science.gov (United States)

    Wang, Jianbing; Fu, Wantao; He, Xuwen; Yang, Shaoxia; Zhu, Wanpeng

    2014-08-01

    The development of highly active carbon material catalysts in catalytic wet air oxidation (CWAO) has attracted a great deal of attention. In this study different carbon material catalysts (multi-walled carbon nanotubes, carbon fibers and graphite) were developed to enhance the CWAO of phenol in aqueous solution. The functionalized carbon materials exhibited excellent catalytic activity in the CWAO of phenol. After 60 min reaction, the removal of phenol was nearly 100% over the functionalized multi-walled carbon, while it was only 14% over the purified multi-walled carbon under the same reaction conditions. Carboxylic acid groups introduced on the surface of the functionalized carbon materials play an important role in the catalytic activity in CWAO. They can promote the production of free radicals, which act as strong oxidants in CWAO. Based on the analysis of the intermediates produced in the CWAO reactions, a new reaction pathway for the CWAO of phenol was proposed in this study. There are some differences between the proposed reaction pathway and that reported in the literature. First, maleic acid is transformed directly into malonic acid. Second, acetic acid is oxidized into an unknown intermediate, which is then oxidized into CO2 and H2O. Finally, formic acid and oxalic acid can mutually interconvert when conditions are favorable.

  6. Pretreatment of Afyon alcaloide factory's wastewater by wet air oxidation (WAO).

    Science.gov (United States)

    Kaçar, Y; Alpay, E; Ceylan, V K

    2003-03-01

    In this study, pretreatment of Afyon (Turkey) alcaloide factory wastewater, a typical high strength industrial wastewater (chemical oxygen demand (COD)=26.65 kgm(-3), biological oxygen demand (BOD(5))=3.95 kgm(-3)), was carried out by wet air oxidation process. The process was performed in a 0.75 litre specially designed bubble reactor. Experiments were conducted to see the advantages of one-stage and two-stage oxidation and the effects of pressure, pH, temperature, catalyst type, catalyst loading and air or oxygen as gas source on the oxidation of the wastewater. In addition, BOD(5)/COD ratios of the effluents, which are generally regarded as an important index of biodegradability of a high-strength industrial wastewater, were determined at the end of some runs. After a 2h oxidation (T=150 degrees C, P=0.65 MPa, airflowrate=1.57 x 10(-5)m(3)s(-1), pH=7.0), the BOD(5)/COD ratio was increased from 0.15 to above 0.5 by using the salts of metals such as Co(2+),Fe(2+),Fe(2+)+Ni(2+),Cu(2+)+Mn(2+) as catalyst.

  7. Optical characteristics of wet-thermally oxidized bulk and nanoporous GaN

    Science.gov (United States)

    Kim, Sinjae; Kadam, Mahadev; Kang, Jin-Ho; Ryu, Sang-Wan

    2016-09-01

    Gallium nitride (GaN) films deposited on sapphire substrates by metal organic chemical vapor deposition were successfully transformed into bulk and nanoporous gallium oxide (Ga2O3) using a wet thermal oxidation technique. Oxidation depth measurements confirmed that the oxide growth appeared to be faster in the case of nanoporous GaN than that of bulk GaN. Spectroscopic ellipsometry was used to evaluate and compare the optical properties of nanoporous and bulk Ga2O3 films, such as refractive index and extinction coefficient, which revealed improved optical properties for nanoporous Ga2O3 compared to the bulk. The simulations conducted on the ellipsometric spectra for bulk and nanoporous Ga2O3 using the Forouhi-Bloomer model and the Bruggeman effective medium approximation revealed the best fit with a low mean square error value. In the case of nanoporous Ga2O3, zero absorption was observed in the wavelength range of 300 nm to 840 nm, supporting the use of this material as a transparent coating in optoelectronic devices.

  8. Pilot Testing of Mercury Oxidation Catalysts for Upstream of Wet FGD Systems

    Energy Technology Data Exchange (ETDEWEB)

    Richard Rhudy

    2006-06-30

    This final report presents and discusses results from a mercury control process development project entitled ''Pilot Testing of Mercury Oxidation Catalysts for Upstream of Wet FGD Systems''. The objective of this project was to demonstrate at pilot scale a mercury control technology that uses solid honeycomb catalysts to promote the oxidation of elemental mercury in the flue gas from coal combustion. Oxidized mercury is removed in downstream wet flue gas desulfurization (FGD) absorbers and leaves with the FGD byproducts. The goal of the project was to achieve 90% oxidation of elemental mercury in the flue gas and 90% overall mercury capture with the downstream wet FGD system. The project was co-funded by EPRI and the U.S. Department of Energy's National Energy Technology Laboratory (DOE NETL) under Cooperative Agreement DE-FC26-01NT41185. Great River Energy (GRE) and City Public Service (now CPS Energy) of San Antonio were also project co-funders and provided host sites. URS Group, Inc. was the prime contractor. Longer-term pilot-scale tests were conducted at two sites to provide catalyst life data. GRE provided the first site, at their Coal Creek Station (CCS), which fires North Dakota lignite, and CPS Energy provided the second site, at their Spruce Plant, which fires Powder River Basin (PRB) coal. Mercury oxidation catalyst testing began at CCS in October 2002 and continued through the end of June 2004, representing nearly 21 months of catalyst operation. An important finding was that, even though the mercury oxidation catalyst pilot unit was installed downstream of a high-efficiency ESP, fly ash buildup began to plug flue gas flow through the horizontal catalyst cells. Sonic horns were installed in each catalyst compartment and appeared to limit fly ash buildup. A palladium-based catalyst showed initial elemental mercury oxidation percentages of 95% across the catalyst, declining to 67% after 21 months in service. A carbon

  9. Inhibition and deactivation effects in catalytic wet oxidation of high-strength alcohol-distillery liquors

    Energy Technology Data Exchange (ETDEWEB)

    Belkacemi, K.; Larachi, F.; Hamoudi, S.; Turcotte, G.; Sayari, A. [Laval Univ., Sainte-Foy, Quebec (Canada)

    1999-06-01

    The removal efficiency of total organic carbon (TOC) from raw high-strength alcohol-distillery waste liquors was evaluated using three different treatments: thermolysis (T), noncatalytic wet oxidation (WO), and solid-catalyzed wet oxidation (CWO). The distillery liquors (TOC = 22,500 mg/l, sugars = 18,000 mg/l, and proteins = 13,500 mg/l) were produced by alcoholic fermentation of enzymatic hydrolyzates from steam-exploded timothy grass. TOC-abatement studies were conducted batchwise in a stirred autoclave to evaluate the influence of the catalyst (7:3, MnO{sub 2}/CeO{sub 2} mixed oxide), oxygen partial pressure (0.5--2.5 MPa), and temperature (453--523 K) on T, WO, and CWO processes. Although CWO outperformed T and WO, TOC conversions did not exceed {approximately}60% at the highest temperature used. Experiments provided prima facie evidence for a gradual fouling of the catalyst and a developing inhibition in the liquors which impaired deep TOC removals. Occurrence of catalyst deactivation by carbonaceous deposits was proven experimentally through quantitative and qualitative experiments such as elemental analysis and X-ray photoelectron spectroscopy. Inhibition toward further degradation of the liquors was ascribed to the occurrence of highly stable antioxidant intermediates via the Maillard reactions between dissolved sugars and proteins. A lumping kinetic model involving both reaction inhibition by dissolved intermediates and catalyst deactivation by carbonaceous deposits was proposed to account for the distribution of carbon in the liquid, solid, and the vapor phases.

  10. Conversion of the refractory ammonia and acetic acid in catalytic wet air oxidation of animal byproducts

    Institute of Scientific and Technical Information of China (English)

    Virginie Fontanier; Sofiane Zalouk; Stéphane Barbati

    2011-01-01

    Wet air oxidation (WAO) and catalytic wet air oxidation (CWAO) of slaughtered animal byproducts (ABPs) were investigated.Two step experiment was carried out consisting ofa non-catalysed WAO run followed by a CWAO run at 170-275℃, 20 MPa, and reaction time 180 min.The WAO (1st step) of sample (5 g/L total organic carbon (TOC)) yielded (82.0 ± 4)% TOC removal and (78.4 ± 13.2)%conversion of the initial organic-N into NH4+-N.Four metal catalysts (Pd, Pt, Rh, Ru) supported over alumina have been tested in catalytic WAO (2nd step) at elevated pH to enhance ammonia conversion and organic matter removal, particularly acetic acid.It was found that the catalysts Ru, Pt, and Rh had significant effects on the TOC removal (95.1%, 99.5% and 96.7%, respectively) and on the abatement of ammonia (93.4%, 96.7% and 96.3%, respectively) with high nitrogen selectivity.The catalyst Pd was found to have the less activity while Pt had the best performance.The X-Ray diffraction analysis showed that the support of catalyst was not stable under the experimental conditions since it reacted with phosphate present in solution.Nitrite and nitrate ions were monitored during the oxidation reaction and it was concluded that CWAO of ammonia in real waste treatment framework was in good agreement with the results obtained from the literature for ideal solutions of ammonia.

  11. Wet oxidation treatment of organic household waste enriched with wheat straw for simultaneous saccharification and fermentation into ethanol

    DEFF Research Database (Denmark)

    Lissens, G.; Klinke, H.B.; Verstraete, W.;

    2004-01-01

    Organic municipal solid waste enriched with wheat straw was subjected to wet-oxidation as a pre-treatment for subsequent enzymatic conversion and fermentation into bio-ethanol. The effect of tempera (185-195degrees C), oxygen pressure (3-12) and sodium carbonate (0-2 g l(-1)) addition on enzymatic...... cellulose and hemicellulose convertibility was studied at a constant wet oxidation retention time of 10 minutes. An enzyme convertibility assay at high enzyme loading (25 filter paper unit (FPU) g(-1) dry solids (DS) added) showed that up to 78% of the cellulose and up to 68% of the hemicellulose...... in the treated waste could be converted into respectively hexose and pentose sugars compared to 46% for cellulose and 36% for hemicellulose in the raw waste. For all wet oxidation conditions tested, total carbohydrate recoveries were high (> 89%) and 44-66% of the original lignin could be converted into non...

  12. Recovery of manganese oxides from spent alkaline and zinc–carbon batteries. An application as catalysts for VOCs elimination

    Energy Technology Data Exchange (ETDEWEB)

    Gallegos, María V., E-mail: plapimu@yahoo.com.ar [Pla.Pi.Mu-Planta Piloto Multipropósito, (CICPBA-UNLP) Cno. Centenario y 505, M.B. Gonnet, Buenos Aires (Argentina); Falco, Lorena R., E-mail: mlfalco@quimica.unlp.edu.ar [Pla.Pi.Mu-Planta Piloto Multipropósito, (CICPBA-UNLP) Cno. Centenario y 505, M.B. Gonnet, Buenos Aires (Argentina); Peluso, Miguel A., E-mail: apelu@quimica.unlp.edu.ar [Centro de Investigación y Desarrollo en Ciencias Aplicadas, “Dr. J. Ronco” CINDECA (CONICET CCT La Plata), 47 N°257, La Plata, Buenos Aires (Argentina); Sambeth, Jorge E., E-mail: sambeth@quimica.unlp.edu.ar [Centro de Investigación y Desarrollo en Ciencias Aplicadas, “Dr. J. Ronco” CINDECA (CONICET CCT La Plata), 47 N°257, La Plata, Buenos Aires (Argentina); Thomas, Horacio J. [Pla.Pi.Mu-Planta Piloto Multipropósito, (CICPBA-UNLP) Cno. Centenario y 505, M.B. Gonnet, Buenos Aires (Argentina)

    2013-06-15

    Highlights: • Manganese oxides were synthesized using spent batteries as raw materials. • Spent alkaline and zinc–carbon size AA batteries were used. • A biohydrometallurgical process was employed to bio-lixiviate batteries. • Manganese oxides were active in the oxidation of VOCs (ethanol and heptane). - Abstract: Manganese, in the form of oxide, was recovered from spent alkaline and zinc–carbon batteries employing a biohydrometallurgy process, using a pilot plant consisting in: an air-lift bioreactor (containing an acid-reducing medium produced by an Acidithiobacillus thiooxidans bacteria immobilized on elemental sulfur); a leaching reactor (were battery powder is mixed with the acid-reducing medium) and a recovery reactor. Two different manganese oxides were recovered from the leachate liquor: one of them by electrolysis (EMO) and the other by a chemical precipitation with KMnO{sub 4} solution (CMO). The non-leached solid residue was also studied (RMO). The solids were compared with a MnO{sub x} synthesized in our laboratory. The characterization by XRD, FTIR and XPS reveal the presence of Mn{sub 2}O{sub 3} in the EMO and the CMO samples, together with some Mn{sup 4+} cations. In the solid not extracted by acidic leaching (RMO) the main phase detected was Mn{sub 3}O{sub 4}. The catalytic performance of the oxides was studied in the complete oxidation of ethanol and heptane. Complete conversion of ethanol occurs at 200 °C, while heptane requires more than 400 °C. The CMO has the highest oxide selectivity to CO{sub 2}. The results show that manganese oxides obtained using spent alkaline and zinc–carbon batteries as raw materials, have an interesting performance as catalysts for elimination of VOCs.

  13. Separating nano graphene oxide from the residual strong-acid filtrate of the modified Hummers method with alkaline solution

    Energy Technology Data Exchange (ETDEWEB)

    Hu, Xuebing, E-mail: xuebinghu2010@gmail.com [Key Laboratory of Inorganic Membrane, Jingdezhen Ceramic Institute, Jingdezhen 333001 (China); Key Laboratory of Inorganic Coating Materials, Shanghai Institute of Ceramics, Chinese Academy of Science, Shanghai 201800 (China); Yu, Yun, E-mail: yunyush@mail.sic.ac.cn [Key Laboratory of Inorganic Coating Materials, Shanghai Institute of Ceramics, Chinese Academy of Science, Shanghai 201800 (China); Wang, Yongqing; Zhou, Jianer [Key Laboratory of Inorganic Membrane, Jingdezhen Ceramic Institute, Jingdezhen 333001 (China); Song, Lixin [Key Laboratory of Inorganic Coating Materials, Shanghai Institute of Ceramics, Chinese Academy of Science, Shanghai 201800 (China)

    2015-02-28

    Graphical abstract: By adding an alkaline (NaOH or KOH) solution, the unprecipitated nano graphene oxide undergoes fast aggregation from the residual strong-acid filtrate of the modified Hummers method and forms the stable floccules when the pH value of the filtrate is about 1.7. The acid–base interaction with the surface functional groups of the carbon layers plays a role in the aggregation of the unprecipitated nano graphene oxide. - Highlights: • The novel and high-efficient method for separating graphene oxide was showed. • Graphene oxide undergoes aggregation and forms the floccules when pH value is ∼1.7. • The acid–base interaction plays a role in the aggregation of graphene oxide. - Abstract: In the modified Hummers method for preparing graphene oxide, the yellow slurry can be obtained. After filtering through a quantitative filter paper, the strong-acid filtrate containing the unprecipitated nano graphene oxide was gained. The corresponding filtrate was added gradually with an alkaline (NaOH or KOH) solution at room temperature. The unprecipitated nano graphene oxide could undergo fast aggregation when the pH value of the filtrate was about 1.7 and formed the stable floccules. X-ray diffraction analysis shows the dominant peak of the floccules is about 11°, which accords to the peak of graphene oxide. Spectra of X-ray photoelectron spectroscopy confirm the presence in the floccules of an abundance of oxygen functional groups and the purified graphene oxide floccules can be obtained. Atomic force microscopy measurement shows the graphene oxide floccules consists of sheet-like objects, mostly containing only a few layers (about 5 layers). Zeta potential analysis demonstrates the surface charge of the graphene oxide is pH-sensitive and its isoelectric point is ∼1.7. The flocculation mechanism of graphene oxide ascribes to the acid–base interaction with the surface functional groups of the carbon layers.

  14. Studies on the synthesis of europium activated yttrium oxide by wet-chemical method

    Energy Technology Data Exchange (ETDEWEB)

    Muresan, Laura [Raluca Ripan Institute for Research in Chemistry, Fantanele 30, 400294 Cluj-Napoca (Romania)], E-mail: laura_muresan2003@yahoo.com; Popovici, Elisabeth-Jeanne; Grecu, Rodica [Raluca Ripan Institute for Research in Chemistry, Fantanele 30, 400294 Cluj-Napoca (Romania); Tudoran, Lucian Barbu [Electronic Microscopy Center, Babes-Bolyai University, 400028 Cluj-Napoca (Romania)

    2009-03-05

    Europium activated yttrium oxide phosphor powders (Y{sub 2}O{sub 3}:Eu{sup 3+}) were prepared from yttrium-europium precursors obtained by wet-chemical method. With this purpose in view, precursors were prepared using the reagent simultaneous addition SimAdd technique from yttrium-europium nitrate and chloride as rare-earth supplier and urea, ammonium oxalate, ammonium carbonate and oxalic acid as precipitating agents. Precursors, obtained under controlled concentration, temperature and pH conditions, were fired at 1200 deg. C in order to generate Y{sub 2}O{sub 3}:Eu{sup 3+} phosphor powders. Yttrium-europium precursors and Y{sub 2}O{sub 3}:Eu{sup 3+} phosphor powders were investigated by FTIR, TGA-DTA, X-ray diffraction (XRD), scanning electronic microscopy (SEM) and photoluminescence spectroscopy (PL) in order to put in evidence the influence of the quality of yttrium-europium precursors obtained by wet-chemical method, using the SimAdd technique on the properties of Y{sub 2}O{sub 3}:Eu{sup 3+} phosphor powders.

  15. Operational wastes management - 'wet oxidation' - an innovative process to manage radiological spent resins

    Energy Technology Data Exchange (ETDEWEB)

    Benvenuto, F.; Maggini, F.; Mazzoni, C.; Orlandi, S.; Ricci, C. [Nuclear System Engineering Department, Ansaldo Nucleare S.p.A., Corso Perrone 25, 16161 Genova (Italy)

    2010-07-01

    A new system using the wet-oxidation process has been studied for the treatment of the organic radioactive waste such spent ion exchange resins. The purpose of the process is to enable a high degree of volume reduction of the waste and compared with various processes for treating sludge and resin, the wet-oxidation system is rather simple and it works in mild conditions. Verification tests have been performed in a large scale pilot plant with not contaminated ion exchange resin samples similar to those ones used in NPPs. (authors)

  16. Catalytic wet oxidation of phenol: the role of promoter and ceramic support.

    Science.gov (United States)

    Hussain, S Tajammul; Jamil, Sadaf; Mazhar, Muhammad

    2009-04-14

    Complete mineralization of phenol has been achieved over a cerium-manganese catalyst, doped with potassium, supported on a modified zeolite with a high surface area, under very mild conditions (110 degrees C, P(O2) = 0.5 MPa). This newly developed supported catalyst restricts the formation of bulk polymeric species on the surface, thus increasing the lifetime of the catalyst. It demonstrates superior textural, structural and surface oxygen properties compared with the reference cerium-manganese oxide catalyst. The supported catalyst maintains not only the high surface area but also the nanoparticle size during the catalytic run, thereby providing the full availability of the surface for reacting molecules. The geometry of the catalyst is modified electronically by the addition of potassium, and the zeolite addition restricts the conversion of Ce, Mn and K to higher oxidation states, thereby maintaining the geometry of catalytic active sites. The performance measured with this novel catalyst indicates a major improvement in the efficient application of the catalytic wet oxidation process for complete purification ofa complex waste stream.

  17. Catalytic wet-air oxidation of a chemical plant wastewater over platinum-based catalysts.

    Science.gov (United States)

    Cybulski, Andrzej; Trawczyński, Janusz

    2006-01-01

    Catalytic wet-air oxidation (CWAO) of wastewater (chemical oxygen demand [COD] = 1800 mg O2/dm3) from a fine chemicals plant was investigated in a fixed-bed reactor at T = 393-473 K under total pressure of 5.0 or 8.0 MPa. Catalysts containing 0.3% wt. of platinum deposited on two supports, mixed silica-titania (SM1) and carbon black composites (CBC) were used. The CBC-supported catalyst appeared to be more active than the SM1-supported one. A slow decrease of activity of the platinum on SM1 (Pt-SM1) during the long-term operation is attributed to recrystallization of titania and leaching of a support component, while the Pt-CBC catalyst is deteriorated, owing to combustion of the support component. The power-law-kinetic equations were used to describe the rate of COD removal at CWAO over the catalysts. The kinetic parameters of COD reduction for the wastewater were determined and compared with the kinetic parameters describing phenol oxidation over the same catalysts. Rates of COD removal for the wastewater were found higher than those for phenol oxidation over the same catalysts and under identical operating conditions.

  18. Influence of wet oxidation on the surface area and the porosity of some lignites

    Energy Technology Data Exchange (ETDEWEB)

    Yaman, S.; Karatepe, N.; Kucukbayrak, S. [Istanbul Technical University, Istanbul (Turkey). Chemical and Metallurgical Engineering Faculty

    2000-07-01

    Influence of wet oxidation on the surface area and the porosity of lignites was investigated using five different Turkish lignites. Lignite samples were oxidised in aqueous medium in a 1 l Parr autoclave at 423 K under 1.5 MPa partial pressure of oxygen for 60 min. Some physical properties such as surface area, bulk density, apparent density, mean pore radius, and porosity of the original and oxidised lignite samples were determined. For this purpose, BET and mercury intrusion porosimetry techniques were performed. In order to examine the effects of oxidation on the functional groups, FT-IR technique was applied for both original and oxidised lignite samples. On the other hand, some inorganic constituents were eliminated from the samples as a result of in situ formation of sulphuric acid from oxidation of sulphur compounds. The changes taken place in the physical properties were studied considering chemical compositions of the samples and the extent of the interaction between the samples and oxygen. 6 refs., 3 figs., 5 tabs.

  19. Manganese zinc ferrite nanoparticles as efficient catalysts for wet peroxide oxidation of organic aqueous wastes

    Indian Academy of Sciences (India)

    Manju Kurian; Divya S Nair

    2015-03-01

    Manganese substituted zinc nanoparticles, MnxZn1−xFe2O4 (x = 0.0, 0.25, 0.5, 0.75, 1.0) prepared by sol gel method were found to be efficient catalysts for wet peroxide oxidation of 4-chlorophenol. Complete degradation of the target pollutant occurred within 90 min at 70°C. Zinc substitution enhanced the catalytic efficiency and the unsubstituted ZnFe2O4 oxidized the target compound completely within 45 min. Studies on the effect of reaction variables revealed that only a small amount of the oxidant, H2O2 (3–4 mL) is required for complete degradation of 4-chlorophenol. More than 80% of 4-chlorophenol was removed at catalyst concentrations of 100 mg/L. Direct correlation between the amount of catalyst present and the extent of degradation of 4-chlorophenol was observed, ruling out hesterogeneous-homogeneous mechanism. The catalysts are reusable and complete degradation of target pollutant occurred after five successive runs. The extent of iron leaching was fairly low after five consecutive cycles indicating the mechanism to be heterogeneous.

  20. TOC reduction of alcohol distillery wastewater by wet oxidation using heterogeneous catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Belkacemi, K.; Hamoudi, S.; Larachi, F.; Montero, J.P.; Sayari, A.; Turcotte, G. [Universite Laval, Quebec (Canada)

    1997-07-01

    We studied the potential of three heterogeneous wet air oxidation (WAO) catalysts to reduce the total organic carbon (TOC) content of two distillery waste liquors. The catalysts were 1% Pt/Al{sub 2}O{sub 3}, Mn/Ce composite oxides, and Cu{sup 2+}-exchanged NaY zeolite. The liquors were produced from alcohol fermentation of enzymatic hydrolyzates originating from steam- and ammonia-exploded forages and agricultural residues. Initial WAO reaction rates of the liquors were measured batchwise in the temperature range 180 to 250{sup o}C under pure oxygen at 0.5 to 2.5 MPa. The WAO initial rates were first order for TOC, and the activation energies of the catalysts varied between 34 and 51 kJ/mol. The highest TOC abatements were achieved over Mn/Ce oxides and Cu{sup 2+}/NaY catalysts. Kinetic tests over extended times revealed the formation of significant amounts of strongly adsorbed carbonaceous foulants, which were responsible for the loss of catalyst activity. Foulants were tentatively characterized by means of X-ray photoelectron spectroscopy (XPS). (author)

  1. Treatment of biomass gasification wastewater using a combined wet air oxidation/activated sludge process

    Energy Technology Data Exchange (ETDEWEB)

    English, C.J.; Petty, S.E.; Sklarew, D.S.

    1983-02-01

    A lab-scale treatability study for using thermal and biological oxidation to treat a biomass gasification wastewater (BGW) having a chemical oxygen demand (COD) of 46,000 mg/l is described. Wet air oxidation (WA0) at 300/sup 0/C and 13.8 MPa (2000 psi) was used to initially treat the BGW and resulted in a COD reduction of 74%. This was followed by conventional activated sludge treatment using operating conditions typical of municipal sewage treatment plants. This resulted in an additional 95% COD removal. Overall COD reduction for the combined process was 99%. A detailed chemical analysis of the raw BGW and thermal and biological effluents was performed using gas chromatography/mass spectrometry (GC/MS). These results showed a 97% decrease in total extractable organics with WA0 and a 99.6% decrease for combined WA0 and activated sludge treatment. Components of the treated waters tended to be fewer in number and more highly oxidized. An experiment was conducted to determine the amount of COD reduction caused by volatilization during biological treatment. Unfortunately, this did not yield conclusive results. Treatment of BGW using WA0 followed by activated sludge appears to be very effective and investigations at a larger scale are recommended.

  2. Relative influence of process variables during non-catalytic wet oxidation of municipal sludge.

    Science.gov (United States)

    Baroutian, Saeid; Smit, Anne-Marie; Gapes, Daniel James

    2013-11-01

    Individual and interactive effects of process variables on the degradation of fermented municipal sludge were examined during wet oxidation. The process was carried out at 220-240°C using 1:1-2:1 oxygen to biomass ratio and 300-500 rpm stirring speed. Response surface methodology coupled with a faced-centred central composite design was used to evaluate the effect of these variables on total suspended solids, volatile suspended solids and total chemical oxygen demand. Multivariate analysis was conducted for the initial and near completion stages of reaction: 5 and 60 min treatments, respectively. Temperature had the most significant effect on degradation rate throughout. During the initial stage the effect of mixing intensity was less significant than that of oxygen ratio. Mixing intensity did not influence degradation rate at the later stage in the process. During the near completion stage, the interaction of temperature and oxygen ratio had significant effect on sludge degradation.

  3. Fe salts as catalyst for the wet oxidation of o-chlorophenol

    Institute of Scientific and Technical Information of China (English)

    XU Xin-hua; HE Ping; JIN Jian; HAO Zhi-wei

    2005-01-01

    Catalytic wet air oxidation (CWAO) of o-chlorophenol in wastewater was studied in a stainless steel autoclave using four different Fe catalysts in the temperature range of 100-200 ℃. Experimental results showed that high rate of o-chlorophenol and CODcr (Chemical Oxygen Demand, mg/L) removal by CWAO was obtained at relatively low temperature and pressure. The catalysts Fe2(SO4)3, FeSO4, Fe2O3 and FeCl3 all exhibited high catalytic activity. More than 93.7% of the initial CODCr and nearly100% of o-chlorophenol were removed at 150 ℃ after 150 min with FeSO4 as catalyst. The CWAO of o-chlorophenol was found to be pseudo-first order reaction with respect to o-chlorophenol, with activation energy of 75.56 k J/mol in the temperature range of100-175 ℃.

  4. Study on Catalytic Wet Oxidation of H2S into Sulfur on Fe/Cu Catalyst

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    A wet catalytic oxidation at room temperature was investigated with solution containing ferric, ferrous and cupric ions for H2S removal. The experiments were carried out in a two step process,and the results obtained show that the removal efficiency of H2S can always reach 100% in a 300 mm scrubbing column with four sieve plates, and the regeneration of ferric ions in 200 mm bubble column can match the consumed ferric species in absorption. Removal of H2S, production of elemental sulfur and regeneration of ferric, cupric ions can all be accomplished at the same time. No raw material is consumed except O2 in flue gas or air, the process has no secondary pollution and no problem of catalyst degradation and congestion.

  5. Optimizing Oily Wastewater Treatment Via Wet Peroxide Oxidation Using Response Surface Methodology

    Energy Technology Data Exchange (ETDEWEB)

    Shi, Jianzhong; Wang, Xiuqing; Wang, Xiaoyin [Wuhan Textile Univ., Wuhan (China)

    2014-02-15

    The process of petroleum involves in a large amount of oily wastewater that contains high levels of chemical oxygen demand (COD) and toxic compounds. So they must be treated before their discharge into the receptor medium. In this paper, wet peroxide oxidation (WPO) was adopted to treat the oily wastewater. Central composite design, an experimental design for response surface methodology (RSM), was used to create a set of 31 experimental runs needed for optimizing of the operating conditions. Quadratic regression models with estimated coefficients were developed to describe the COD removals. The experimental results show that WPO could effectively reduce COD by 96.8% at the optimum conditions of temperature 290 .deg. C, H{sub 2}O{sub 2} excess (HE) 0.8, the initial concentration of oily wastewater 3855 mg/L and reaction time 9 min. RSM could be effectively adopted to optimize the operating multifactors in complex WPO process.

  6. A 3D AgCl hierarchical superstructure synthesized by a wet chemical oxidation method.

    Science.gov (United States)

    Lou, Zaizhu; Huang, Baibiao; Ma, Xiangchao; Zhang, Xiaoyang; Qin, Xiaoyan; Wang, Zeyan; Dai, Ying; Liu, Yuanyuan

    2012-12-07

    A novel 3D AgCl hierarchical superstructure, with fast growth along the 〈111〉 directions of cubic seeds, is synthesized by using a wet chemical oxidation method. The morphological structures and the growth process are investigated by scanning electron microscopy and X-ray diffraction. The crystal structures are analyzed by their crystallographic orientations. The surface energy of AgCl facets {100}, {110}, and {111} with absorbance of Cl(-) ions is studied by density functional theory calculations. Based on the experimental and computational results, a plausible mechanism is proposed to illustrate the formation of the 3D AgCl hierarchical superstructures. With more active sites, the photocatalytic activity of the 3D AgCl hierarchical superstructures is better than those of concave and cubic ones in oxygen evolution under irradiation by visible light.

  7. Ethanol production from maize silage as lignocellulosic biomass in anaerobically digested and wet-oxidized manure.

    Science.gov (United States)

    Oleskowicz-Popiel, Piotr; Lisiecki, Przemyslaw; Holm-Nielsen, Jens Bo; Thomsen, Anne Belinda; Thomsen, Mette Hedegaard

    2008-09-01

    In this communication, pretreatment of the anaerobically digested (AD) manure and the application of the pretreated AD manure as liquid medium for the simultaneous saccharification and fermentation (SSF) were described. Furthermore, fermentation of pretreated maize silage and wheat straw was investigated using 2l bioreactors. Wet oxidation performed for 20 min at 121 degrees C was found as the most suitable pretreatment conditions for AD manure. High ammonia concentration and significant amount of macro- and micro-nutrients in the AD manure had a positive influence on the ethanol fermentation. No extra nitrogen source was needed in the fermentation broth. It was shown that the AD manure could successfully substitute process water in SSF of pretreated lignocellulosic fibres. Theoretical ethanol yields of 82% were achieved, giving 30.8 kg ethanol per 100 kg dry mass of maize silage.

  8. Degradation of phenylamine by catalytic wet air oxidation using metal catalysts with modified supports.

    Science.gov (United States)

    Torrellas, Silvia A; Escudero, Gabriel O; Rodriguez, Araceli R; Rodriguez, Juan G

    2015-01-01

    The effect of acid treatments with HCl and HNO3 on the surface area and surface chemistry of three granular activated carbons was studied. These supports were characterized and the hydrochloric acid treatment leads to the best activated carbon support (AC2-C). The catalytic behavior of Pt, Ru and Fe (1 wt.%) supported on granular activated carbon treated with HCl was tested in the phenylamine continuous catalytic wet air oxidation in a three-phase, high-pressure catalytic reactor over a range of reaction temperatures 130-170ºC and total pressure of 1.0-3.0 MPa at LHSV = 0.4-1 h(-1), whereas the phenylamine concentration range and the catalyst loading were 5-16 mol.m(-3) and 0.5-1.5 g, respectively. Activity as well as conversion varied as a function of the metal, the catalyst preparation method and operation conditions. Higher activities were obtained with Pt incorporated on hydrochloric acid -treated activated carbon by the ion exchange method. In steady state, approximately 98% phenylamine conversion, 77% of TOC and 94% of COD removal, was recorded at 150ºC, 11 mol m(-3) of phenylamine concentration and 1.5 g of catalyst, and the selectivity to non-organic compounds was 78%. Several reaction intermediaries were detected. A Langmuir-Hinshelwood model gave an excellent fit of the kinetic data of phenylamine continuous catalytic wet air oxidation over the catalysts of this work.

  9. Stability of ZnMgO oxide in a weak alkaline solution

    Energy Technology Data Exchange (ETDEWEB)

    Diler, E. [Laboratoire de Magnetisme de Bretagne, EA 4522, CNRS, Universite de Brest, UBO, 6 av. Le Gorgeu, 29285 Brest Cedex (France); Institut de la Corrosion, 220 rue Pierre Rivoalon, 29200 Brest (France); Rioual, S., E-mail: rioual@univ-brest.fr [Laboratoire de Magnetisme de Bretagne, EA 4522, CNRS, Universite de Brest, UBO, 6 av. Le Gorgeu, 29285 Brest Cedex (France); Lescop, B. [Laboratoire de Magnetisme de Bretagne, EA 4522, CNRS, Universite de Brest, UBO, 6 av. Le Gorgeu, 29285 Brest Cedex (France); Thierry, D. [Institut de la Corrosion, 220 rue Pierre Rivoalon, 29200 Brest (France); Rouvellou, B. [Laboratoire de Magnetisme de Bretagne, EA 4522, CNRS, Universite de Brest, UBO, 6 av. Le Gorgeu, 29285 Brest Cedex (France)

    2012-01-31

    Zinc oxide (ZnO) is a chemical compound of great interest used, for example, as photocatalyst in the purification of wastewater or polluted air. However, neither dissolution, nor photo-dissolution of ZnO is negligible: indeed, both processes reduce significantly the efficiency of photocatalysis and then lead to a secondary pollution by free Zn{sup 2+}. In the present study, the stability of ZnMgO thin films in weak alkaline solution is investigated. We demonstrate that the replacement of Zn{sup 2+} ion with Mg{sup 2+} ion results in the production of a Zn{sub 0.84}Mg{sub 0.16}O solid solution, whose stability is higher than that of the ZnO sample. This alloy, thus, constitutes an alternative to the use of ZnO in photocatalysis applications. To gain more insights into the higher resistance of such alloys to the dissolution process, X-Ray photoelectron spectroscopy measurements were performed. They highlighted the role of OH group adsorption in the experimentally observed enhancement of ZnMgO stability.

  10. Pilot Testing of Mercury Oxidation Catalysts for Upstream of Wet FGD Systems

    Energy Technology Data Exchange (ETDEWEB)

    Richard Rhudy

    2006-06-30

    This final report presents and discusses results from a mercury control process development project entitled ''Pilot Testing of Mercury Oxidation Catalysts for Upstream of Wet FGD Systems''. The objective of this project was to demonstrate at pilot scale a mercury control technology that uses solid honeycomb catalysts to promote the oxidation of elemental mercury in the flue gas from coal combustion. Oxidized mercury is removed in downstream wet flue gas desulfurization (FGD) absorbers and leaves with the FGD byproducts. The goal of the project was to achieve 90% oxidation of elemental mercury in the flue gas and 90% overall mercury capture with the downstream wet FGD system. The project was co-funded by EPRI and the U.S. Department of Energy's National Energy Technology Laboratory (DOE NETL) under Cooperative Agreement DE-FC26-01NT41185. Great River Energy (GRE) and City Public Service (now CPS Energy) of San Antonio were also project co-funders and provided host sites. URS Group, Inc. was the prime contractor. Longer-term pilot-scale tests were conducted at two sites to provide catalyst life data. GRE provided the first site, at their Coal Creek Station (CCS), which fires North Dakota lignite, and CPS Energy provided the second site, at their Spruce Plant, which fires Powder River Basin (PRB) coal. Mercury oxidation catalyst testing began at CCS in October 2002 and continued through the end of June 2004, representing nearly 21 months of catalyst operation. An important finding was that, even though the mercury oxidation catalyst pilot unit was installed downstream of a high-efficiency ESP, fly ash buildup began to plug flue gas flow through the horizontal catalyst cells. Sonic horns were installed in each catalyst compartment and appeared to limit fly ash buildup. A palladium-based catalyst showed initial elemental mercury oxidation percentages of 95% across the catalyst, declining to 67% after 21 months in service. A carbon

  11. Enhanced wet hydrogen peroxide catalytic oxidation performances based on CuS nanocrystals/reduced graphene oxide composites

    Science.gov (United States)

    Qian, Jing; Wang, Kun; Guan, Qingmeng; Li, Henan; Xu, Hui; Liu, Qian; Liu, Wei; Qiu, Baijing

    2014-01-01

    CuS nanocrystals/reduced graphene oxide (CuS NCs/rGO) composites were prepared by a facile one-pot solvothermal reaction. In this solvothermal system, thioacetamide was found to perform the dual roles of sulphide source and reducing agent, resulting in the formation of CuS NCs and simultaneous reduction of graphene oxide (GO) sheets to rGO sheets. In addition, CuS NCs/rGO composites were further used as heterogeneous catalysts in the wet hydrogen peroxide catalytic oxidation process, with methylene blue as a model organic dye. The introduction of rGO to CuS NCs could effectively enhance the catalytic activity of CuS NCs, and the resultant CuS NCs/rGO composites with a starting GO amount of 5 wt% showed the highest catalytic activity. Furthermore, the CuS NCs/rGO composites showed high catalytic activity over a broad pH operation range from 3.0 to 11.0 under ambient conditions, and still retained 90% of the original catalytic activity after reuse in five cycles.

  12. Oxide property of SG tube materials exposed to an alkaline environment as a secondary side of a PWR

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Dongjin; Mun, Byung Hak; Kim, Hong Pyo; Hwang, Seong Sik [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of)

    2014-05-15

    Stress corrosion cracking (SCC) is an issue that should be overcome in nuclear power plants (NPP). Recognizing that cracks initiate and propagate through unavoidable breakdowns and alterations of the surface oxide on Alloy 600, the SCC behavior is closely related to the oxide property. Corrosion resistance against SCC, in particular, was improved through a newly developed heat treatment process from LTMA (low temperature mill annealed) Alloy 600 to HTMA (high temperature mill annealed) Alloy 600, and then TT (thermally treated) Alloy 600. Intra-granular carbide widely spread in LTMA Alloy 600 dissolves, and inter-granular carbide is then formed during high-temperature mill annealing and cooling, which leads to a great SCC resistance enhancement. Inter-granular carbide is well developed, healing chromium depletion at a grain boundary, and residual stress is removed during additional thermal treatment following mill annealing, which improves the SCC resistance more. In spite of this improvement of TT Alloy 600, Seabrook and Vogtle 1 in the US, using TT Alloy 600, also showed SCC due to a non-optimum microstructure, residual stress, Pb existence, and so on over a 20-year operation of an NPP even though SCC occurs less frequently than LTMA and (or) HTMA Alloy 600s. SCC has also occurred for TT Alloy 600 tubes in Korea, whose main causes resemble US cases. The pH at high temperature in the crevice of SG tubes distributes from acidic of 4 to alkaline above 10 at high temperature depending on the impurity concentration such as chloride and hydroxide ions including other corrosive impurities such as Pb known as very detrimental species even though the bulk pH of secondary water is a mild alkaline solution. Regarding the aggressiveness of Pb, even Alloy 690 is also susceptible to SCC in a strong alkaline solution with lead. Therefore, in the present work, the oxides were investigated in a leaded alkaline solution of pH(T) 9.9 at 315 .deg. C as a function of immersion time

  13. Hollow raspberry-like PdAg alloy nanospheres: High electrocatalytic activity for ethanol oxidation in alkaline media

    Science.gov (United States)

    Peng, Cheng; Hu, Yongli; Liu, Mingrui; Zheng, Yixiong

    2015-03-01

    Palladium-silver (PdAg) alloy nanospheres with unique structure were prepared using a one-pot procedure based on the galvanic replacement reaction. Their electrocatalytic activity for ethanol oxidation in alkaline media was evaluated. The morphology and crystal structure of the samples were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray diffraction (XRD). Electrochemical characterization techniques, including cyclic voltammetry (CV) and chronoamperometry (CA) measurements were used to analyze the electrochemical performance of the PdAg alloy nanospheres. The SEM and TEM images showed that the PdAg alloy nanospheres exhibit a hierarchical nanostructure with hollow interiors and porous walls. Compared to the commercial Pd/C catalyst, the as-prepared PdAg alloy nanospheres exhibit superior electrocatalytic activity and stability towards ethanol electro-oxidation in alkaline media, showing its potential as a new non-Pt electro-catalyst for direct alcohol fuel cells (DAFCs).

  14. Mechanistic investigation on the oxidation of kinetin by Ag(III) periodate complex in aqueous alkaline media: A kinetic approach

    Indian Academy of Sciences (India)

    S D Lamani; A M Tatagar; S T Nandibewoor

    2010-11-01

    The oxidation of amino acid, kinetin (KNT) by diperiodatoargentate(III) (DPA) in alkaline medium at a constant ionic strength of 0.5 mol dm-3 was studied spectrophtometrically. The reaction between KNT and DPA in alkaline medium exhibits 1 : 3 stoichiometry (KNT : DPA). Intervention of free radicals was observed in the reaction. Based on the observed orders and experimental evidences, a mechanism involving the monoperiodatoargentate(III) (MPA) as the reactive oxidant species has been proposed. The products, furon-2-methanol and para-nitro-purine were identified by spot test and characterized by spectral studies. The rate constants and associated activation parameters for the proposed mechanism as well as the thermodynamic quantities for different equilibrium steps are reported and discussed.

  15. High electrocatalytic performance of nitrogen-doped carbon nanofiber-supported nickel oxide nanocomposite for methanol oxidation in alkaline medium

    Science.gov (United States)

    Al-Enizi, Abdullah M.; Elzatahry, Ahmed A.; Abdullah, Aboubakr M.; Vinu, Ajayan; Iwai, Hideo; Al-Deyab, Salem S.

    2017-04-01

    Nitrogen-Doped Carbon Nanofiber (N-CNF)-supported NiO composite was prepared by electrospinning a sol-gel mixture of graphene and polyaniline (PANi) with aqueous solutions of Polyvinylpyrrolidone (PVP) followed by a high-temperature annealing process. The electrospun was stabilized for 2 h at 280 °C, carbonized for 5 h at 1200 °C then loaded by 10% NiO. The electrocatalytic activities of the produced nanocomposite have been studied using cyclic voltammetry, and chronoamperometry. Also, N-CNF was characterized by X-ray diffraction (XRD), thermogravimetric analysis (TGA), surface area (BET), X-ray photoelectron spectroscopy (XPS), transmission electron microscope (TEM), and scanning-electron microscopy (SEM). The obtained N-doped carbon nanofiber was found to have a nitrogen content of 2.6 atomic% with a diameter range of (140-160) nm, and a surface area (393.3 m2 g-1). In addition, it showed a high electrocatalytic behavior towards methanol oxidation reaction in alkaline medium and high stability and resistivity to the adsorption of intermediates.

  16. Recovery of manganese oxides from spent alkaline and zinc-carbon batteries. An application as catalysts for VOCs elimination.

    Science.gov (United States)

    Gallegos, María V; Falco, Lorena R; Peluso, Miguel A; Sambeth, Jorge E; Thomas, Horacio J

    2013-06-01

    Manganese, in the form of oxide, was recovered from spent alkaline and zinc-carbon batteries employing a biohydrometallurgy process, using a pilot plant consisting in: an air-lift bioreactor (containing an acid-reducing medium produced by an Acidithiobacillus thiooxidans bacteria immobilized on elemental sulfur); a leaching reactor (were battery powder is mixed with the acid-reducing medium) and a recovery reactor. Two different manganese oxides were recovered from the leachate liquor: one of them by electrolysis (EMO) and the other by a chemical precipitation with KMnO4 solution (CMO). The non-leached solid residue was also studied (RMO). The solids were compared with a MnOx synthesized in our laboratory. The characterization by XRD, FTIR and XPS reveal the presence of Mn2O3 in the EMO and the CMO samples, together with some Mn(4+) cations. In the solid not extracted by acidic leaching (RMO) the main phase detected was Mn3O4. The catalytic performance of the oxides was studied in the complete oxidation of ethanol and heptane. Complete conversion of ethanol occurs at 200°C, while heptane requires more than 400°C. The CMO has the highest oxide selectivity to CO2. The results show that manganese oxides obtained using spent alkaline and zinc-carbon batteries as raw materials, have an interesting performance as catalysts for elimination of VOCs.

  17. Catalytic Wet Air Oxidation of Oxalic Acid using Platinum Catalysts in Bubble Column Reactor: A Review

    Directory of Open Access Journals (Sweden)

    A. K. Saroha

    2010-01-01

    Full Text Available Wastewater treatment and re-use of industrial process water are critical issue for the development of human activities andenvironment conservation. Catalytic wet air oxidation (CWAO is an attractive and useful technique for treatment of effluentswhere the concentrations of organic pollutants are too low, for the incineration and other pollution control techniquesto be economically feasible and when biological treatments are ineffective, e.g. in the case of toxic effluents. In CWAO,combustion takes place on a Pt/Al2O3 catalysts usually at temperatures several degrees below those required forthermal incineration. In CWAO process, the organic contaminants dissolved in water are either partially degraded by meansof an oxidizing agent into biodegradable intermediates or mineralized into innocuous inorganic compounds such as CO2,H2O and inorganic salts, which remain in the aqueous phase. In contrast to other thermal processes CWAO produces no NOx,SO2, HCl, dioxins, furans, fly ash, etc. This review paper presents the application of platinum catalysts in bubble columnreactor for CWAO of oxalic acid.

  18. P-chlorophenol wastewater treatment by microwave-enhanced catalytic wet peroxide oxidation.

    Science.gov (United States)

    Zhao, Guohua; Lv, Baoying; Jin, Yan; Li, Dongming

    2010-02-01

    A microwave-enhanced catalytic wet peroxide oxidation (MW-CWPO) technology was investigated to treat a high concentration of p-chlorophenol wastewater under a mild condition. The MW-CWPO experiments were carried out in a microwave autoclave using copper(II) oxide (CuO)-loaded active carbon as a catalyst. The p-chlorophenol was directly ring-opened within 5 minutes at 343 K and 0.3 MPa and then mineralized to carbon dioxide and water. More than 90% of the total organic carbon was removed within 15 minutes. The reaction activation energy (Ea) of hydrogen peroxide (H2O2) decomposition was decreased from 47.7 to 43.1 kJ/mol under microwave irradiation. The H2O2 catalytic decomposition was fitted to a second-order reaction under microwave irradiation, while it followed a first-order reaction without microwave irradiation. The experimental results indicate that the MW-CWPO method has significant potential applications for a high concentration of p-chlorophenol wastewater.

  19. Catalytic wet air oxidation of 2-chlorophenol over sewage sludge-derived carbon-based catalysts.

    Science.gov (United States)

    Tu, Yuting; Xiong, Ya; Tian, Shuanghong; Kong, Lingjun; Descorme, Claude

    2014-07-15

    A sewage sludge derived carbon-supported iron oxide catalyst (FeSC) was prepared and used in the Catalytic Wet Air Oxidation (CWAO) of 2-chlorophenol (2-CP). The catalysts were characterized in terms of elemental composition, surface area, pHPZC, XRD and SEM. The performances of the FeSC catalyst in the CWAO of 2-CP was assessed in a batch reactor operated at 120°C under 0.9MPa oxygen partial pressure. Complete decomposition of 2-CP was achieved within 5h and 90% Total Organic Carbon (TOC) was removed after 24h of reaction. Quite a straight correlation was observed between the 2-CP conversion, the amount of iron leached in solution and the pH of the reaction mixture at a given reaction time, indicating a strong predominance of the homogeneous catalysis contribution. The iron leaching could be efficiently prevented when the pH of the solution was maintained at values higher than 4.5, while the catalytic activity was only slightly reduced. Upon four successive batch CWAO experiments, using the same FeSC catalyst recovered by filtration after pH adjustment, only a very minor catalyst deactivation was observed. Finally, based on all the identified intermediates, a simplified reaction pathway was proposed for the CWAO of 2-CP over the FeSC catalyst.

  20. [Copper leaching in catalytic wet oxidation of phenol with Cu-containing spinel].

    Science.gov (United States)

    Xu, Ai-hua; He, Song-bo; Yang, Min; Du, Hong-zhang; Sun, Cheng-lin

    2008-09-01

    The Cu0.10, Zn0.90 Al1.90 Fe0.10 O4 spinel type catalyst prepared by sol-gel method was tested for catalytic wet air oxidation of phenol. The performances of Cu0.10 Zn0.90 Al1.90 Fe0.10 O4 catalyst in TPR experiment, the influence of phenol as reducer, reaction temperature and phenol-to-catalyst mass ratio on copper leaching were checked respectively. According to the experimental results, it is suggested that the reduced active species can not be easily re-oxidized under low reaction temperature and high phenol-to-catalyst mass ratio are the main reasons for copper leaching. Under high enough reaction temperature and low phenol-to-catalyst mass ratio, the copper leaching reduces remarkably. At 190 degrees C in the presence of 100 mL aqueous solution of 4.29 g x L(-1) of phenol and 2.5 g catalyst, the copper leaching was only 0.96 mg x L(-1) after 2 h of reaction.

  1. Activity and leaching features of zinc-aluminum ferrites in catalytic wet oxidation of phenol.

    Science.gov (United States)

    Xu, Aihua; Yang, Min; Qiao, Ruiping; Du, Hongzhang; Sun, Chenglin

    2007-08-17

    A series of ZnFe(2-x)Al(x)O(4) spinel type catalysts prepared by sol-gel method have been characterized and tested for catalytic wet oxidation (CWO) of phenol with pure oxygen. The iron species existed in these materials as aggregated iron oxide clusters and Fe3+ species in octahedral sites. With a decrease in iron content the concentration of the first iron species decreased and the latter increased. Complete phenol conversions and high chemical oxygen demand (COD) removals were obtained for all catalysts during phenol degradation at mild reaction conditions (160 degrees C and 1.0 MPa of oxygen pressure). Increasing with the concentration of Fe3+ species in octahedral sites, induction period became significantly shortened. After phenol was completely degraded, the concomitant recycling of the leaching Fe3+ ions back to the catalyst surface was observed, and in this case it is possible to perform successful CWO reactions with some cycles. It is also suggested that during the reaction the Fe3+ cations coordinated in octahedral sites in the ZnFe(2-x)Al(x)O(4) catalysts are resistant to acid leaching, but the reduced Fe2+ cations become much more labile, leading to increased Fe leaching.

  2. Ruthenium versus platinum on cerium materials in wet air oxidation of acetic acid

    Energy Technology Data Exchange (ETDEWEB)

    Gaalova, J. [Institute of Chemical Process Fundamentals of the CAS, Rozvojova 135, 165 02 Prague 6, CZ (Czech Republic); Barbier, J., E-mail: Jacques.barbier.jr@univ-poitiers.fr [University of Poitiers, LACCO UMR 6503, Laboratoire de Catalyse par les Metaux, 40 Avenue du Recteur Pineau, F-86022 POITIERS Cedex (France); Rossignol, S. [University of Limoges, ENSCI, 47 Avenue Albert Thomas 87000 Limoges France (France)

    2010-09-15

    This study was a comparison between Ru-catalysts and similar, previously investigated, Pt-catalysts. In this paper, ruthenium catalysts for catalytic wet air oxidation are prepared, characterized and tested. Both catalysts were supported on commercial CeO{sub 2} as well as mixed oxide Zr{sub 0.1}(Ce{sub 0.75}Pr{sub 0.25}){sub 0.9}O{sub 2}. The catalysts were characterized by measuring the oxygen storage capacities (OSC), BET, XRD, FTIR and chemisorption of hydrogen. In addition, the effect of sintering (treatments under H{sub 2}) was compared with both of the catalysts. The comparison of the results showed that initial intrinsic activity of ruthenium is not significantly influenced by the type of the support, which is contrast to platinum. Furthermore, the particle size of Ru had an important effect on CWAO activity: the higher the particle size, the better the activity. This was different with Pt-catalysts, where the optimal particle size was smaller, having about 15% of metal dispersion.

  3. Analytical aspects of the remediation of soil by wet oxidation - Characterisation of tar contaminants and their degradation products

    DEFF Research Database (Denmark)

    Thomsen, A.B.; Nielsen, T.; Plöger, A.;

    1999-01-01

    Wet oxidation of tar compounds gives rise to a wide range of products. Due to the incorporation of oxygen, these products become increasingly more water soluble and the analytical strategy has to take into account the different physical/chemicalproperties of the compounds. An interplay between gas...

  4. Experimental coupling and modelling of wet air oxidation and packed-bed biofilm reactor as an enhanced phenol removal technology.

    Science.gov (United States)

    Minière, Marine; Boutin, Olivier; Soric, Audrey

    2017-01-25

    Experimental coupling of wet air oxidation process and aerobic packed-bed biofilm reactor is presented. It has been tested on phenol as a model refractory compound. At 30 MPa and 250 °C, wet air oxidation batch experiments led to a phenol degradation of 97% and a total organic carbon removal of 84%. This total organic carbon was mainly due to acetic acid. To study the interest of coupling processes, wet air oxidation effluent was treated in a biological treatment process. This step was made up of two packed-bed biofilm reactors in series: the first one acclimated to phenol and the second one to acetic acid. After biological treatment, phenol and total organic carbon removal was 99 and 97% respectively. Thanks to parameters from literature, previous studies (kinetic and thermodynamic) and experimental data from this work (hydrodynamic parameters and biomass characteristics), both treatment steps were modelled. This modelling allows the simulation of the coupling process. Experimental results were finally well reproduced by the continuous coupled process model: relative error on phenol removal efficiency was 1 and 5.5% for wet air oxidation process and packed-bed biofilm reactor respectively.

  5. Substrate inhibition: Oxidation of D-sorbitol and D-mannitol by potassium periodate in alkaline medium

    Science.gov (United States)

    Lakshman Kumar, Y.; Venkata Nadh, R.; Radhakrishnamurti, P. S.

    2014-05-01

    In the oxidation of D-sorbitol and D-mannitol by potassium periodate in alkaline media, substrate inhibition was observed with both substrates, i.e., a decrease in the rate of the reaction was observed with an increase in the concentration of substrate. The substrate inhibition was attributed to the formation of stable complex between the substrate and periodate. The reactions were found to be first order in case of periodate and a positive fractional order with hydroxide ions. Arrhenius parameters were calculated for the oxidation of sorbitol and mannitol by potassium periodate in alkali media.

  6. Zinc(II) oxide stability in alkaline sodium phosphate solutions at elevated temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Ziemniak, S.E.; Opalka, E.P.

    1993-04-01

    Zinc oxide (ZnO) is shown to transform into either of two phosphate-containing compounds in relatively dilute alkaline sodium phosphate solutions at elevated temperatures via ZnO(s) + Na{sup +} + H{sub 2}PO{sub 4}{sup {minus}} {r_reversible} NaZnPO{sub 4}(s) + H{sub 2}O or 2 ZnO(s) + H{sub 3}PO{sub 4}(aq) {r_reversible} Zn{sub 2}(OH)PO{sub 4}(s) + H{sub 2}O. X-ray diffraction analyses indicate that NaZnPO{sub 4} possesses an orthorhombic unit cell having lattice parameters a = 8.710 {+-} 0.013, b = 15.175 {+-} 0.010, and c = 8.027 {+-} 0.004 {angstrom}. The thermodynamic equilibria for these reactions were defined in the system ZnO-Na{sub 2}O-P{sub 2}O{sub 5}-H{sub 2}O for Na/P molar ratios between 2.1 and 3. Based on observed reaction threshold values for sodium phosphate concentration and temperature, the standard entropy (S{degrees}) and free energy of formation ({Delta}G{sub f}{degrees}) for NaZnPO{sub 4} were calculated to be 169.0 J/mol-K and {minus}1510.6 kJ/mol, respectively; similar values for Zn{sub 2}(OH)PO{sub 4} (tarbuttite) were 235.9 J/mol-K and {minus}1604.6 kJ/mol. Additions of sodium sulfite and sulfate did not alter the above reactions.

  7. Influence of beryllium cations on the electrochemical oxidation of methanol on stepped platinum surfaces in alkaline solution

    Science.gov (United States)

    García, Gonzalo; Stoffelsma, Chantal; Rodriguez, Paramaconi; Koper, Marc T. M.

    2015-01-01

    The role of beryllium on the oxidation of methanol on Pt stepped surfaces (Pt[(n-1) (111)x(110)]) orientation-Pt(553) with n = 5, Pt(554) n = 10, Pt(151514) n = 30), Pt(111) and Pt(110) single crystals in alkaline media was studied by cyclic voltammetry and Fourier transform infrared spectroscopy (FTIRS). The results suggest that under the conditions of the experiment, the methanol oxidation reaction follows a direct pathway with formaldehyde and formate as reaction intermediates. The combination of OHads and beryllium blocks the adsorption and oxidation of methanol on Pt(111), but appears to promote the complete oxidation of methanol to carbon dioxide/carbonate on Pt(110).

  8. Thermodynamic, kinetic and mechanistic investigations of Piperazine oxidation by Diperiodatocuprate(III) complex in aqueous alkaline medium

    Indian Academy of Sciences (India)

    Vijay P Pattar; Prashant A Magdum; Deepa G Patil; Sharanappa T Nandibewoor

    2016-03-01

    The kinetics of oxidation of piperazine by the copper complex, diperiodatocuprate(III) in alkaline medium was studied at 298 K, at an ionic strength of 2.0*10-2 mol dm-3. The reaction between piperazine and diperiodatocuprate(III) in aqueous alkaline medium exhibited 1:2 stoichiometry. The oxidation products were identified by UV-Visible, GC-MS and IR spectral studies. In the present study we have obtained different kinetic observations. The reaction exhibited unit order in case of diperiodatocuprate(III), while less than unit order with respect to piperazine. The addition of alkali and periodate retarded the rate of reaction. The effects of added products, ionic strength and dielectric constant on the rate of the reaction were also studied. The active species of diperiodatocuprate(III) in alkaline media is [Cu(OH)2(H3IO6)]-. The activation parameters with respect to the rate determining step and the thermodynamic quantities with respect to the equilibrium steps were evaluated and discussed. The plausible mechanism consistent with the experimental results was proposed and discussed in detail.

  9. Polymer Film Supported Bimetallic Au-Ag Catalysts for Electrocatalytic Oxidation of Ammonia Borane in Alkaline Media

    Institute of Scientific and Technical Information of China (English)

    Şükriye Ulubay Karabiberoglu; ÇagrCeylan Koçak; Süleyman Kocak; Zekerya Dursun

    2016-01-01

    Ammonia borane is widely used in most areas including fuel cell applications. The present paper describes electrochemical behavior of ammonia borane in alkaline media on the poly(p-aminophenol) film modified with Au and Ag bimetallic nanoparticles. The glassy carbon electrode was firstly covered with polymeric film electrochemically and then, Au, Ag, and Au–Ag nanoparticles were deposited on the polymeric film, respectively. The surface morphology and chemical composition of these electrodes were examined by scanning electron microscopy, transmission electron microscopy, electrochemical impedance spectroscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. It was found that alloyed Au–Ag bimetallic nanoparticles are formed. Electrochemical measurements indicate that the developed electrode modified by Au–Ag bimetallic nanoparticles exhibit the highest electrocatalytic activity for ammonia borane oxidation in alkaline media. The rotating disk electrode voltammetry demonstrates that the developed electrode can catalyze almost six-electron oxidation pathway of ammonia borane. Our results may be attractive for anode materials of ammonia borane fuel cells under alkaline conditions.

  10. Conditioning of Si-interfaces by wet-chemical oxidation: Electronic interface properties study by surface photovoltage measurements

    Science.gov (United States)

    Angermann, Heike

    2014-09-01

    The field-modulated surface photovoltage (SPV) method, a very surface sensitive technique, was utilized to determine electronic interface properties on wet-chemically oxidized and etched silicon (Si) interfaces. The influence of preparation-induced surface micro-roughness and un-stoichiometric oxides on the resulting the surface charge, energetic distribution Dit(E), and density Dit,min of rechargeable states was studied by simultaneous, spectroscopic ellipsometry (SE) measurements on polished Si(111) and Si(100) substrates. Based on previous findings and new research, a study of conventional and newly developed wet-chemical oxidation methods was established, correlating the interactions between involved oxidizing and etching solutions and the initial substrate morphology to the final surface conditioning. It is shown, which sequences of wet-chemical oxidation and oxide removal, have to be combined in order to achieve atomically smooth, hydrogen terminated surfaces, as well as ultra-thin oxide layers with low densities of rechargeable states on flat, saw damage etched, and textured Si substrates, as commonly applied in silicon device and solar cell manufacturing. These conventional strategies for wet-chemical pre-treatment are mainly based on concentrated solutions. Therefore, special attention was put on the development of more environmentally acceptable processes, utilizing e.g. hot pure water with low contents of oxygen or hydrochloric acid, and of ozone, working at ambient temperatures. According to our results, these methods could be a high quality and low cost alternative to current approaches with liquid chemicals for the preparation of hydrophobic Si substrate surfaces and ultra-thin passivating oxide layers. As demonstrated for selected examples, the effect of optimized wet-chemical pre-treatments can be preserved during subsequent soft plasma enhanced chemical vapor depositions of Si oxides (SiOx), or amorphous materials such as Si (a-Si:H), Si nitride (a

  11. Mechanistic study of ruthenium (III) catalysed oxidation of L-lysine by diperiodatoargentate (III) in aqueous alkaline medium

    Indian Academy of Sciences (India)

    R R Hosamani; S T Nandibewoor

    2009-05-01

    The kinetics of Ru(III) catalysed oxidation of L-lysine by diperiodatoargentate (III) (DPA) in alkaline medium at 298 K and a constant ionic strength of 0.50 mol dm-3 was studied spectrophotometrically. The oxidation products are aldehyde (5-aminopentanal) and Ag (I). The stoichiometry is i.e. [L-lysine] : [DPA] = 1 : 1. The reaction is of first order in [Ru(III)] and [DPA] and is less than unit order in both [L-lys] and [alkali]. Addition of periodate had a retarding effect on the reaction. The oxidation reaction in alkaline medium has been shown to proceed via a Ru(III)-L-lysine complex, which further reacts with one molecule of monoperiodatoargentate(III) (MPA) in a rate determining step followed by other fast steps to give the products. The main products were identified by spot test, IR, GC-MS studies. The activation parameters with respect to slow step of the mechanism are computed and discussed and thermodynamic quantities are also determined. The active species of catalyst and oxidant have been identified.

  12. Toluene removal by oxidation reaction in spray wet scrubber: experimental, modeling and optimization

    Directory of Open Access Journals (Sweden)

    Roumporn Nikom

    2006-11-01

    Full Text Available Toluene, an important volatile organic compound (VOC, is used in many kinds of industries, such as painting, printing, coating, and petrochemical industries. The emission of toluene causes serious air pollution, odor problem, flammability problem and affects human health. This paper proposes the removal of toluene from waste air using a spray wet scrubber combining the absorption and oxidation reaction. Aqueous sodium hypochlorite (NaOCl solution was used as the scrubbing liquid in the system. NaOCl, the strongest oxidative agent, presents an effective toluene removal. As the scrubbed toluene is reacted, recirculation of the scrubbing liquid could be operated with a constant removal efficiency throughout the operting time. The investigated variables affecting the removal efficiency were air flow rate, inlet toluene concentration, NaOCl concentration, scrubbing liquid flow rate and size of spray nozzle. Influence of the scrubbing parameters was experimentally studied to develop a mathematical model of the toluene removal efficiency. The removal model reveals that the increase of scrubbing liquid flow rate, toluene concentration, and NaOCl concentration together with the decrease of air flow rate and size of spray nozzle can increase the toluene removal efficiency. Optimization problem with an objective function and constraints was set to provide the maximum toluene removal efficiency and solved by Matlab optimization toolbox. The optimization constraints were formed from the mathematical model and process limitation. The solution of the optimization was an air flow rate of 100 m3/h, toluene concentration of 1500 ppm, NaOCl concentration of 0.02 mol/l, NaOCl solution feed rate of 0.8 m3/h, and spray nozzle size of 0.5 mm. Solution of the optimization gave the highest toluene removal efficiency of 91.7%.

  13. Effect of wet oxidation on the fingerprints of polymeric substances from an activated sludge.

    Science.gov (United States)

    Urrea, José Luis; Collado, Sergio; Oulego, Paula; Díaz, Mario

    2016-11-15

    Thermal pre-treatments of activated sludge involve the release of a high amount of polymeric substances into the bulk medium. The molecular size of these polymers will largely define the subsequent biological treatment of the liquid effluent generated. In this work, the effects of wet oxidation treatment (WO) on the fingerprints of the polymeric substances which compose the activated sludge, were analysed. For a better understanding of these transformations, the sludge was separated into its main fractions: soluble microbial products (SMP), loosely bound extracellular polymeric substances (LB-EPS), tightly bound extracellular polymeric substances (TB-EPS) and naked cells, and then each one was subjected to WO separately (190 °C and 65 bar), determining the fingerprints evolution by size exclusion technique. Results revealed a fast degradation of larger molecules (over 500 kDa) during the first minutes of treatment (40 min). WO also increases the absorptive properties of proteins (especially for 30 kDa), which is possibly due to the hydroxylation of phenylalanine amino acids in their structure. WO of naked cells involved the formation of molecules between 23 and 190 kDa, which are related to the release of cytoplasmic polymers, and more hydrophobic polymers, probably from the cell membrane. The results allowed to establish a relationship between the location of polymeric material and its facility to become oxidised; thus, the more internal the polymeric material in the cell, the easier its oxidation. When working directly with the raw sludge, hydrolysis mechanisms played a key role during the starting period. Once a high degree of solubilisation was reached, the molecules were rapidly oxidised into other compounds with refractory characteristics. The final effluent after WO showed almost 90% of low molecular weight solubilised substances (0-35 kDa).

  14. Anaerobic treatability of liquid residue from wet oxidation of sewage sludge.

    Science.gov (United States)

    Bertanza, Giorgio; Galessi, Raniero; Menoni, Laura; Pedrazzani, Roberta; Salvetti, Roberta; Zanaboni, Sabrina

    2015-05-01

    Wet Oxidation (WO) of sewage sludge is a chemical oxidation of sludge at high temperatures and pressures by means of an oxygen-containing gas. The liquid stream originated by WO is easily biodegradable, and therefore, the recirculation to the biological Waste Water Treatment Plant (WWTP) may be a feasible solution. However, the WO effluent has a residual organic and nitrogen content so that its treatment may be required when the receiving WWTP has no surplus treatment capacity left. The aim of this research was the assessment of the anaerobic treatability of the WO liquid residue, in order to reduce the organic load to be recirculated to the WWTP, simultaneously promoting energy recovery. For this purpose, the liquid residue obtained during full scale WO tests on two different types of sludge was submitted to anaerobic digestion in a continuous flow pilot reactor (V = 5 L). Furthermore, batch tests were carried out in order to evaluate possible inhibition factors. Experimental results showed that, after the start-up/acclimation period (~130 days), Chemical Oxygen Demand (COD) removal efficiency was stably around 60% for about 120 days, despite the change in operating conditions. In the last phase of the experimental activity, COD removal reached 70% under the following treatment conditions: Hydraulic Retention Time (HRT) = 20 days, Volumetric Organic Loading Rate (VOLR) = 0.868 kg COD/m(3)/day, Organic Loading Rate per Volatile Suspended Solids (OLRvss) = 0.078 kg COD/kg VSS/day, temperature (T) = 36.5 °C, pH = 8. Energy balance calculation demonstrated anaerobic treatment sustainability.

  15. Advanced treatment of wet-spun acrylic fiber manufacturing wastewater using three-dimensional electrochemical oxidation.

    Science.gov (United States)

    Zheng, Tianlong; Wang, Qunhui; Shi, Zhining; Fang, Yue; Shi, Shanshan; Wang, Juan; Wu, Chuanfu

    2016-12-01

    A three-dimensional electrochemical oxidation (3D-EC) reactor with introduction of activated carbon (AC) as particle micro-electrodes was applied for the advanced treatment of secondary wastewater effluent of a wet-spun acrylic fiber manufacturing plant. Under the optimized conditions (current density of 500A/m(2), circulation rate of 5mL/min, AC dosage of 50g, and chloride concentration of 1.0g/L), the average removal efficiencies of chemical oxygen demand (CODcr), NH3-N, total organic carbon (TOC), and ultraviolet absorption at 254nm (UV254) of the 3D-EC reactor were 64.5%, 60.8%, 46.4%, and 64.8%, respectively; while the corresponding effluent concentrations of CODcr, NH3-N, TOC, and UV254 were 76.6, 20.1, and 42.5mg/L, and 0.08Abs/cm, respectively. The effluent concentration of CODcr was less than 100mg/L, which showed that the treated wastewater satisfied the demand of the integrated wastewater discharge standard (GB 8978-1996). The 3D-EC process remarkably improved the treatment efficiencies with synergistic effects for CODcr, NH3-N, TOC, and UV254 during the stable stage of 44.5%, 38.8%, 27.2%, and 10.9%, respectively, as compared with the sum of the efficiencies of a two-dimensional electrochemical oxidation (2D-EC) reactor and an AC adsorption process, which was ascribed to the numerous micro-electrodes of AC in the 3D-EC reactor. Gas chromatography mass spectrometry (GC-MS) analysis revealed that electrochemical treatment did not generate more toxic organics, and it was proved that the increase in acute biotoxicity was caused primarily by the production of free chlorine.

  16. Low adhesion, non-wetting phosphonate self-assembled monolayer films formed on copper oxide surfaces.

    Science.gov (United States)

    Hoque, E; DeRose, J A; Bhushan, B; Hipps, K W

    2009-07-01

    Self-assembled monolayer (SAM) films have been formed on oxidized copper (Cu) substrates by reaction with 1H,1H,2H,2H-perfluorodecylphosphonic acid (PFDP), octadecylphosphonic acid (ODP), decylphosphonic acid (DP), and octylphosphonic acid (OP) and then investigated by X-ray photoelectron spectroscopy (XPS), contact angle measurement (CAM), and atomic force microscopy (AFM). The presence of alkyl phosphonate molecules, PFDP, ODP, DP, and OP, on Cu were confirmed by CAM and XPS analysis. No alkyl phosphonate molecules were seen by XPS on unmodified Cu as a control. The PFDP/Cu and ODP/Cu SAMs were found to be very hydrophobic having water sessile drop static contact angles of more than 140 degrees , while DP/Cu and OP/Cu have contact angles of 119 degrees and 76 degrees , respectively. PFDP/Cu, ODP/Cu, DP/Cu, and OP/Cu SAMs were studied by friction force microscopy, a derivative of AFM, to better understand their micro/nanotribological properties. PFDP/Cu, ODP/Cu, and DP/Cu had comparable adhesive force, which is much lower than that for unmodified Cu. ODP/Cu had the lowest friction coefficient followed by PFDP/Cu, DP/Cu, and OP/Cu while unmodified Cu had the highest. XPS data gives some indication that a bidentate bond forms between the alkyl phosphonate molecules and the oxidized Cu surface. Hydrophobic phosphonate SAMs could be useful as corrosion inhibitors in micro/nanoelectronic devices and/or as promoters for anti-wetting, low adhesion surfaces.

  17. Supported noble metal catalysts in the catalytic wet air oxidation of industrial wastewaters and sewage sludges.

    Science.gov (United States)

    Besson, M; Descorme, C; Bernardi, M; Gallezot, P; di Gregorio, F; Grosjean, N; Minh, D Pham; Pintar, A

    2010-12-01

    This paper reviews some catalytic wet air oxidation (CWAO) investigations of industrial wastewaters over platinum and ruthenium catalysts supported on TiO2 and ZrO2 formulated to be active and resistant to leaching, with particular focus on the stability of the catalyst. Catalyst recycling experiments were performed in batch reactors and long-term stability tests were conducted in trickle-bed reactors. The catalyst did not leach upon treatment of Kraft bleaching plant and olive oil mill effluents, and could be either recycled or used for long periods of time in continuous reactors. Conversely, these catalysts were rapidly leached when used to treat effluents from the production of polymeric membranes containing N,N-dimethylformamide. The intermediate formation of amines, such as dimethylamine and methylamine with a high complexing capacity for the metal, was shown to be responsible for the metal leaching. These heterogeneous catalysts also deactivated upon CWAO of sewage sludges due to the adsorption of the solid organic matter. Pre-sonication of the sludge to disintegrate the flocs and improve solubility was inefficient.

  18. Catalytic wet oxidation of the pretreated synthetic pulp and paper mill effluent under moderate conditions.

    Science.gov (United States)

    Garg, Anurag; Mishra, I M; Chand, Shri

    2007-01-01

    In the present study, catalytic wet oxidation (CWO) was investigated for the destruction of organic pollutants in the thermally pretreated effluent from a pulp and paper mill under moderate temperature and pressure conditions. The thermal pretreatment studies were conducted at atmospheric pressure and 368K using copper sulfate as a catalyst. The thermal pretreatment reduced COD by about 61%. The filtrate of the thermal pretreatment step was used at pH 8.0 for CWO at 383-443K temperature and a total pressure of 0.85MPa for 4h. Catalysts used for the reaction include copper sulfate, 5% CuO/95% activated carbon, 60% CuO/40% MnO(2), and 60% CuO/40% CeO(2). Maximum COD reduction was found to be 89% during CWO step using 5% CuO/95% activated carbon with a catalyst loading of 8gl(-1) at 443K and 0.85MPa total pressure. Overall COD reduction for the pretreatment and the CWO was found to be 96%. Besides this, 60% CuO/40% CeO(2) catalyst also exhibited the similar activity as that of obtained with 5% CuO/95% activated carbon catalyst at 423K temperature and 0.85MPa total pressure. The pH of the solution during the experimental runs decreases initially due to the formation of carboxylic acid and then increases due to the decomposition of acids.

  19. Catalytic wet peroxide oxidation of azo dye (Congo red) using modified Y zeolite as catalyst.

    Science.gov (United States)

    Kondru, Arun Kumar; Kumar, Pradeep; Chand, Shri

    2009-07-15

    The present study explores the degradation of azo dye (Congo red) by catalytic wet peroxide oxidation using Fe exchanged commercial Y zeolite as a catalyst. The effects of various operating parameters like temperature, initial pH, hydrogen peroxide concentration and catalyst loading on the removal of dye, color and COD from an aqueous solution were studied at atmospheric pressure. The percent removals of dye, color and COD at optimum pH(0) 7, 90 degrees C using 0.6 ml H(2)O(2)/350 ml solution and 1g/l catalyst was 97% (in 4h), 100% (in 45 min) and 58% (in 4h), respectively. The % dye removal has been found to be less in comparison to % color removal at all conditions, e.g. dye removal in 45 min and at above conditions was 82%, whereas the color removal was 100%. The results indicate that the Fe exchanged Y zeolite is a promising catalyst for dye removal. Fe exchanged catalyst is characterized using XRD, SEM/EDAX, surface area analyzer and FTIR. Though the dye, color and COD removals were maximum at pH(0) 2 but as the leaching of Fe from the catalyst was more in acidic pH range, pH(0) 7 was taken as operating pH due to almost comparable removals as of pH(0) 2 and no leaching of Fe ions.

  20. Wet adhesion of buckypaper produced from oxidized multiwalled carbon nanotubes on soft animal tissue.

    Science.gov (United States)

    Martinelli, Andrea; Carru, Giovanna A; D'Ilario, Lucio; Caprioli, Fabrizio; Chiaretti, Massimo; Crisante, Fernanda; Francolini, Iolanda; Piozzi, Antonella

    2013-05-22

    Buckypaper (BP) is the general definition of a macroscopic assembly of entangled carbon nanotubes. In this paper, a new property of a BP film produced from oxidized multiwalled carbon nanotubes was investigated. In particular, BP shows to be able to promptly and strongly adhere to animal internal soft and wet tissues, as evaluated by peeling and shear tests. BP adhesion strength is higher than that recorded for a commercial prosthetic fabric (sealed to the tissue by fibrin glue) and comparable with that of other reported optimized nanopatterned surfaces. In order to give an interpretation of the observed behavior, the BP composition, morphology, porosity, water wettability, and mechanical properties were analyzed by AFM, X-ray photoelectron spectroscopy, wicking tests, contact angle, and stress-strain measurements. Although further investigations are needed to assess the biocompatibility and safety of the BP film used in this work, the obtained results pave the way for a possible future use of buckypaper as adhesive tape in abdominal prosthetic surgery. This would allow the substitution of conventional sealants or the reduction in the use of perforating fixation.

  1. Wet oxidation of sewage sludge: full-scale experience and process modeling.

    Science.gov (United States)

    Bertanza, Giorgio; Galessi, Raniero; Menoni, Laura; Salvetti, Roberta; Slavik, Edoardo; Zanaboni, Sabrina

    2015-05-01

    Nowadays, sewage sludge management represents one of the most important issues in wastewater treatment. Within the European project "ROUTES," wet oxidation (WO) was proposed for sludge minimization. Four different types of sludge were treated in an industrial WO plant: (1) municipal primary sludge (chemical oxygen demand COD: 73.0 g/L; volatile suspended solid VSS: 44.1 g/L); (2) secondary sludge from an industrial wastewater treatment plant (WWTP) without primary sedimentation (COD: 71.8 g/L; VSS: 34.2 g/L); (3) secondary sludge from a mixed municipal and industrial WWTP without primary sedimentation (COD: 61.9 g/L; VSS: 38.7 g/L); and (4) mixed primary (70%) and secondary (30%) municipal sludge (COD: 81.2 g/L; VSS: 40.6 g/L). The effect of process parameters (temperature, reaction time, oxygen dosage) on WO performance was investigated. Depending on operating conditions, VSS and COD removal efficiency varied in the range 80-97% and 43-71%, respectively. A correlation between process efficiency and the initial VSS/TSS (total suspended solids) ratio was highlighted. Furthermore, a mathematical model of WO process for simulating VSS and COD profiles was developed.

  2. Decomposition and Mineralization of Dimethyl Phthalate in an Aqueous Solution by Wet Oxidation.

    Science.gov (United States)

    Ji, Dar-Ren; Chang, Chia-Chi; Chen, Shih-Yun; Chiu, Chun-Yu; Tseng, Jyi-Yeong; Chang, Ching-Yuan; Chang, Chiung-Fen; Chiang, Sheng-Wei; Hung, Zang-Sie; Shie, Je-Lueng; Chen, Yi-Hung; Yuan, Min-Hao

    2015-01-01

    Dimethyl phthalate (DMP) was treated via wet oxygen oxidation process (WOP). The decomposition efficiency η DMP of DMP and mineralization efficiency η TOC of total organic carbons were measured to evaluate the effects of operation parameters on the performance of WOP. The results revealed that reaction temperature T is the most affecting factor, with a higher T offering higher η DMP and η TOC as expected. The η DMP increases as rotating speed increases from 300 to 500 rpm with stirring enhancement of gas liquid mass transfer. However, it exhibits reduction effect at 700 rpm due to purging of dissolved oxygen by overstirring. Regarding the effects of pressure P T, a higher P T provides more oxygen for the forward reaction with DMP, while overhigh P T increases the absorption of gaseous products such as CO2 and decomposes short-chain hydrocarbon fragments back into the solution thus hindering the forward reaction. For the tested P T of 2.41 to 3.45 MPa, the results indicated that 2.41 MPa is appropriate. A longer reaction time of course gives better performance. At 500 rpm, 483 K, 2.41 MPa, and 180 min, the η DMP and η TOC are 93 and 36%, respectively.

  3. Techno-economic and environmental assessment of sewage sludge wet oxidation.

    Science.gov (United States)

    Bertanza, Giorgio; Canato, Matteo; Heimersson, Sara; Laera, Giuseppe; Salvetti, Roberta; Slavik, Edoardo; Svanström, Magdalena

    2015-05-01

    Today, several technologies and management strategies are proposed and applied in wastewater treatment plants (WWTPs) to minimise sludge production and contamination. In order to avoid a shifting of burdens between different areas, their techno-economic and environmental performance has to be carefully evaluated. Wet oxidation (WO) is an alternative solution to incineration for recovering energy in sewage sludge while converting it to mostly inorganic residues. This paper deals with an experimentation carried out within the EU project "ROUTES". A mass balance was made for a WWTP (500,000 person equivalents) in which a WO stage for sludge minimisation was considered to be installed. Both bench- and full-scale test results were used. Design of treatment units and estimation of capital and operational costs were then performed. Subsequently, technical and economic aspects were evaluated by means of a detailed methodology which was developed within the ROUTES project. Finally, an assessment of environmental impacts from a life cycle perspective was performed. The integrated assessment showed that for the specific upgrade considered in this study, WO technology, although requiring a certain increase of technical complexity at the WWTP, may contribute to environmental and economic advantages. The paper provides guidance in terms of which aspects need a more thorough evaluation in relation to the specific case in which an upgrade with WO is considered.

  4. Pretreatment of corn stover using wet oxidation to enhance enzymatic digestibility.

    Science.gov (United States)

    Varga, Eniko; Schmidt, Anette S; Réczey, Kati; Thomsen, Anne Belinda

    2003-01-01

    Corn stover is an abundant, promising raw material for fuel ethanol production. Although it has a high cellulose content, without pretreatment it resists enzymatic hydrolysis, like most lignocellulosic materials. Wet oxidation (water, oxygen, mild alkali or acid, elevated temperature and pressure) was investigated to enhance the enzymatic digestibility of corn stover. Six different combinations of reaction temperature, time, and pH were applied. The best conditions (60 g/L of corn stover, 195 degrees C, 15 min, 12 bar O2, 2 g/L of Na2CO3) increased the enzymatic conversion of corn stover four times, compared to untreated material. Under these conditions 60% of hemicellulose and 30% of lignin were solubilized, whereas 90% of cellulose remained in the solid fraction. After 24-h hydrolysis at 50 degrees C using 25 filter paper units (FPU)/g of drymatter (DM) biomass, the achieved conversion of cellulose to glucose was about 85%. Decreasing the hydrolysis temperature to 40 degrees C increased hydrolysis time from 24 to 72 h. Decreasing the enzyme loading to 5 FPU/g of DM biomass slightly decreased the enzymatic conversion from 83.4 to 71%. Thus, enzyme loading can be reduced without significantly affecting the efficiency of hydrolysis, an important economical aspect.

  5. Degradation of acid red 97 dye in aqueous medium using wet oxidation and electro-Fenton techniques.

    Science.gov (United States)

    Kayan, Berkant; Gözmen, Belgin; Demirel, Muhammet; Gizir, A Murat

    2010-05-15

    Degradation of the acid red 97 dye using wet oxidation, by different oxidants, and electro-Fenton systems was investigated in this study. The oxidation effect of different oxidants such as molecular oxygen, periodate, persulfate, bromate, and hydrogen peroxide in wet oxidation system was compared. Mineralization of AR97 with periodate appeared more effective when compared with that of the other oxidants at equal initial concentration. When 5 mM of periodate was used, at the first minute of the oxidative treatment, the decolorization percentage of AR97 solution at 150 and 200 degrees C reached 88 and 98%, respectively. The total organic carbon removal efficiency at these temperatures also reached 60 and 80%. The degradation of AR97 was also studied by electro-Fenton process. The optimal current value and Fe(2+) concentration were found to be 300 mA and 0.2 mM, respectively. The results showed that electro-Fenton process can lead to 70 and 95% mineralization of the dye solution after 3 and 5h giving carboxylic acids and inorganic ions as final end-products before mineralization. The products obtained from degradation were identified by GC/MS as 1,2-naphthalenediol, 1,1'-biphenyl-4-amino-4-ol, 2-naphthalenol diazonium, 2-naphthalenol, 2,3-dihydroxy-1,4-naphthalenedion, phthalic anhydride, 1,2-benzenedicarboxylic acid, phthaldehyde, 3-hydroxy-1,2-benzenedicarboxylic acid, 4-amino-benzoic acid, and 2-formyl-benzoic acid.

  6. Fate of Zinc Oxide Nanoparticles Coated onto Macronutrient Fertilizers in an Alkaline Calcareous Soil.

    Directory of Open Access Journals (Sweden)

    Narges Milani

    Full Text Available Zinc oxide (ZnO nanoparticles may provide a more soluble and plant available source of Zn in Zn fertilizers due to their greater reactivity compared to equivalent micron- or millimetre-sized (bulk particles. However, the effect of soil on solubility, spatial distribution and speciation of ZnO nanoparticles has not yet been investigated. In this study, we examined the diffusion and solid phase speciation of Zn in an alkaline calcareous soil following application of nanoparticulate and bulk ZnO coated fertilizer products (monoammonium phosphate (MAP and urea using laboratory-based x-ray techniques and synchrotron-based μ-x-ray fluorescence (μ-XRF mapping and absorption fine structure spectroscopy (μ-XAFS. Mapping of the soil-fertilizer reaction zones revealed that most of the applied Zn for all treatments remained on the coated fertilizer granule or close to the point of application after five weeks of incubation in soil. Zinc precipitated mainly as scholzite (CaZn2(PO42.2H2O and zinc ammonium phosphate (Zn(NH4PO4 species at the surface of MAP granules. These reactions reduced dissolution and diffusion of Zn from the MAP granules. Although Zn remained as zincite (ZnO at the surface of urea granules, limited diffusion of Zn from ZnO-coated urea granules was also observed for both bulk and nanoparticulate ZnO treatments. This might be due to either the high pH of urea granules, which reduced solubility of Zn, or aggregation (due to high ionic strength of released ZnO nanoparticles around the granule/point of application. The relative proportion of Zn(OH2 and ZnCO3 species increased for all Zn treatments with increasing distance from coated MAP and urea granules in the calcareous soil. When coated on macronutrient fertilizers, Zn from ZnO nanoparticles (without surface modifiers was not more mobile or diffusible compared to bulk forms of ZnO. The results also suggest that risk associated with the presence of ZnO NPs in calcareous soils would be

  7. Fate of Zinc Oxide Nanoparticles Coated onto Macronutrient Fertilizers in an Alkaline Calcareous Soil.

    Science.gov (United States)

    Milani, Narges; Hettiarachchi, Ganga M; Kirby, Jason K; Beak, Douglas G; Stacey, Samuel P; McLaughlin, Mike J

    2015-01-01

    Zinc oxide (ZnO) nanoparticles may provide a more soluble and plant available source of Zn in Zn fertilizers due to their greater reactivity compared to equivalent micron- or millimetre-sized (bulk) particles. However, the effect of soil on solubility, spatial distribution and speciation of ZnO nanoparticles has not yet been investigated. In this study, we examined the diffusion and solid phase speciation of Zn in an alkaline calcareous soil following application of nanoparticulate and bulk ZnO coated fertilizer products (monoammonium phosphate (MAP) and urea) using laboratory-based x-ray techniques and synchrotron-based μ-x-ray fluorescence (μ-XRF) mapping and absorption fine structure spectroscopy (μ-XAFS). Mapping of the soil-fertilizer reaction zones revealed that most of the applied Zn for all treatments remained on the coated fertilizer granule or close to the point of application after five weeks of incubation in soil. Zinc precipitated mainly as scholzite (CaZn2(PO4)2.2H2O) and zinc ammonium phosphate (Zn(NH4)PO4) species at the surface of MAP granules. These reactions reduced dissolution and diffusion of Zn from the MAP granules. Although Zn remained as zincite (ZnO) at the surface of urea granules, limited diffusion of Zn from ZnO-coated urea granules was also observed for both bulk and nanoparticulate ZnO treatments. This might be due to either the high pH of urea granules, which reduced solubility of Zn, or aggregation (due to high ionic strength) of released ZnO nanoparticles around the granule/point of application. The relative proportion of Zn(OH)2 and ZnCO3 species increased for all Zn treatments with increasing distance from coated MAP and urea granules in the calcareous soil. When coated on macronutrient fertilizers, Zn from ZnO nanoparticles (without surface modifiers) was not more mobile or diffusible compared to bulk forms of ZnO. The results also suggest that risk associated with the presence of ZnO NPs in calcareous soils would be the same

  8. Pretreatment of refinery waste water by wet oxidation. LOPROX {sup registered} procedure: Alternative treatment of sulfidic waste lyes by wet oxidation; Vorbehandlung von Raffinerieabwasser durch Nassoxidation. LOPROX {sup registered} -Verfahren: Alternative Behandlung von sulfidischen Ablaugen durch Nassoxidation

    Energy Technology Data Exchange (ETDEWEB)

    Leonhaeuser, Johannes; Weissenberg, Dirk; Birkenbeul, Udo [Bayer Technology Services GmbH (BTS), Leverkusen (Germany). Technology Development and Engineering; Bloecher, Christoph [Currenta (Germany)

    2012-05-15

    The authors of the contribution under consideration report on the treatment of refinery wastewater by means of the wet oxidation. The authors present the LOPROX {sup registered} method as an alternative treatment of sulfidic waste lyes. This method can not only treat successfully organic polluted wastewater from the chemical industry, but also various waste lyes from refinery processes. Based on a customer-specific process optimization in pilot scale, a cost-effective treatment can be achieved.

  9. Wet air oxidation as a pretreatment option for selective biodegradability enhancement and biogas generation potential from complex effluent.

    Science.gov (United States)

    Padoley, K V; Tembhekar, P D; Saratchandra, T; Pandit, A B; Pandey, R A; Mudliar, S N

    2012-09-01

    This study looks at the possibility of wet air oxidation (WAO) based pretreatment of complex effluent to selectively enhance the biodegradability (without substantial COD destruction) and facilitate biogas generation potential. A lab-scale wet air oxidation reactor with biomethanated distillery wastewater (B-DWW) as a model complex effluent (COD 40,000 mg L(-1)) was used to demonstrate the proof-of-concept. The studies were conducted using a designed set of experiments and reaction temperature (150-200°C), air pressure (6-12 bar) and reaction time (15-120 min) were the main process variables of concern for WAO process optimization. WAO pretreatment of B-DWW enhanced the biodegradability of the complex wastewater by the virtue of enhancing its biodegradability index (BI) from 0.2 to 0.88, which indicate favorable Biochemical Methane Potential (BMP) for biogas generation. The kinetics of COD destruction and BI enhancement has also been reported.

  10. Kinetics and Mechanism of Oxidation of Leucine and Alanine by Ag(III Complex in Alkaline Medium

    Directory of Open Access Journals (Sweden)

    Changying Song

    2008-01-01

    Full Text Available Kinetics and mechanism of oxidation of leucine and alanine by Ag(III complex were studied spectrophotometrically in alkaline medium at constant ion strength. The reaction was in first order with respect to Ag(III complex and amino acids (leucine, alanine. The second-order rate constant, k−, decreased with the increasing in [OH−] and [IO4−]. A plausible mechanism was proposed from the kinetics study, and the rate equations derived from mechanism can explain all experimental phenomena. The activation parameters were calculated at 298.2 K.

  11. A Kinetically Mechanistic Investigation of Oxidation of 1,4-Butanediamine by Ag(Ⅲ)Complex in Alkaline Medium

    Institute of Scientific and Technical Information of China (English)

    SONG,Changying; SHAN,Jinhuan; Shen,Shigang; Sun,Hanwen

    2009-01-01

    Kinetics and mechanism of oxidation of 1,4-butanediamine by a Ag (Ⅲ)complex were studied spectropho-tometrically in alkaline medium at constant ion strength. The reaction shows first order with respect to the Ag(Ⅲ)complex and 1,4.butanediamine respectively. The second order rate constant,k`:increased with the increasing in[OH-],and decreased with the increasing in[IO4-4].A plausible mechanism was proposed from the kinetics study.The rate equations derived from the mechanism Can explain all experimental phenomena. The activation parameters were calculated.

  12. Thermodynamic and kinetic study of phenol degradation by a non-catalytic wet air oxidation process.

    Science.gov (United States)

    Lefèvre, Sébastien; Boutin, Olivier; Ferrasse, Jean-Henry; Malleret, Laure; Faucherand, Rémy; Viand, Alain

    2011-08-01

    This work is dedicated to an accurate evaluation of thermodynamic and kinetics aspects of phenol degradation using wet air oxidation process. Phenol is a well known polluting molecule and therefore it is important having data of its behaviour during this process. A view cell is used for the experimental study, with an internal volume of 150 mL, able to reach pressures up to 30 MPa and temperatures up to 350°C. Concerning the thermodynamic phase equilibria, experimental and modelling results are obtained for different binary systems (water/nitrogen, water/air) and ternary system (water/nitrogen/phenol). The best model is the Predictive Soave Redlich Kwong one. This information is necessary to predict the composition of the gas phase during the process. It is also important for an implementation in a process simulation. The second part is dedicated to kinetics evaluation of the degradation of phenol. Different compounds have been detected using GC coupled with a MS. A kinetic scheme is deduced, taking into account the evolution of phenol, hydroquinones, catechol, resorcinol and acetic acid. The kinetic parameters are calculated for this scheme. These data are important to evaluate the evolution of the concentration of the different polluting molecules during the process. A simplified kinetic scheme, which can be easily implemented in a process simulation, is also determined for the direct degradation of phenol into H(2)O and CO(2). The Arrhenius law data obtained for the phenol disappearance are the following: k=1.8×10(6)±3.9×10(5)M(-1)s(-1) (pre-exponential factor) and E(a)=77±8 kJ mol(-1) (activation energy).

  13. Catalytic oxidation with Al-Ce-Fe-PILC as a post-treatment system for coffee wet processing wastewater.

    Science.gov (United States)

    Sanabria, Nancy R; Peralta, Yury M; Montañez, Mardelly K; Rodríguez-Valencia, Nelson; Molina, Rafael; Moreno, Sonia

    2012-01-01

    The effluent from the anaerobic biological treatment of coffee wet processing wastewater (CWPW) contains a non-biodegradable compound that must be treated before it is discharged into a water source. In this paper, the wet hydrogen peroxide catalytic oxidation (WHPCO) process using Al-Ce-Fe-PILC catalysts was researched as a post-treatment system for CWPW and tested in a semi-batch reactor at atmospheric pressure and 25 °C. The Al-Ce-Fe-PILC achieved a high conversion rate of total phenolic compounds (70%) and mineralization to CO(2) (50%) after 5 h reaction time. The chemical oxygen demand (COD) of coffee processing wastewater after wet hydrogen peroxide catalytic oxidation was reduced in 66%. The combination of the two treatment methods, biological (developed by Cenicafé) and catalytic oxidation with Al-Ce-Fe-PILC, achieved a 97% reduction of COD in CWPW. Therefore, the WHPCO using Al-Ce-Fe-PILC catalysts is a viable alternative for the post-treatment of coffee processing wastewater.

  14. Wet oxidation pre-treatment of woody yard waste: Parameter optimization and enzymatic digestibility for ethanol production

    DEFF Research Database (Denmark)

    Lissens, G.; Klinke, H.B.; Verstraete, W.

    2004-01-01

    Woody yard waste with high lignin content (22% of dry matter (DM)) was subjected to wet oxidation pre-treatment for subsequent enzymatic conversion and fermentation. The effects of temperature (185-200 degreesC), oxygen pressure (3-12 bar) and addition of sodium carbonate (0-3.3 g per 100 g DM...... biomass) on enzymatic cellulose and hemicellulose (xylan) convertibility were studied. The enzymatic cellulose conversion was highest after wet oxidation for 15 min at 185 degreesC with addition of 12 bars of oxygen and 3.3 g Na2CO3 per 100g waste. At 25 FPU (filter paper unit) cellulase g(-1) DM added......% conversion efficiency was still reached at 15 FPU g(-1) DM. Total carbohydrate recoveries were high (91-100% for cellulose and 72-100% for hemicellulose) and up to 49% of the original lignin and 79% of the hemicellulose could be solubilized during wet oxidation treatment and converted into carboxylic acids...

  15. Catalytic wet peroxide oxidation of aniline in wastewater using copper modified SBA-15 as catalyst.

    Science.gov (United States)

    Kong, Liming; Zhou, Xiang; Yao, Yuan; Jian, Panming; Diao, Guowang

    2016-01-01

    SBA-15 mesoporous molecular sieves modified with copper (Cu-SBA-15) were prepared by pH-adjusting hydrothermal method and characterized by X-ray diffraction, BET, transmission electron microscopy, UV-Vis and (29)Si MAS NMR. The pH of the synthesis gel has a significant effect on the amount and the dispersion of copper on SBA-15. The Cu-SBA-15(4.5) (where 4.5 denotes the pH value of the synthesis gel) modified with highly dispersed copper was used as catalyst for the oxidation of aniline by H2O2. The Cu-SBA-15(4.5) shows a higher catalytic activity compared to CuO on the surface of SBA-15. The influences of reaction conditions, such as initial pH of the aqueous solutions, temperature, as well as the dosages of H2O2 and catalyst were investigated. Under weakly alkaline aqueous solution conditions, the aniline conversion, the H2O2 decomposition and the total organic carbon (TOC) removal could be increased significantly compared to the acid conditions. The percentage of leaching Cu(2+) could be decreased from 45.0% to 3.66% when the initial pH of solution was increased from 5 to 10. The TOC removal could be enhanced with the increases of temperature, H2O2 and catalyst dosage, but the aniline conversion and H2O2 decomposition change slightly with further increasing dosage of catalyst and H2O2. At 343 K and pH 8.0, 100% aniline conversion and 66.9% TOC removal can be achieved under the conditions of 1.0 g/L catalyst and 0.05 mol/L H2O2 after 180 min. Although copper might be slightly leached from catalyst, the homogeneous Cu(2+) contribution to the whole catalytic activity is unimportant, and the highly dispersed copper on SBA-15 plays a dominant role.

  16. Characterization of alkaline-earth oxide additions to the MnO{sub 2} cathode in an aqueous secondary battery

    Energy Technology Data Exchange (ETDEWEB)

    Minakshi, Manickam, E-mail: minakshi@murdoch.edu.au [Extractive Metallurgy, Murdoch University, Murdoch, WA 6150 (Australia); Blackford, Mark [Institute of Materials Engineering, ANSTO, Lucas Heights, NSW 2234 (Australia); Ionescu, Mihail [Institute for Environment Research, ANSTO, Lucas Heights, NSW 2234 (Australia)

    2011-05-19

    Highlights: > Adding MgO in MnO{sub 2} cathode enhances the battery discharge capacity. > Mechanism appears to be different with those of our previously published results. > Capacity fade with subsequent cycling is reduced only for MgO but not for BaO. > Transferred the primary battery into a secondary while using LiOH as electrolyte. - Abstract: The effect of alkaline-earth oxide additions on aqueous rechargeable battery is investigated using microscopic and spectroscopic techniques. The alkaline-earth oxide additions such as magnesium oxide (MgO) and barium oxide (BaO) were physically mixed to the manganese dioxide (MnO{sub 2}) cathode of a cell comprising zinc as an anode and aqueous lithium hydroxide as the electrolyte. The results showed that such additions greatly improved the discharge capacity of the battery (from 145 to 195 for MgO and 265 mAh/g for BaO). Capacity fade with subsequent cycling is reduced only for MgO but not for BaO. With an aim to understand the role of these additives and its improvement in cell performance, we have used microscopy, spectroscopy, ion beam analysis and diffraction based techniques to study the process. Transmission electron microscopy (TEM), and energy dispersive X-ray spectroscopy analysis (EDS) results showed evidence of crystalline MnO{sub 2} particles for MgO as additive, whereas, MnO{sub 2} particles with diffused structure leading to mixture of phases is observed for BaO additives which is in agreement with X-ray diffraction (XRD) data. This work relates to improvement in the electrochemical behaviour of the Zn-MnO{sub 2} battery while the MgO additive helps to reduce the formation of manganese and zinc such as hetaerolite that hinders the lithium intercalation.

  17. Wet Oxidation of Crude Manure and Manure Fibers: Substrate Characteristics Influencing the Pretreatment Efficiency for Increasing the Biogas Yield of Manure

    DEFF Research Database (Denmark)

    Uellendahl, Hinrich; Mladenovska, Zuzana; Ahring, Birgitte Kiær

    2007-01-01

    The biogas yield of manure is typically lower than 25 m3/t due to its low dry matter content and its high ratio of lignocellulosic fibers that are recalcitrant towards anaerobic digestion. A new pre-treatment method – wet oxidation – has been tested for disruption of the lignocellulosic fiber...... structure with subsequent higher degradation efficiencies and methane yields. A screening of crude manure and the separated fiber fraction shows that wet oxidation is more adequate for treatment of high concentrated solid fraction than for crude manure and an increase of 35% in biogas yield can be gained...... from wet oxidation of digested fibers. The wet oxidation treatment of the manure fiber fraction has to be carefully adjusted in order to achieve the highest increase in biogas yield for the manure fiber fraction under low production of inhibiting compounds and low losses of valuable organic matter....

  18. Wet hydrogen peroxide catalytic oxidation of phenol with FeAC (iron-embedded activated carbon) catalysts.

    Science.gov (United States)

    Liou, Rey-May; Chen, Shih-Hsiung; Huang, Cheng-Hsien; Hung, Mu-Ya; Chang, Jing-Song; Lai, Cheng-Lee

    2010-01-01

    This investigation aims at exploring the catalytic oxidation activity of iron-embedded activated carbon (FeAC) and the application for the degradation of phenol in the wet hydrogen peroxide catalytic oxidation (WHPCO). FeAC catalysts were prepared by pre-impregnating iron in coconut shell with various iron loadings in the range of 27.5 to 46.5% before they were activated. The FeAC catalysts were characterised by measuring their surface area, pore distribution, functional groups on the surface, and X-ray diffraction patterns. The effects of iron loading strongly inhibited the pore development of the catalyst but benefited the oxidation activity in WHPCO. It was found that the complete conversion of phenol was observed with all FeAC catalysts in oxidation. High level of chemical oxygen demand (COD) abatement can be achieved within the first 30 minutes of oxidation. The iron embedded in the activated carbon showed good performance in the degradation and mineralisation of phenol during the oxidation due to the active sites as iron oxides formed on the surface of the activated carbon. It was found that the embedding irons were presented in gamma-Fe(2)O(3), alpha-Fe(2)O(3), and alpha-FeCOOH forms on the activated carbon. The aging tests on FeAC catalysts showed less activity loss, and less iron leaching was found after four oxidation runs.

  19. Role of Bismuth Oxide in Bi-MCo2O4(M=Co,Ni,Cu,Zn) Catalysts for Wet Air Oxidation of Acetic Acid

    Institute of Scientific and Technical Information of China (English)

    JIANG Peng-bo; CHENG Tie-xin; ZHUANG Hong; CUI Xiang-hao; BI Ying-li; ZHEN Kai-ji

    2004-01-01

    Two series of cobalt(Ⅲ)-containing spinel catalysts were prepared by the decomposition of the corresponding nitrates. The catalysts doped with bismuth oxide exhibit a higher activity in the wet air oxidation of acetic acid than those without dopant bismuth oxide. The catalysts were investigated by XRD, TEM, ESR, UV-DRS and XPS, and the interaction between Co and Bi was studied as well. It has been found that nano-sized bismuth oxide is paved on the surface of cobalt spinel crystal and the structures of cobalt(Ⅲ)-containing spinel are still maintained. The shift of the binding energy of Bi4f7/2 is related to the catalytic activity of these catalysts doped with bismuth oxide.

  20. Wet air oxidation of formic acid using nanoparticle-modified polysulfone hollow fibers as gas-liquid contactors.

    Science.gov (United States)

    Hogg, Seth R; Muthu, Satish; O'Callaghan, Michael; Lahitte, Jean-Francois; Bruening, Merlin L

    2012-03-01

    Catalytic wet air oxidation (CWAO) using membrane contactors is attractive for remediation of aqueous pollutants, but previous studies of even simple reactions such as formic acid oxidation required multiple passes through tubular ceramic membrane contactors to achieve high conversion. This work aims to increase single-pass CWAO conversions by using polysulfone (PS) hollow fibers as contactors to reduce diffusion distances in the fiber lumen. Alternating adsorption of polycations and citrate-stabilized platinum colloids in fiber walls provides catalytically active PS hollow fibers. Using a single PS fiber, 50% oxidation of a 50 mM formic acid feed solution results from a single pass through the fiber lumen (15 cm length) with a solution residence time of 40 s. Increasing the number of PS fibers to five while maintaining the same volumetric flow rate leads to over 90% oxidation, suggesting that further scale up in the number of fibers will facilitate high single pass conversions at increased flow rates. The high conversion compared to prior studies with ceramic fibers stems from shorter diffusion distances in the fiber lumen. However, the activity of the Pt catalyst is 20-fold lower than in previous ceramic fibers. Focusing the Pt deposition near the fiber lumen and limiting pore wetting to this region might increase the activity of the catalyst.

  1. Wetting and evaporation behaviors of molten Mg-Al alloy drops on partially oxidized {alpha}-SiC substrates

    Energy Technology Data Exchange (ETDEWEB)

    Shi Laixin [Key Laboratory of Automobile Materials (Ministry of Education), Department of Materials Science and Engineering, Jilin University, No. 5988 Renmin Street, Changchun 130025 (China); Shen Ping, E-mail: shenping@jlu.edu.cn [Key Laboratory of Automobile Materials (Ministry of Education), Department of Materials Science and Engineering, Jilin University, No. 5988 Renmin Street, Changchun 130025 (China); Zhang Dan; Jiang Qichuan [Key Laboratory of Automobile Materials (Ministry of Education), Department of Materials Science and Engineering, Jilin University, No. 5988 Renmin Street, Changchun 130025 (China)

    2011-11-01

    Highlights: {yields} The wetting in the Mg-Al/SiC system was coupled with reaction and evaporation. {yields} The effect of the alloy composition on the wettability was investigated. {yields} Representative wetting stages were identified. {yields} A mechanism for the time-dependent diminishing in the drop volume was proposed. {yields} The interfacial reaction was analyzed based on thermodynamic considerations. - Abstract: The wetting and evaporation behaviors of Mg-Al alloys over a full composition range on partially oxidized polycrystalline {alpha}-SiC substrates were studied in a flowing Ar atmosphere using an improved sessile drop method. The time dependence of the changes in contact angle and drop geometry was monitored and representative wetting stages were identified. The initial contact angles at 1173 K were 100{sup o} for pure Al and 76{sup o} for pure Mg, with the maximum value of 106{sup o} for the 7.6 mol.% Mg-Al alloy. The interfacial reaction and the evaporation of Mg led to the decrease in the apparent contact angle in the spreading stage and their respective contribution was evaluated. After the pinning of the triple line, the decrease in the contact angle resulted from the diminishing drop volume as a consequence of the Mg evaporation. The effects of Mg concentration on the wetting and evaporation behaviors were discussed. A mechanism for the time-dependent diminishing drop volume was proposed in light of the competition between the Mg evaporation and its diffusion from the drop bulk to the surface. Finally, the interfacial reaction was analyzed based on thermodynamic considerations.

  2. Effect of wet etching process on the morphology and transmittance of fluorine doped tin oxide (FTO)

    Science.gov (United States)

    Triana, S. L.; Kusumandari; Suryana, R.

    2016-11-01

    Wet etching process was performed on the surface of FTO. The FTO coated glasses subtrates with size of 2×2 cm covered by screen were patterned using zinc powder and concentrated hydrochloric acid (1 M). The substrates were then cleaned in ultrasonic baths of special detergent(helmanex) diluted in deionized water and isopropanol in sequence. The screens with various of hole size denotes by T32, T49 and T55 were used in order to create a pattern of surface textured. The atomic force microscopy (AFM) image revealed that wet etching process changes the morphology of FTO. It indicates that texturization occured. Moreover, from the UV-Vis Spectrophotometer measurement, the transmittance of FTO increase after wet etching process. The time of etching and pattern of screen were affect to the morphology and the transmittance of FTO.

  3. Electrosynthesized polytyramine-copper oxalate nanocomposite on copper electrode for electrocatalytic oxidation of methanol in alkaline medium

    Institute of Scientific and Technical Information of China (English)

    Robab Abbasi a; Khalil Farhadi a; Sepideh Banisaeid a; Nader Nowroozi Pesyan a; Arezu Jamali a; Fatemeh Rahmani b

    2014-01-01

    A polytyramine-copper oxalate nanocomposite modified copper (PTCOxNMC) electrode prepared by electropolymerization was examined for electrocatalytic activity towards the oxidation of meth-anol in alkaline solution using cyclic voltammetry and impedance spectroscopy. The prepared PTCOxNMC electrode showed a significantly high response for adsorbed methanol oxidation. The effects of various parameters such as potential scan rate and methanol concentration on the elec-trocatalytic oxidation at the surface of the PTCOxNMC electrode were investigated. Spectrometry techniques such as Fourier transform infrared spectroscopy and scanning electron microscopy were used to determine the surface physical characteristics of the modified electrode and revealed that the polytyramine-copper oxalate nanocomposite particles were highly dispersed on the surface of the copper electrode with a narrow size up to 40 nm. The very high current density obtained for the catalytic oxidation may have resulted from the high electrode surface area caused by modifica-tion with the poly-tyramine-copper oxalate nanocomposite.

  4. TASK TECHNICAL AND QUALITY ASSURANCE PLAN FOR OUT-OF-TANK DESTRUCTION OF TETRAPHENYLBORATE VIA WET AIR OXIDATION TECHNOLOGY: PHASE I - BENCH SCALE TESTS

    Energy Technology Data Exchange (ETDEWEB)

    Adu-Wusu, K

    2006-03-31

    Tank 48H return to service is critical to the processing of high level waste (HLW) at Savannah River Site (SRS). Liquid Waste Disposition (LWD) management has the goal of returning Tank 48H to routine service by January 2010 or as soon as practical. Tank 48H currently holds legacy material containing organic tetraphenylborate (TPB) compounds from the operation of the In-Tank Precipitation process. This material is not compatible with the waste treatment facilities at SRS and must be removed or undergo treatment to destroy the organic compounds before the tank can be returned to Tank Farm service. Tank 48H currently contains {approx}240,000 gallons of alkaline slurry with about 2 wt % potassium and cesium tetraphenylborate (KTPB and CsTPB). The main radioactive component in Tank 48H is {sup 137}Cs. The waste also contains {approx}0.15 wt % Monosodium Titanate (MST) which has adsorbed {sup 90}Sr, U, and Pu isotopes. A System Engineering Evaluation of technologies/ideas for the treatment of TPB identified Wet Air Oxidation (WAO) as a leading alternative technology to the baseline aggregation approach. Over 75 technologies/ideas were evaluated overall. Forty-one technologies/ideas passed the initial screening evaluation. The 41 technologies/ideas were then combined to 16 complete solutions for the disposition of TPB and evaluated in detail. Wet Air Oxidation (WAO) is an aqueous phase process in which soluble or suspended waste components are oxidized using molecular oxygen contained in air. The process operates at elevated temperatures and pressures ranging from 150 to 320 C and 7 to 210 atmospheres, respectively. The products of the reaction are CO{sub 2}, H{sub 2}O, and low molecular weight oxygenated organics (e.g. acetate, oxalate). The basic flow scheme for a typical WAO system is as follows. The waste solution or slurry is pumped through a high-pressure feed pump. An air stream containing sufficient oxygen to meet the oxygen requirements of the waste stream is

  5. Solubility Behavior and Phase Stability of Transition Metal Oxides in Alkaline Hydrothermal Environments

    Energy Technology Data Exchange (ETDEWEB)

    S.E. Ziemniak

    2000-05-18

    The solubility behavior of transition metal oxides in high temperature water is interpreted by recognizing three types of chemical reaction equilibria: metal oxide hydration/dehydration, metal oxide dissolution and metal ion hydroxocomplex formation. The equilibria are quantified using thermodynamic concepts and the thermochemical properties of the metal oxides/ions representative of the most common constituents of construction metal alloys, i.e., element shaving atomic numbers between Z = 22 (Ti) and Z = 30 (Zn), are summarized on the basis of metal oxide solubility studies conducted in the laboratory. Particular attention is devoted to the uncharged metal ion hydrocomplex, M{sup Z}(OH){sub Z}(aq), since its thermochemical properties define minimum solubilities of the metal oxide at a given temperature. Experimentally-extracted values of standard partial molal entropy (S{sup 0}) for the transition metal ion neutral hydroxocomplex are shown to be influenced by ligand field stabilization energies and complex symmetry.

  6. Influence of the different oxidation treatment on the performance of multi-walled carbon nanotubes in the catalytic wet air oxidation of phenol.

    Science.gov (United States)

    Yang, Shaoxia; Wang, Xingang; Yang, Hongwei; Sun, Yu; Liu, Yunxia

    2012-09-30

    Multi-walled carbon nanotubes (MWCNTs) functionalized by different oxidants (HNO(3)/H(2)SO(4), H(2)O(2), O(3) and air) have been used as catalysts for the wet air oxidation of phenol. To investigate the effect of the oxidation conditions on the structure of the functionalized MWCNTs, various characterization techniques, e.g., scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectroscopy, Fourier-transform infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS) have been used. The MWCNTs treated with O(3) and H(2)O(2) show higher amounts of oxygen-containing functional groups and carboxylic acid groups, and a weaker acidic nature, in comparison with those treated with other oxidizing agents. All the functionalized MWCNTs exhibit good activity in the catalytic wet air oxidation (CWAO) of phenol. However, the MWCNTs treated with O(3) show the highest activity with desirable stability in comparison with other functionalized MWCNTs, indicating that the functionalization of carbon nanotubes with O(3) is a very promising strategy in synthesizing efficient catalysts for CWAO.

  7. Ruthenium catalysts supported on high-surface-area zirconia for the catalytic wet oxidation of N,N-dimethyl formamide.

    Science.gov (United States)

    Sun, Guanglu; Xu, Aihua; He, Yu; Yang, Min; Du, Hongzhang; Sun, Chenglin

    2008-08-15

    Three weight percent ruthenium catalysts were prepared by incipient-wet impregnation of two different zirconium oxides, and characterized by BET, XRD and TPR. Their activity was evaluated in the catalytic wet oxidation (CWO) of N,N-dimethyl formamide (DMF) in an autoclave reactor. Due to a better dispersion, Ru catalyst supported on a high-surface-area zirconia (Ru/ZrO(2)-A) possessed higher catalytic properties. Due to over-oxidation of Ru particles, the catalytic activity of the both catalysts decreased during successive tests. The effect of oxygen partial pressure and reaction temperature on the DMF reactivity in the CWO on Ru/ZrO(2)-A was also investigated. 98.6% of DMF conversion was obtained through hydrothermal decomposition within 300 min at conditions of 200 degrees C and 2.0 MPa of nitrogen pressure. At 240 degrees C and 2.0 MPa of oxygen pressure 98.3% of DMF conversion was obtained within 150 min.

  8. Sodic alkaline stress mitigation by interaction of nitric oxide and polyamines involves antioxidants and physiological strategies in Solanum lycopersicum.

    Science.gov (United States)

    Gong, Biao; Li, Xiu; Bloszies, Sean; Wen, Dan; Sun, Shasha; Wei, Min; Li, Yan; Yang, Fengjuan; Shi, Qinghua; Wang, Xiufeng

    2014-06-01

    Nitric oxide (NO) and polyamines (PAs) are two kinds of important signal in mediating plant tolerance to abiotic stress. In this study, we observed that both NO and PAs decreased alkaline stress in tomato plants, which may be a result of their role in regulating nutrient balance and reactive oxygen species (ROS), thereby protecting the photosynthetic system from damage. Further investigation indicated that NO and PAs induced accumulation of each other. Furthermore, the function of PAs could be removed by a NO scavenger, cPTIO. On the other hand, application of MGBG, a PA synthesis inhibitor, did little to abolish the function of NO. To further elucidate the mechanism by which NO and PAs alleviate alkaline stress, the expression of several genes associated with abiotic stress was analyzed by qRT-PCR. NO and PAs significantly upregulated ion transporters such as the plasma membrane Na(+)/H(+) antiporter (SlSOS1), vacuolar Na(+)/H(+) exchanger (SlNHX1 and SlNHX2), and Na(+) transporter and signal components including ROS, MAPK, and Ca(2+) signal pathways, as well as several transcription factors. All of these play important roles in plant adaptation to stress conditions.

  9. Kinetic, mechanistic and spectral investigation of ruthenium (III)-catalysed oxidation of atenolol by alkaline permanganate (stopped-flow technique)

    Indian Academy of Sciences (India)

    Rahamatalla M Mulla; Gurubasavaraj C Hiremath; Sharanappa T Nandibewoor

    2005-01-01

    Kinetics of ruthenium (III) catalyzed oxidation of atenolol by permanganate in alkaline medium at constant ionic strength of 0.30 mol dm3 has been studied spectrophotometrically using a rapid kinetic accessory. Reaction between permanganate and atenolol in alkaline medium exhibits 1 : 8 stoichiometry (atenolol : KMnO4). The reaction shows first-order dependence on [permanganate] and [ruthenium (III)] and apparently less than unit order on both atenolol and alkali concentrations. Reaction rate decreases with increase in ionic strength and increases with decreasing dielectric constant of the medium. Initial addition of reaction products does not affect the rate significantly. A mechanism involving the formation of a complex between catalyst and substrate has been proposed. The active species of ruthenium (III) is understood as [Ru(H2O)5OH]2+. The reaction constants involved in the different steps of mechanism are calculated. Activation parameters with respect to the slow step of the mechanism are computed and discussed and thermodynamic quantities are also calculated.

  10. Production of zinc and manganese oxide particles by pyrolysis of alkaline and Zn-C battery waste.

    Science.gov (United States)

    Ebin, Burçak; Petranikova, Martina; Steenari, Britt-Marie; Ekberg, Christian

    2016-05-01

    Production of zinc and manganese oxide particles from alkaline and zinc-carbon battery black mass was studied by a pyrolysis process at 850-950°C with various residence times under 1L/minN2(g) flow rate conditions without using any additive. The particular and chemical properties of the battery waste were characterized to investigate the possible reactions and effects on the properties of the reaction products. The thermodynamics of the pyrolysis process were studied using the HSC Chemistry 5.11 software. The carbothermic reduction reaction of battery black mass takes place and makes it possible to produce fine zinc particles by a rapid condensation, after the evaporation of zinc from a pyrolysis batch. The amount of zinc that can be separated from the black mass is increased by both pyrolysis temperature and residence time. Zinc recovery of 97% was achieved at 950°C and 1h residence time using the proposed alkaline battery recycling process. The pyrolysis residue is mainly MnO powder with a low amount of zinc, iron and potassium impurities and has an average particle size of 2.9μm. The obtained zinc particles have an average particle size of about 860nm and consist of hexagonal crystals around 110nm in size. The morphology of the zinc particles changes from a hexagonal shape to s spherical morphology by elevating the pyrolysis temperature.

  11. [Catalytic wet air oxidation of phenol with Ru/ZrO2-CeO2 catalyst].

    Science.gov (United States)

    Wang, Jian-bing; Zhu, Wan-peng; Wang, Wei; Yang, Shao-xia

    2007-07-01

    Wet air oxidation of phenol with Ru/ZrO2-CeO2 was systematically investigated and results showed that Ru/ZrO2-CeO2 could significantly increase the removal of COD and phenol. At the reaction temperature of 170 degrees C and pressure of 3MPa, about 99% COD and 100% phenol was removed respectively after 120 min. The optimal conditions were: reaction temperature, 170 degrees C; reaction pressure, 3 MPa; catalyst dosage, 5 g/L; agitator speed, 500 r/min. By analyzing intermediates, a simplified scheme of phenol oxidation was brought out. It includes two main steps. The first step is the production of organic acids, which is fast. The second step is the oxidation of organic acid, in which the oxidation of acetic acid is slow. Complete oxidation of acetic acid needs high temperature at which the radicals assault the C-H bond of a carbon and acetic acid is oxidized into carbon dioxide and water through formic acid.

  12. Application of advanced oxidation processes for cleaning of industrial water generated in wet dedusting of shaft furnace gases.

    Science.gov (United States)

    Czaplicka, Marianna; Kurowski, Ryszard; Jaworek, Katarzyna; Bratek, Łukasz

    2013-01-01

    The paper presents results of studies into advanced oxidation processes in 03 and 03/UV systems. An advanced oxidation process (AOP) was conducted to reduce the load of impurities in circulating waters from wet de-dusting of shaft furnace gases. Besides inorganic impurities, i.e. mainly arsenic compounds (16 g As L(-1) on average), lead, zinc, chlorides and sulphates, the waters also contain some organic material. The organic material is composed of a complex mixture that contains, amongst others, aliphatic compounds, phenol and its derivatives, pyridine bases, including pyridine, and its derivatives. The test results show degradation of organic and inorganic compounds during ozonation and photo-oxidation processes. Analysis of the solutions from the processes demonstrated that the complex organic material in the industrial water was oxidized in ozonation and in photo-oxidation, which resulted in formation of aldehydes and carboxylic acids. Kinetic degradation of selected pollutants is presented. Obtained results indicated that the O3/UV process is more effective in degradation of organic matter than ozonation. Depending on the process type, precipitation of the solid phase was observed. The efficiency of solid-phase formation was higher in photo-oxidation with ozone. It was found that the precipitated solid phase is composed mainly of arsenic, iron and oxygen.

  13. Energy balance and cost-benefit analysis of biogas production from perennial energy crops pretreated by wet oxidation

    DEFF Research Database (Denmark)

    Uellendahl, Hinrich; Wang, Guangtao; Møller, H.B.

    2008-01-01

    oxidation to the perennial crops, however, the specific methane yield increases significantly and the ratio of energy output to input and of costs to benefit for the whole chain of biomass supply and conversion into biogas becomes higher than for corn. This will make the use of perennial crops as energy....... The conversion into biogas in anaerobic digestion plants shows however much lower specific methane yields for the raw perennial crops like miscanthus and willow due to their lignocellulosic structure. Without pretreatment the net energy gain is therefore lower for the perennials than for corn. When applying wet...

  14. Kinetics and Mechanism of Oxidation of Triethylene Glycol and Tetraethylene Glycol by Ditelluratoargentate (III in Alkaline Medium

    Directory of Open Access Journals (Sweden)

    Jinhuan Shan

    2013-01-01

    Full Text Available The kinetics of oxidation of triethylene glycol and tetraethylene glycol by ditelluratoargentate (III (DTA in alkaline liquids has been studied spectrophotometrically in the temperature range of 293.2 K–313.2 K. The reaction rate showed first-order dependence in DTA and fractional order with respect to triethylene glycol or tetraethylene glycol. It was found that the pseudo-first-order rate constant (kobs increased with an increase in concentration of OH− and a decrease in concentration of H4TeO6 2−. There was a negative salt effect and no free radicals were detected. A plausible mechanism involving a two-electron transfer was proposed, and the rate equations derived from the mechanism explained all the experimental results and observations. The activation parameters along with the rate constants of the rate-determining step were calculated.

  15. X-ray Diffraction Studies of the Structure and Thermochemistry of Alkaline-Earth Oxide-Coated Thermionic Cathodes

    Science.gov (United States)

    Karikari, E. K.; Bassey, E.; Wintucky, Edwin G.

    1998-01-01

    NASA LeRC has a broad, active cathode technology development program in which both experimental and theoretical studies are being employed to further development of thermionic cathodes for use as electron sources in vacuum devices for communications and other space applications. One important type of thermionic cathode under development is the alkaline-earth oxide-coated (BaO, SrO, CaO) cathode. Significant improvements in the emission characteristics of this cathode have been obtained through modification of the chemical composition and morphology of the oxide coating, with the best result thus far coming from the addition of In2O3 and Sc2O3. Whereas the In2O3 produces a finer, more uniform particle structure, the exact chemical state and role of the Sc2O3 in the emission enhancement is unknown. The purpose of this cooperative agreement is to combine the studies of the surface chemistry and electron emission at NASA LeRC of chemically modified oxide coatings with a study of the thermochemistry and crystal structure using X-ray diffraction equipment and expertise at Clark Atlanta University (CAU). The study at CAU is intended to provide the description and understanding of the structure and thermochemistry needed for further improvement and optimization of the modified coatings. A description of the experimental procedure, preliminary X-ray diffraction test results, together with the design of an ultrahigh vacuum chamber necessary for high temperature thermochemistry studies will be presented.

  16. Evaluation of metal oxide and carbonate nanoparticle stability in soybean oil: Implications for controlled release of alkalinity during subsurface remediation

    Science.gov (United States)

    Ramsburg, C. A.; Leach, O. I.; Sebik, J.; Muller, K.

    2011-12-01

    Traditional methods for adjusting groundwater pH rely on injection of aqueous solutes and therefore, amendment distribution is reliant upon aqueous phase flow and transport. This reliance can limit mixing and sustention of amendments within the treatment zone. Oil-in-water emulsions offer an alternative for amendment delivery - one that has potential to enhance control of the distribution and release of buffering agents within the subsurface. Focus here is placed on using metal oxide and carbonate nanoparticles to release alkalinity from soybean oil, a common dispersed phase within emulsions designed to support remediation activities. Batch reactor systems were employed to examine the influence of dispersed phase composition on particle stability and solubility. The stability of uncoated MgO and CaCO3 particles in unmodified soybean oil was explored in a series of sedimentation studies conducted at solid loadings of 0.05, 0.1, and 0.2% mass. Three nominal sizes of MgO particles were examined (20, 50, and 100 nm) and one CaCO3 particle size (60 nm). Results from sedimentation studies conducted over four hours suggest that the viscosity of the soybean oil imparts a kinetic stability, for all sizes of the uncoated MgO and CaCO3 nanoparticles, which is sufficient time for particle encapsulation within oil-in-water emulsions. Based upon these results, the sedimentation of the 50 nm and 100 nm MgO, and 60 nm CaCO3 particles was assessed over longer durations (≥72 hr). Results from these stability tests suggest that the 50 nm and 100 nm MgO particles have greater kinetic stability than the 60 nm CaCO3. Batch studies were also used to assess the influence of n-butanol, a co-solvent hypothesized to aid in controlling the rate of alkalinity release, on phase behavior and metal (Mg2+ and Ca2+) solubility. Phase behavior studies suggest that n-butanol has a limited region of miscibility within the soybean oil-water system. Use of n-butanol and water within this region of

  17. Combination of wet irrigation and nitrification inhibitor reduced nitrous oxide and methane emissions from a rice cropping system.

    Science.gov (United States)

    Liu, Gang; Yu, Haiyang; Zhang, Guangbin; Xu, Hua; Ma, Jing

    2016-09-01

    To conserve water resources and guarantee food security, a new technology termed as "wet irrigation" is developed and practiced in rice fields; thus, its impact on radiative forcing derived from nitrous oxide (N2O) and methane (CH4) emissions merits serious attention. Dicyandiamide (DCD), a kind of nitrification inhibitor, is proposed as a viable means to mitigate greenhouse gas (GHG) emission while enhancing crop productivity. However, little is known about the response of GHG emission and grain yield to DCD application in a rice system under wet irrigation. In these regard, effects of water regime and DCD application on CH4 and N2O emissions, grain yield, global warming potential (GWP), and greenhouse gas intensity (GHGI) from rice fields were studied. For this study, a field experiment, designed: Treatment II (intermittent irrigation), Treatment WI (wet irrigation), Treatment IID (II plus DCD), and Treatment WID (WI plus DCD), was conducted in Jurong, Jiangsu Province, China, from 2011 to 2012. Relative to Treatment II, Treatment WI decreased CH4 emission significantly by 49-71 % while increasing N2O emission by 33-72 %. By integrating CH4 and N2O emissions and grain yield, Treatment WI was 20-28 and 11-15 % lower than Treatment II in GWP and GHGI, respectively. The use of DCD under wet irrigation reduced N2O emission significantly by 25-38 % (p < 0.05) and CH4 emission by 7-8 %, relative to Treatment WI, resulting in a decline of 18-30 % in GWP. Due to the increase in N use efficiency, maximal grain yield (6-7 %) and minimal GHGI (22-34 %) was observed in Treatment WID. These findings indicate that combined application of N fertilizer and DCD is a win-win strategy in water-saving high-yield rice production with less GHG emission.

  18. Catalytic wet-air oxidation of lignin in a three-phase reactor with aromatic aldehyde production

    Directory of Open Access Journals (Sweden)

    Sales F.G.

    2004-01-01

    Full Text Available In the present work a process of catalytic wet air oxidation of lignin obtained from sugar-cane bagasse is developed with the objective of producing vanillin, syringaldehyde and p-hydroxybenzaldehyde in a continuous regime. Palladium supported on g-alumina was used as the catalyst. The reactions in the lignin degradation and aldehyde production were described by a kinetic model as a system of complex parallel and series reactions, in which pseudo-first-order steps are found. For the purpose of producing aromatic aldehydes in continuous regime, a three-phase fluidized reactor was built, and it was operated using atmospheric air as the oxidizer. The best yield in aromatic aldehydes was of 12%. The experimental results were compatible with those values obtained by the pseudo-heterogeneous axial dispersion model (PHADM applied to the liquid phase.

  19. Catalytic wet air oxidation of coke-plant wastewater on ruthenium-based eggshell catalysts in a bubbling bed reactor.

    Science.gov (United States)

    Yang, M; Sun, Y; Xu, A H; Lu, X Y; Du, H Z; Sun, C L; Li, C

    2007-07-01

    Catalytic wet air of coke-plant wastewater was studied in a bubbling bed reactor. Two types of supported Ru-based catalysts, eggshell and uniform catalysts, were employed. Compared with the results in the wet air oxidation of coke-plant wastewater, supported Ru uniform catalysts showed high activity for chemical oxygen demand (COD) and ammonia/ammonium compounds (NH3-N) removal at temperature of 250 degrees C and pressure of 4.8 MPa, and it has been demonstrated that the catalytic activity of uniform catalyst depended strongly on the distribution of active sites of Ru on catalyst. Compared to the corresponding uniform catalysts with the same Ru loading (0.25 wt.% and 0.1 wt.%, respectively), the eggshell catalysts showed higher activities for CODcr removal and much higher activities for NH3-N degradation. The high activity of eggshell catalyst for treatment of coke-plant wastewater can be attributed to the higher density of active Ru sites in the shell layer than that of the corresponding uniform catalyst with the same Ru loading. It has been also evidenced that the active Ru sites in the internal core of uniform catalyst have very little or no contribution to CODcr and NH3-N removal in the total oxidation of coke-plant wastewater.

  20. A compact process for the treatment of olive mill wastewater by combining wet hydrogen peroxide catalytic oxidation and biological techniques.

    Science.gov (United States)

    Azabou, Samia; Najjar, Wahiba; Bouaziz, Mohamed; Ghorbel, Abdelhamid; Sayadi, Sami

    2010-11-15

    A system based on combined actions of catalytic wet oxidation and microbial technologies for the treatment of highly polluted OMW containing polyphenols was studied. The wet hydrogen peroxide catalytic oxidation (WHPCO) process has been investigated in the semi-batch mode at atmospheric pressure, using aluminium-iron-pillared inter layer clay ((Al-Fe)PILC), under two different catalytic processes: ((Al-Fe)PILC/H(2)O(2)/ultraviolet radiations) at 25°C and ((Al-Fe)PILC/H(2)O(2)) at 50°C. The results show that raw OMW was resistant to the photocatalytic process. However ((Al-Fe)PILC/H(2)O(2)), system operating at 50°C reduced considerably the COD, colour and total phenolic contents, and thus decreased the inhibition of the marine photobacteria Vibrio fischeri luminescence by 70%. This study also examined the feasibility of coupling WHPCO and anaerobic digestion treatment. Biomethanisation experiments performed with raw OMW or pre-treated OMW proved that pre-treatments with ((Al-Fe)PILC/H(2)O(2)) system, for more than 2 h, resulted in higher methane production. Both untreated OMW as well as 2-h pre-treated OMW revealed as toxic to anaerobic bacteria.

  1. Purification and characterization of thiol dependent, oxidation-stable serine alkaline protease from thermophilic Bacillus sp.

    Directory of Open Access Journals (Sweden)

    Aysha Kamran

    2015-06-01

    Full Text Available Alkaline serine protease was purified to homogeneity from culture supernatant of a thermophilic, alkaliphilic Bacillus sp. by 80% ammonium sulphate precipitation followed by CM-cellulose and DEAE-cellulose ion exchange column chromatography. The enzyme was purified up to 16.5-fold with 6900 U/mg activity. The protease exhibited maximum activity towards casein at pH 8.0 and at 80 °C. The enzyme was stable at pH 8.0 and 80 °C temperature up to 2 h. The Ca2+ and Mn2+ enhanced the proteolytic activity up to 44% and 36% as compared to control, respectively. However, Zn2+, K+, Ba2+, Co2+, Hg2+ and Cu2+ significantly reduced the enzyme activity. PMSF (phenyl methyl sulphonyl fluoride completely inhibited the protease activity, whereas the activity of protease was stimulated up to two folds in the presence of 5 mM 2-mercaptoethanol. The enzyme was also stable in surfactant (Tween-80 and other commercial detergents (SDS, Triton X-100.

  2. Alkaline ameliorants increase nitrous oxide emission from acidified black soil in Northeastern China.

    Science.gov (United States)

    Han, Zuoqiang; Zhang, Xilin; Qiao, Yanjiao; Wang, Lianfeng

    2011-06-01

    Lime and plant ash are common management used to achieve optimum pH for plant growth and improve soil properties in agricultural soils. Laboratory incubation was conducted to assess N20 emissions as influenced by different soil amendments (lime and plant ash) in a slightly acidic arable soil (pH 5.34). The experimental treatments consisted of CK, lime and plant ash fertilized with NH4(+)-N or N03(-)-N as nitrogen resource. The results show that lime and plant ash dramatically increases the soil pH and N20 emission. For N03(-)-N fertilization, the cumulative N20 emissions from CK, lime and ash are 421, 1669 and 921 μg N20-N/kg, respectively. For NH4(+)-N fertilization, the cumulative N20 emissions from CK, lime and ash are 361, 576 and 559 μg N20-N/kg, respectively. N03(-)-N addition leads to more N20 emission than that of NH4(+)-N addition, and lime increases more N20 emission than that of plant ash. After incubation, N03(-)-N content decreased largely. The findings suggested that alkaline ameliorants increase N20 emissions due to enhancement of soil denitrification.

  3. Surface Oxidation Study of Uranium Dioxide Under Wet and Dry Conditions

    Science.gov (United States)

    2005-03-01

    oxygen [ Colmenares , 1984]. This oxidation rate has been reported in the time frame of minutes to hours. During the preparation of the UO2 powder...Science (Seventh Edition). Prentice-Hall, Inc. 1997. Colmenares , C., Oxidation Mechanisms and Catalytic Properties of the Actinides, Progress in

  4. Direct synthesis of nanocrystalline oxide powders by wet-chemical techniques

    Directory of Open Access Journals (Sweden)

    Vladimir V. Srdić

    2010-09-01

    Full Text Available In a recent period there is a great need for increasing the knowledge of tailoring the innovative procedures for the synthesis of electroceramic nanopowders and materials with improved quality for specific application. In order to produce electroceramics with desirable microstructure and properties, synthesis of stoichiometric, ultra-fine and agglomerate free powders with narrow size distributions is one of the most important steps. Within this scope, in the present paper we summarize our recent results on direct synthesis of some important perovskites and ferrites nanopowders by wet-chemical techniques.

  5. Assessment of methane emission and oxidation at Air Hitam Landfill site cover soil in wet tropical climate.

    Science.gov (United States)

    Abushammala, Mohammed F M; Basri, Noor Ezlin Ahmad; Elfithri, Rahmah

    2013-12-01

    Methane (CH₄) emissions and oxidation were measured at the Air Hitam sanitary landfill in Malaysia and were modeled using the Intergovernmental Panel on Climate Change waste model to estimate the CH₄ generation rate constant, k. The emissions were measured at several locations using a fabricated static flux chamber. A combination of gas concentrations in soil profiles and surface CH₄ and carbon dioxide (CO₂) emissions at four monitoring locations were used to estimate the CH₄ oxidation capacity. The temporal variations in CH₄ and CO₂ emissions were also investigated in this study. Geospatial means using point kriging and inverse distance weight (IDW), as well as arithmetic and geometric means, were used to estimate total CH₄ emissions. The point kriging, IDW, and arithmetic means were almost identical and were two times higher than the geometric mean. The CH₄ emission geospatial means estimated using the kriging and IDW methods were 30.81 and 30.49 gm(−2) day(−1), respectively. The total CH₄ emissions from the studied area were 53.8 kg day(−1). The mean of the CH₄ oxidation capacity was 27.5 %. The estimated value of k is 0.138 year(−1). Special consideration must be given to the CH₄ oxidation in the wet tropical climate for enhancing CH₄ emission reduction.

  6. Kinetics of Passive Oxidation of Hi-Nicalon-S SiC Fibers in Wet Air: Relationships between Si02 Scale Thickness, Crystallization, and Fiber Strength (Preprint)

    Science.gov (United States)

    2012-07-01

    crystallize to cristobalite and tridymite in 100 hours at 1000°C or in one hour at 1300°C. Crystallization kinetics for oxidation in wet air were...measured by TEM. Oxidation initially produces an amorphous scale that starts to crystallize to cristobalite and tridymite in 100 hours at 1000°C or in...using reflected light interference fringes observed by optical microscopy. Cross-sectional TEM specimens were prepared from oxidized fibers by

  7. Characterization of Pt-Pd/C Electrocatalyst for Methanol Oxidation in Alkaline Medium

    Directory of Open Access Journals (Sweden)

    S. S. Mahapatra

    2011-01-01

    Full Text Available The Pt-Pd/C electrocatalyst was synthesized on graphite substrate by the electrochemical codeposition technique. The physicochemical characterization of the catalyst was done by SEM, XRD, and EDX. The electrochemical characterization of the Pt-Pd/C catalyst for methanol electro-oxidation was studied over a range of NaOH and methanol concentrations using cyclic voltammetry, quasisteady-state polarization, chronoamperometry, and electrochemical impedance spectroscopy. The activity of methanol oxidation increased with pH due to better OH species coverage on the electrode surface. At methanol concentration (>1.0 M, there is no change in the oxidation peak current density because of excess methanol at the electrode surface and/or depletion of OH− at the electrode surface. The Pt-Pd/C catalyst shows good stability and the low value of Tafel slope and charge transfer resistance. The enhanced electrocatalytic activity of the electrodes is ascribed to the synergistic effect of higher electrochemical surface area, preferred OH− adsorption, and ad-atom contribution on the alloyed surface.

  8. FTIR AND SOME PHYSICAL PROPERTIES OF ALKALINE EARTH BORATE GLASSES CONTAINING HEAVY METAL OXIDES

    Directory of Open Access Journals (Sweden)

    RAMADEVUDU.G

    2011-09-01

    Full Text Available The FTIR spectra of heavy metal oxide doped borate glasses with the general formula RO-MO-B2O3 (RO= MgO, CaO, SrO and BaO, MO=ZnO, TeO2, PbO and Bi2O3 were studied in the spectral range 400-4400cm-1 toobtain information about the influence of the glass composition on the spectra. The FTIR studies revealed that MO acted differently in RO-B2O3 glass matrix and produced small variations in the glass structure. RO oxides also affected the glass structure slightly due to mixed oxide effect. However the structural groupings present ineach series of glasses are not much affected by the composition. The effect of composition on some physical properties like density, molar volume was also carried out. The increase in the values of physical parameters such as density and glass transition temperature is attributed to conversion of [BO3]3- triangular units into BO4-tetrahedral units.

  9. Catalytic Wet Air Oxidation of o-Chlorophenol in Wastewater%邻氯苯酚废水的催化湿式氧化处理

    Institute of Scientific and Technical Information of China (English)

    徐新华; 汪大翚

    2003-01-01

    Catalytic wet air oxidation (CWAO) was investigated in laboratory-scale experiments for the treatmentof o-chlorophenol in wastewater. Experimental results showed that wet air oxidation (WAO) process in the absence ofcatalyst was also effective for o-chlorophenol in wastewater treatment. Up to 80% of the initial CODCr was removedby wet air oxidation at 270℃ with twice amount of the required stoichiometric oxygen supply. At temperatureof 150℃, the removal rate of CODCr was only 30%. Fe2(SO4)3, CuSO4, Cu(NO3)2 and MnSO4 exhibited highcatalytic activity. Higher removal rate of CODCr was obtained by CWAO. More than 96% of the initial CODCrwas removed at 270℃ and 84.6%-93.6% of the initial CODCr was removed at 150℃. Mixed catalysts had bettercatalytic activity for the degradation of o-chlorophenol in wastewater.

  10. Investigation of the Alkaline Electrochemical Interface and Development of Composite Metal/Metal-Oxides for Hydrogen and Oxygen Electrodes

    Science.gov (United States)

    Bates, Michael

    Understanding the fundamentals of electrochemical interfaces will undoubtedly reveal a path forward towards a society based on clean and renewable energy. In particular, it has been proposed that hydrogen can play a major role as an energy carrier of the future. To fully utilize the clean energy potential of a hydrogen economy, it is vital to produce hydrogen via water electrolysis, thus avoiding co-production of CO2 inherent to reformate hydrogen. While significant research efforts elsewhere are focused on photo-chemical hydrogen production from water, the inherent low efficiency of this method would require a massive land-use footprint to achieve sufficient hydrogen production rates to integrate hydrogen into energy markets. Thus, this research has primarily focused on the water splitting reactions on base-metal catalysts in the alkaline environment. Development of high-performance base-metal catalysts will help move alkaline water electrolysis to the forefront of hydrogen production methods, and when paired with solar and wind energy production, represents a clean and renewable energy economy. In addition to the water electrolysis reactions, research was conducted to understand the de-activation of reversible hydrogen electrodes in the corrosive environment of the hydrogen-bromine redox flow battery. Redox flow batteries represent a promising energy storage option to overcome the intermittency challenge of wind and solar energy production methods. Optimization of modular and scalable energy storage technology will allow higher penetration of renewable wind and solar energy into the grid. In Chapter 1, an overview of renewable energy production methods and energy storage options is presented. In addition, the fundamentals of electrochemical analysis and physical characterization of the catalysts are discussed. Chapter 2 reports the development of a Ni-Cr/C electrocatalyst with unprecedented mass-activity for the hydrogen evolution reaction (HER) in alkaline

  11. Carbon isotope analysis of dissolved organic carbon in fresh and saline (NaCl) water via continuous flow cavity ring-down spectroscopy following wet chemical oxidation.

    Science.gov (United States)

    Conaway, Christopher H; Thomas, Burt; Saad, Nabil; Thordsen, James J; Kharaka, Yousif K

    2015-01-01

    This work examines the performance and limitations of a wet chemical oxidation carbon analyser interfaced with a cavity ring-down spectrometer (WCO-CRDS) in a continuous flow (CF) configuration for measuring δ(13)C of dissolved organic carbon (δ(13)C-DOC) in natural water samples. Low-chloride matrix (oxidation despite using high-concentration oxidant, extended reaction time, or post-wet chemical oxidation gas-phase combustion. However, through a combination of dilution, chloride removal, and increasing the oxidant:sample ratio, high-salinity samples with sufficient DOC (>22.5 µg C/aliquot) may be analysed. The WCO-CRDS approach requires more total carbon (µg C/aliquot) than conventional CF-isotope ratio mass spectrometer, but is nonetheless applicable to a wide range of DOC concentration and water types, including brackish water, produced water, and basinal brines.

  12. Photocatalytic activities of wet oxidation synthesized ZnO and ZnO-TiO2 thick porous films

    Science.gov (United States)

    Chen, Ruiqun; Han, Jie; Yan, Xiaodong; Zou, Chongwen; Bian, Jiming; Alyamani, Ahmed; Gao, Wei

    2011-05-01

    Highly porous zinc oxide (ZnO) film was produced by using reactive magnetron sputtering zinc target followed by wet oxidation. Titanium dioxide (TiO2) was mixed to the porous films by using either TiO2 target magnetron sputter deposition or sol-spin method. The film thickness could reach 50 μm with uniform porosity. On the sputtering prepared ZnO-TiO2 film surface, fine nanorods with small anatase TiO2 nano-clusters on the tips were observed by SEM and TEM, and the titanium (Ti) composition was determined by XPS as 0.37%. The sol-spin treatment could increase the Ti composition to 4.9%, with reduced pore size compared to the untreated ZnO porous film. Photoluminescence measurements showed that the Ti containing porous film has strong ultraviolet-visible light emission. In the photo-catalysis testing, ZnO and ZnO-TiO2 have similar photo-catalysis activity under 365 nm UV irradiation, but under visible light, the photocatalysis activities of ZnO-TiO2 films were twice higher than that of ZnO porous film, implying promising applications of this porous oxide composite for industrial and dairy farm wastewater treatment.

  13. Simulation Analysis of Sludge Disposal and Volatile Fatty Acids Production from Gravity Pressure Reactor via Wet Air Oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Park, Gwon Woo [Biomass and Waste Energy Laboratory, KIER, Daejeon (Korea, Republic of); Seo, Tae Wan; Lee, Hong-Cheol; Hwang, In-Ju [Environmental and Plant Engineering Research Institute, KICT, Goyang (Korea, Republic of)

    2016-04-15

    Efficacious wastewater treatment is essential for increasing sewage sludge volume and implementing strict environmental regulations. The operation cost of sludge treatment amounts up to 50% of the total costs for wastewater treatment plants, therefore, an economical sludge destruction method is crucially needed. Amid several destruction methods, wet air oxidation (WAO) can efficiently treat wastewater containing organic pollutants. It can be used not only for sludge destruction but also for useful by-product production. Volatile fatty acids (VFAs), one of many byproducts, is considered to be an important precursor of biofuel and chemical materials. Its high reaction condition has instituted the study of gravity pressure reactor (GPR) for an economical process of WAO to reduce operation cost. Simulation of subcritical condition was conducted using Aspen Plus with predictive Soave-Redlich-Kwong (PSRK) equation of state. Conjointly, simulation analysis for GPR depth, oxidizer type, sludge flow rate and oxidizer injection position was carried out. At GPR depth of 1000m and flow rate of 2 ton/h, the conversion and yield of VFAs were 92.02% and 0.17g/g, respectively.

  14. Effect of Composition and Mass Ratio on the Catalytic Wet Air Oxidation Catalyst Cu–Fe–La/FSC

    Directory of Open Access Journals (Sweden)

    Wu Chao

    2016-01-01

    Full Text Available The catalytic wet air oxidation (CWAO technology is used for the treatment of the simulated printing and dyeing wastewater and also for investigating the catalyst performance indicators such as catalyst activity and stability. The catalyst activity is mainly reflected from the water decolorization and CODCr removal rates, and the stability of the catalyst is mainly reflected by the quantity of metal dissolution. The experimental results showed that the prepared Cu–Fe–La/FSC catalyst with a 1:1:2 ratio of Cu–Fe–La by the impregnation method exhibited good activity for the treatment of the simulated printing and dyeing wastewater by the CWAO method, and the decolorization and CODCr removal rates using this catalyst were 98.7% and 78.6%, respectively, with a higher catalytic activity, lower concentration of metal dissolution, and good stability.

  15. Wet air oxidation pretreatment of biomethanated distillery effluent: mapping pretreatment efficiency in terms color, toxicity reduction and biogas generation.

    Science.gov (United States)

    Sarat Chandra, T; Malik, S N; Suvidha, G; Padmere, M L; Shanmugam, P; Mudliar, S N

    2014-04-01

    The effluents from molasses-based distilleries after biomethanation are beset with problems of intensified dark brown color, high residual COD, low biodegradability index (BOD/COD ratio Wet air oxidation (WAO) pretreatment of biomethanated distillery effluent resulted in substantial enhancement in the biodegradability index (BI) (up to 0.8). WAO pretreated effluent on anaerobic digestion indicated favorable biogas generation with methane content up to 64% along with concomitant COD reduction up to 54.75%. The HPLC analysis indicated that the pretreatment facilitated degradation of major color containing compounds-namely melanoidins, up to 97.8%. The pretreated effluent with enhanced biodegradability along with substantially reduced color also indicated positive effect on seed germination (up to 100%), implying toxicity reduction of the effluent post WAO pretreatment.

  16. Wetting characteristics of the anodic aluminum oxide template and fabrication of cracks using ultraviolet curable resin solution

    Science.gov (United States)

    Sung Yoon, Jae; Phuong, NguyenThi; Hwan Kim, Jeong; Choi, Doo-Sun; Whang, Kyung-hyun; Yoo, Yeong-eun

    2014-03-01

    We have investigated the wetting characteristics of the anodic aluminum oxide (AAO) template with ultraviolet curable polymer resin. The wettability of the template depends on the pore size on the surface, where it is improved with smaller pores and vice versa. Plasma treatment on the surface of the template is used to improve the wettability and the adhesion of the cured polymer to the template. And we also introduce the cracks on the polymer layer for possible application as nano-sized cavities. The resin within the pore is cleaved during the curing process so that cavities or cracks could be made which are much smaller than the original pores of the AAO template.

  17. Energy balance and cost-benefit analysis of biogas production from perennial energy crops pretreated by wet oxidation

    DEFF Research Database (Denmark)

    Uellendahl, Hinrich; Wang, Guangtao; Møller, Henrik B.

    2008-01-01

    Perennial crops need far less energy to plant, require less fertilizer and pesticides, and show a lower negative environmental impact compared with annual crops like for example corn. This makes the cultivation of perennial crops as energy crops more sustainable than the use of annual crops....... The conversion into biogas in anaerobic digestion plants shows however much lower specific methane yields for the raw perennial crops like miscanthus and willow due to their lignocellulosic structure. Without pretreatment the net energy gain is therefore lower for the perennials than for corn. When applying wet...... oxidation to the perennial crops, however, the specific methane yield increases significantly and the ratio of energy output to input and of costs to benefit for the whole chain of biomass supply and conversion into biogas becomes higher than for corn. This will make the use of perennial crops as energy...

  18. Electrocatalytic Oxidation of Formic Acid in an Alkaline Solution with Graphene-Oxide- Supported Ag and Pd Alloy Nanoparticles.

    Science.gov (United States)

    Han, Hyoung Soon; Yun, Mira; Jeong, Haesang; Jeon, Seungwon

    2015-08-01

    The electrocatalytic activities of metal-decorated graphene oxide (GO) catalysts were investigated. Electrochemically reduced GO-S-(CH2)4-S-Pd [ERGO-S-(CH2)4-S-Pd] and GO-S-(CH2)4-S-PdAg alloy [ERGO-S-(CH2)4-S-PdAg] were obtained through the electrochemical reduction of GO-S-(CH2)4-S-Pd and GO-S-(CH2)4-S-PdAg in a pH 5 PBS solution. It was demonstrated that the application of ERGO-S-(CH2)4-S-Pd and ERGO-S-(CH2)4-S-PdAg used in a modified GCE improves the electrocatalytic oxidation of formic acid. The addition of an Ag nanoparticle with a carbon chain-Pd in the electrode provides an electrode with very interesting properties for the electrocatalytic oxidation of formic acid. The ERGO-S-(CH2)4-S-Pd and ERGO-S-(CH2)4-S-PdAg were characterized via X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). ERGO-S-(CH2)4-S-Pd and ERGO-S-(CH2)4-S-PdAg can be employed for the electrocatalytic oxidation of formic acid. The electrochemical behaviors of this electrode were investigated using cyclic voltammetry (CV), chronoamperometry (CA) and electrochemical impedance spectroscopy (EIS).

  19. Development of the Monolith Froth Reactor for Catalytic Wet Oxidation of CELSS Model Wastes

    Science.gov (United States)

    Abraham, Martin; Fisher, John W.

    1995-01-01

    The aqueous phase oxidation of acetic acid, used as a model compound for the treatment of CELSS (Controlled Ecological Life Support System) waste, was carried out in the monolith froth reactor which utilizes two-phase flow in the monolith channels. The catalytic oxidation of acetic acid was carried out over a Pt/Al2O3 catalyst, prepared at The University of Tulsa, at temperatures and pressures below the critical point of water. The effect of externally controllable parameters (temperature, liquid flow rate, distributor plate orifice size, pitch, and catalyst distance from the distributor plate) on the rate of acetic acid oxidation was investigated. Results indicate reaction rate increased with increasing temperature and exhibited a maximum with respect to liquid flow rate. The apparent activation energy calculated from reaction rate data was 99.7 kJ/mol. This value is similar to values reported for the oxidation of acetic acid in other systems and is comparable to intrinsic values calculated for oxidation reactions. The kinetic data were modeled using simple power law kinetics. The effect of "froth" feed system characteristics was also investigated. Results indicate that the reaction rate exhibits a maximum with respect to distributor plate orifice size, pitch, and catalyst distance from the distributor plate. Fundamental results obtained were used to extrapolate where the complete removal of acetic acid would be obtained and for the design and operation of a full scale CELSS treatment system.

  20. Hydrolysis of solubilized hemicellulose derived from wet-oxidized wheat straw by a mixture of commercial fungal enzyme preparations

    Energy Technology Data Exchange (ETDEWEB)

    Skammelsen Schmidt, Anette; Thomsen, Alle Belinda; Woidemann, Anders [Risoe National Lab. (Denmark); Tenkanen, Maija [VTT Biotechnology and Food Research (Finland)

    1998-04-01

    The enzymatic hydrolysis of the solubilized hemicellulose fraction from wet-oxidized wheat straw was investigated for quantification purposes. An optimal hydrolysis depends on factors such as composition of the applied enzyme mixture and the hydrolysis conditions (enzyme loading, hydrolysis time, pH-value, and temperature). A concentrated enzyme mixture was used in this study prepared at VTT Biotechnology and Food Research, Finland, by mixing four commercial enzyme preparations. No distinctive pH-value and temperature optima were identified after a prolonged incubation of 24 hours. By reducing the hydrolysis time to 2 hours a temperature optimum was found at 50 deg. C, where a pH-value higher than 5.2 resulted in reduced activity. An enzyme-substrate-volume-ratio of 0.042, a pH-value of 5.0, and a temperature of 50 deg. C were chosen as the best hydrolysis conditions due to an improved monosaccharide yield. The hydrolysis time was chosen to be 24 hours to ensure equilibrium and total quantification. Even under the best hydrolysis conditions, the overall sugar yield from the enzymatic hydrolysis was only 85% of that of the optimal acid hydrolysis. The glucose yield were approximately the same for the two types of hydrolyses, probably due to the high cellulase activity in the VTT-enzyme mixture. For xylose and arabinose the enzymatic hydrolysis yielded only 80% of that of the acid hydrolysis. As the pentoses existed mainly as complex polymers their degradation required many different enzymes, some of which might be missing from the VTT-enzyme mixture. Furthermore, the removal of side-choins from the xylan backbone during the wet-oxidation pretreatment process might enable the hemicellulosic polymers to interact and precipitate, hence, reducing the enzymatic digestibility of the hemicellulose. (au) 8 tabs., 10 ills., 65 refs.

  1. Development of Alkaline Oxidative Dissolution Methods for Chromium (III) Compounds Present in Hanford Site Tank Sludges

    Energy Technology Data Exchange (ETDEWEB)

    NN Krot; VP Shilov; AM Fedoseev; NA Budantseva; MV Nikonov; AB Yusov; AYu Garnov; IA Charushnikova; VP Perminov; LN Astafurova; TS Lapitskaya; VI Makarenkov

    1999-07-02

    The high-level radioactive waste sludge in the underground storage tanks at the Hanford Site contains various chromium(III)solid phases. Dissolution and removal of chromium from tank waste sludges is desirable prior to high-level waste vitrification because increased volume is required to incorporate the residual chromium. Unfortunately, dissolution of chromium from the sludge to form Cr(OH){sub 4}{sup {minus}} through treatment with heated NaOH solution (also used to dissolve aluminum phases and metathesize phosphates to sodium salts) generally has been unsuccessful in tests with both simulated and genuine Hanford waste sludges. Oxidative dissolution of the Cr(III) compounds to form soluble chromate has been proposed as an alternative chromium solid phase dissolution method and results of limited prior testing have been reported.

  2. Ni/Pd-Decorated Carbon NFs as an Efficient Electrocatalyst for Methanol Oxidation in Alkaline Medium

    Science.gov (United States)

    Mohamed, Ibrahim M. A.; Khalil, Khalil Abdelrazek; Mousa, Hamouda M.; Barakat, Nasser A. M.

    2017-01-01

    In this study, Ni/Pd-decorated carbon nanofibers (NFs) were fabricated as an electrocatalyst for methanol oxidation. These NFs were synthesized based on carbonization of poly(vinyl alcohol), which has high carbon content compared to many polymers used to prepare carbon NFs. Typically, calcination of an electrospun mat composed of nickel acetate, palladium acetate, and poly(vinyl alcohol) can produce Ni/Pd-doped carbon NFs. The introduced NFs were characterized by scanning electron microscopy, transmission electron microscopy (TEM), high-resolution transmission electron microscopy, line TEM energy dispersive x-ray spectrometry, field emission scanning electron microscopy, and x-ray powder diffraction. These physicochemical characterizations are acceptable tools to investigate the crystallinity and chemistry of the fabricated Ni/Pd-carbon NFs. Accordingly, the prepared NFs were tested to enhance the economic and catalytic behavior of methanol electrooxidation. Experimentally, the obtained onset potential was small compared to many reported materials; 0.32 V (versus Ag/AgCl as a reference electrode). At the same time, the current density changed from 5.08 mA/cm2 in free methanol at 0.6 V to 12.68 mA/cm2 in 0.1 mol/L methanol, which can be attributed to the MeOH oxidation. Compared to nanoparticles, the NFs have a distinct effect on the electrocatalytic performance of material due to the effect of the one-dimensional structure, which facilitates the electron transfer. Overall, the presented work opens a new way for non-precious one-dimensional nanostructured catalysts for direct methanol fuel cell technology.

  3. Ni/Pd-Decorated Carbon NFs as an Efficient Electrocatalyst for Methanol Oxidation in Alkaline Medium

    Science.gov (United States)

    Mohamed, Ibrahim M. A.; Khalil, Khalil Abdelrazek; Mousa, Hamouda M.; Barakat, Nasser A. M.

    2016-09-01

    In this study, Ni/Pd-decorated carbon nanofibers (NFs) were fabricated as an electrocatalyst for methanol oxidation. These NFs were synthesized based on carbonization of poly(vinyl alcohol), which has high carbon content compared to many polymers used to prepare carbon NFs. Typically, calcination of an electrospun mat composed of nickel acetate, palladium acetate, and poly(vinyl alcohol) can produce Ni/Pd-doped carbon NFs. The introduced NFs were characterized by scanning electron microscopy, transmission electron microscopy (TEM), high-resolution transmission electron microscopy, line TEM energy dispersive x-ray spectrometry, field emission scanning electron microscopy, and x-ray powder diffraction. These physicochemical characterizations are acceptable tools to investigate the crystallinity and chemistry of the fabricated Ni/Pd-carbon NFs. Accordingly, the prepared NFs were tested to enhance the economic and catalytic behavior of methanol electrooxidation. Experimentally, the obtained onset potential was small compared to many reported materials; 0.32 V (versus Ag/AgCl as a reference electrode). At the same time, the current density changed from 5.08 mA/cm2 in free methanol at 0.6 V to 12.68 mA/cm2 in 0.1 mol/L methanol, which can be attributed to the MeOH oxidation. Compared to nanoparticles, the NFs have a distinct effect on the electrocatalytic performance of material due to the effect of the one-dimensional structure, which facilitates the electron transfer. Overall, the presented work opens a new way for non-precious one-dimensional nanostructured catalysts for direct methanol fuel cell technology.

  4. Alkaline, Endo III and FPG modified comet assay as biomarkers for the detection of oxidative DNA damage in rats with experimentally induced diabetes.

    Science.gov (United States)

    Kushwaha, S; Vikram, A; Trivedi, P P; Jena, G B

    2011-12-24

    Increased production of reactive oxygen species under diabetic condition underlines the higher oxidatively damaged DNA in different tissues. However, it is practically difficult to assess the oxidatively damaged DNA in different internal organs. Therefore, the present study was aimed to evaluate the extent of oxidative stress-induced DNA damage in different organs with the progression of diabetes. Diabetic and control Sprague Dawley rats were sacrificed in time-dependent manner and the lung, liver, heart, aorta, kidney, pancreas and peripheral blood lymphocytes (PBL) were analyzed for both alkaline and modified comet assay with endonuclease-III (Endo III) and formamidopyrimidine-DNA glycosylase (FPG) (hereafter called modified comet assay) for the detection of oxidative DNA damage. The statistically significant increase in olive tail moment (OTM) was found in all the tested tissues. The extent of DNA damage was increased with the progression of diabetes as revealed by the parameter of OTM in alkaline and modified comet assay. Further, the positive correlations were observed between OTM of the lung, liver, heart, aorta, kidney and pancreas with PBL of diabetic rat in the alkaline and modified comet assay. Moreover, significant increase in the 8-oxodG positive nuclei in the lung, liver, heart, aorta, kidney and pancreas was observed in 4th and 8th week diabetic rat as compared to control. Results of the present study clearly indicated the suitability of alkaline and modified comet assay for the detection of multi-organ oxidative DNA damage in streptozotocin (STZ)-induced diabetic rat and showed that damaged DNA of PBL can be used as a suitable biomarker to assess the internal organs response to DNA damage in diabetes.

  5. Fragment size for calculations on alkaline-earth oxides by the crystal cluster SCF-X/sub approx. /-RW method

    Energy Technology Data Exchange (ETDEWEB)

    Lobach, V.A.; Sobolev, A.B.; Shul' gin, B.V.

    1987-05-01

    Calculations have been performed on the clusters (A/sub x/B/sub y/) (x = 1, 13; y = 6, 14), corresponding to perfect crystals of the alkaline-earth oxides (AEO) MgO, CaO, and SrO by means of methods involving molecular clusters (MC) and crystalline clusters (CC) in the SCF-X/sub approx./-RW method. It is found that MC is unsuitable for describing perfect AEO, because they have a long-range Coulomb interaction and a potential cluster effect. Even in the CC method, the nonstoichiometric composition of (A/sub x/B/sub y/) for x < 13 and y < 14 does not allow one to obtain satisfactory agreement with the observed optical and x-ray spectra. The (A/sub 13/B/sub 14/) and (B/sub 13/A/sub 14/) clusters reproduce satisfactorily the partial composition of the valence band (VB) and the conduction band (CB), as well as the widths of those bands, the fine structure of the K emission spectrum for oxygen in MgO, and the observed electron-density distribution. A study is made of the effects of varying the radii of the spheres on the error from the region between the spheres with muffin-tin averaging.

  6. Size of the fragment for crystal cluster SCF-X/sub /-SW calculations of alkaline earth metal oxides

    Energy Technology Data Exchange (ETDEWEB)

    Lobach, V.A.; Sobolev, A.B.; Shul' gin, B.V.

    Calculation of (A/sub x/B/sub y/) (x=1, 13; y=6, 14) clusters, corresponding to ideal crystals of alkaline earth metal oxides (AEMO) MgO, CaO, SrO by means of molecular cluster (MC) and crystal cluster (CC) SCF-X/sub /-SW method is carried out. MC method is not suitable for description of ideal AEMO electron structure due to long-range Coulomb interaction and potential cluster effect. Even in CC method at x < 13 and y < 14 (A/sub x/B/sub y/) cluster nonstoichiometry is inhibitory to the obtaining of satisfactory agreement with the experimental optical and X-ray spectra. (A13B14) and (B13A14) clusters satisfactorily reproduce partial composition of valence band (VB) and conduction band (CB), VB and CB widths, a fine structure of oxygen K-emission spectra in MgO and also experimental distribution of electron density. Sphere radii variation effect on the value of intersphere region error with muffin-tin averaging is considered.

  7. Facile and scalable fabrication engineering of fullerenol nanoparticles by improved alkaline-oxidation approach and its antioxidant potential in maize

    Science.gov (United States)

    Liu, Fu-yang; Xiong, Feng-xia; Fan, Yi-kang; Li, Juan; Wang, He-zhong; Xing, Geng-mei; Yan, Feng-ming; Tai, Fu-ju; He, Rui

    2016-11-01

    A feasible in operation, labor-saving and low-cost one-step technology to fabricate fullerenol nanoparticles (FNPs) up to 10 g in laboratory was developed by improved alkaline-oxidation approach using moderately concentrated sodium hydroxide solution as the hydroxylation agent and o-dichlorobenzene as the solvent. This strategy paves the avenue for industrial-scale bulk production of FNPs. The resulted product, [C60(OH)22·8H2O]n, were characterized by various measurements including matrix-assisted laser desorption ionization time-of-flight mass spectrometry, high-resolution 1H nuclear magnetic resonance spectrometry, Fourier transform infrared spectroscopy, UV-Visible spectrophotometer, thermogravimetric analysis, differential scanning calorimetry, dynamic light scattering analysis, scanning electron microscopy, and electron spin resonance spectrometer. Radical scavenging assay in vitro confirmed the high efficiency of water-soluble [C60(OH)22·8H2O]n as a novel radical scavenger. Furthermore, [C60(OH)22·8H2O]n as an excellent candidate has the potential to serve as the plant defense stimulation agent in maize.

  8. Isolation of a Sulfur-oxidizing Bacterium That can Grow under Alkaline pH, from Corroded Concrete.

    Science.gov (United States)

    Maeda, T; Negishi, A; Oshima, Y; Nogami, Y; Kamimura, K; Sugio, T

    1998-01-01

    To study the early stages of concrete corrosion by bacteria, sulfur-oxidizing bacterium strain RO-1, which grows in an alkaline thiosulfate medium (pH 10.0) was isolated from corroded concreate and characterized. Strain RO-1 was a Gram negative, rod-shaped bacterium (0.5-0.6×0.9-1.5 μm). The mean G+C content of the DNA of strain RO-1 was 65.0 mol%. Optimum pH and temperature for growth were 8.0. and 30-37°C, respectively. When grown in thiosulfate medium with pH 10.0, growth rate of the strain was 48% of that observed at the optimum pH for growth. Strain RO-1 used sulfide, thiosulfate, and glucose, but not elemental sulfur or tetrathionate, as a sole energy source. Strain RO-1 grew under anaerobic conditions in pepton-NO3 (-) medium containing sodium nitrate as an electron acceptor, and had enzyme activities that oxidized sulfide, elemental sulfur, thiosulfate, sulfite, and glucose, but not tetrathionate. The bacterium had an activity to assimilate (14)CO2 into the cells when thiosulfate was used as an energy source. These results suggest that strain RO-1 is Thiobacillus versutus. Strain RO-1 exuded Ca(2+) from concrete blocks added to thiosulfate medium with pH 9.0 and the pH of the medium decreased from 9.0 to 5.5 after 22 days of cultivation. In contrast, Thiobacillus thiooxidans strain NB1-3 could not exude Ca(2+) in the same thiosulfate medium, suggesting that strain RO-1, but not T. thiooxidans NB1-3, is involved in the early stage of concrete corrosion because concrete structures just after construction contain calcium hydroxide and have a pH of 12-13.

  9. Oxidation kinetics of thin copper films and wetting behaviour of copper and Organic Solderability Preservatives (OSP) with lead-free solder

    Energy Technology Data Exchange (ETDEWEB)

    Ramirez, Mauricio, E-mail: mauricio.ramirez2@de.bosch.com [Robert Bosch GmbH, Robert-Bosch-Strasse 2, 71701 Schwieberdingen (Germany); Chair for Surface Science and Corrosion, University of Erlangen-Nuremberg, Martensstrasse 7, 91058 Erlangen (Germany); Henneken, Lothar [Robert Bosch GmbH, Robert-Bosch-Strasse 2, 71701 Schwieberdingen (Germany); Virtanen, Sannakaisa [Chair for Surface Science and Corrosion, University of Erlangen-Nuremberg, Martensstrasse 7, 91058 Erlangen (Germany)

    2011-05-15

    The oxide formation on thin copper films deposited on Si wafer was studied by XPS, SEM and Sequential Electrochemical Reduction Analysis SERA. The surfaces were oxidized in air with a reflow oven as used in electronic assembly at temperatures of 100 deg. C, 155 deg. C, 200 deg. C, 230 deg. C and 260 deg. C. The SERA analyses detected only the formation of Cu{sub 2}O but the XPS analysis done for the calibration of the SERA equipment proved also the presence of a CuO layer smaller than 2 nm above the Cu{sub 2}O oxide. The oxide growth follows a power-law dependence on time within this temperature range and an activation energy of 33.1 kJ/mol was obtained. The wettability of these surfaces was also determined by measuring the contact angle between solder and copper substrate after the soldering process. A correlation between oxide thickness and wetting angle was established. It was found that the wetting is acceptable only when the oxide thickness is smaller than 16 nm. An activation energy of 27 kJ/mol was acquired for the spreading of lead free solder on oxidized copper surfaces. From wetting tests on copper surfaces protected by Organic Solderability Preservatives (OSP), it was possible to calculate the activation energy for the thermal decomposition of these protective layers.

  10. 49 CFR 173.159 - Batteries, wet.

    Science.gov (United States)

    2010-10-01

    ... 49 Transportation 2 2010-10-01 2010-10-01 false Batteries, wet. 173.159 Section 173.159... Batteries, wet. (a) Electric storage batteries, containing electrolyte acid or alkaline corrosive battery fluid (wet batteries), may not be packed with other materials except as provided in paragraphs (g)...

  11. Ruthenium(III) catalyzed oxidation of sulfanilic acid by diperiodatocuprate(III) in aqueous alkaline medium. A kinetic and mechanistic approach

    Science.gov (United States)

    Munavalli, D. S.; Patil, R. K.; Chimatadar, S. A.; Nandibewoor, S. T.

    2009-12-01

    The kinetics of ruthenium(III) catalyzed oxidation of sulfanilic acid by diperiodatocuprate(III) (DPC) in alkaline medium at a constant ionic strength of (0.50 mol dm-3) has been studied spectrophoto-metrically. The reaction between sulfanilic acid and DPC in alkaline medium exhibits 1: 4 stoichiometry (sulfanilic acid: DPC). The reaction is first order with respect to [DPC] and [RuIII] and has less than unit order both in [sulfanilic acid] and [alkali]. The active species of catalyst and oxidant have been identified. Intervention of free radicals was observed in the reaction. The main products were identified by spot test and IR. Probable mechanism is proposed and discussed. The reaction constants involved in the different steps of the mechanism are calculated. The activation parameters with respect to the slow step of the mechanism are computed and discussed. Thermodynamic quantities are also determined.

  12. CATALYTIC WET PEROXIDE OXIDATION OF HYDROQUINONE WITH Co(Ⅱ)/ACTIVE CARBON CATALYST LOADED IN STATIC BED

    Institute of Scientific and Technical Information of China (English)

    LI Chunxiang; YAN Yongsheng; XU Wanzhen

    2008-01-01

    Catalysts based on Co(Ⅱ) supported on active carbon were prepared and loaded in static bed.The hydroquinone wouid be degraded completely after treated by Catalytic wet peroxide oxidation method with Co(Ⅱ)/active carbon catalyst.After activate treatment, the active carbon was immerged in cobaltoas nitrate solution, then put into a drying oven, Co(Ⅱ) could be loaded on the micro-surface of carbon.Taking the static bed as the equipment, the absorption of active carbon and catalysis of Co(Ⅱ) was used to reduce activation energy of hydroquinone.Thus hydroquinone could be drastically degraded and the effluent can be drained under the standard.Referring to Fenton reaction mechanism, experiment had been done to study the heterogeneous catalyzed oxidation mechanism of Co(Ⅱ).The degradation rate of hydroquinone effluent could be achieved to 92% when treated in four columns at H2O2 concentration 10%, reaction temperature 40℃, pH 5 and reaction time 2.5h.

  13. CATALYTIC WET PEROXIDE OXIDATION OF HYDROQUINONE WITH Co(II)/ACTIVE CARBON CATALYST LOADED IN STATIC BED

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    Catalysts based on Co(II) supported on active carbon were prepared and loaded in static bed. The hydroquinone would be degraded completely after treated by Catalytic wet peroxide oxidation method with Co(II)/active carbon catalyst. After activate treatment, the active carbon was immerged in cobaltous nitrate solution, then put into a drying oven, Co(II) could be loaded on the micro-surface of carbon. Taking the static bed as the equipment, the absorption of active carbon and catalysis of Co(II) was used to reduce activation energy of hydroquinone. Thus hydroquinone could be drastically degraded and the effluent can be drained under the standard. Referring to Fenton reaction mechanism, experiment had been done to study the heterogeneous catalyzed oxidation mechanism of Co(II). The degradation rate of hydroquinone effluent could be achieved to 92% when treated in four columns at H2O2 concentration 10%, reaction temperature 40℃ , pH 5 and reaction time 2.5h.

  14. [Quantitative and qualitative analysis of total bacteria and ammonia-oxidizing bacteria in Buji River in wet season].

    Science.gov (United States)

    Sun, Hai-mei; Bai, Jiao-jiao; Sun, Wei-ling; Shao, Jun

    2012-08-01

    Microbial community structure and biomass in river water can reflect the situation of water quality in some extent. Nitrogen removal was mainly achieved by the nitrification and denitrification processes, and ammonia oxidation catalyzed by ammonia-oxidizing bacteria (AOB) is the first and rate-limiting step of nitrification. To explore the AOB community structure and biomass in nitrogen polluted river, water samples were collected from Buji River (Shenzhen) in wet season. Quantification of 16S rRNA copy numbers of total bacteria and AOB were performed by real-time PCR, and the microbial community structures were studied by denaturing gradient gel electrophoresis (DGGE). The results showed that the number of total bacterial 16S rRNA changed from 4.73 x 10(10) - 3.90 x 10(11) copies x L(-1) in the water samples. The copy numbers of AOB varied from 5.44 x 10(6) - 5.96 x 10(8)copies x L(-1). Redundancy discrimination analysis (RDA) showed that the main factors affecting the structure and the numbers of bacteria were different. For total bacteria, nitrate influenced the biomass significantly (P analysis showed that water pollution in downstream resulted in evident difference in microbial community structure between upstream and downstream water samples.

  15. Treatment of refractory nano-filtration reject from a tannery using Pd-catalyzed wet air oxidation.

    Science.gov (United States)

    Tripathi, Pranav K; Rao, Nageswara N; Chauhan, Chetan; Pophali, Girish R; Kashyap, Sanjay M; Lokhande, Satish K; Gan, Lihua

    2013-10-15

    We attempted catalytic wet air oxidation (CWAO) of nanofiltration (NF)-reject using Pd based catalyst viz., Pd/activated charcoal (AC) and PdCl2 with the objective of degradation of refractory organic pollutants. Refractory organic pollutants in NF-reject before and after WAO and CWAO were confirmed by GC-MS analysis. Experiments were conducted to investigate the effects of temperature, catalyst dosage and air partial pressure on the rate of removal of total organic carbon (TOC). The reaction kinetics can be conveniently described by considering two-stage first order kinetics. The use of Pd/AC afforded 85% TOC removal, the corresponding rate constant (k) was 2.90 ± 0.075 × 10(-3)min(-1) (Pd/AC, 100mg/L; T, 473.15K; Pair, 0.69 MPa). On the other hand, 75% TOC was removed with k=2.31 ± 0.075 × 10(-3)min(-1) using Pd(2+) catalyst (Pd(2+), 16.66 mg/L; T, 473.15K; Pair, 0.69 MPa). The observed rate of mineralization under Pd-catalyzed conditions was significantly higher than that of the uncatalyzed oxidation (41%) under the similar experimental conditions. Catalyst stability experiments were performed and TEM, SEM, XRD, Raman and XPS characterization data collected. Despite some morphological transformation of support, Pd catalyst was stable under CWAO conditions.

  16. Unprecedented Catalytic Wet Oxidation of Glucose to Succinic Acid Induced by the Addition of n-Butylamine to a Ru(III) Catalyst.

    Science.gov (United States)

    Podolean, Iunia; Rizescu, Cristina; Bala, Camelia; Rotariu, Lucian; Parvulescu, Vasile I; Coman, Simona M; Garcia, Hermenegildo

    2016-09-08

    A new pathway for the catalytic wet oxidation (CWO) of glucose is described. Employing a cationic Ru@MNP catalyst, succinic acid is obtained in unprecedently high yield (87.5 %) for a >99.9 % conversion of glucose, most probably through a free radical mechanism combined with catalytic didehydroxylation of vicinal diols and hydrogenation of the resulted unsaturated intermediate.

  17. Wet carbon-based solid acid/potassium permanganate as an efficient heterogeneous reagents for oxidation of alcohols under mild conditions

    Institute of Scientific and Technical Information of China (English)

    Arash Shokrolahi; Abbas Zali; Mohammad Hossein Kes

    2008-01-01

    Wet carbon-based solid acid and potassium permanganate were used as new reagents for oxidation of alcohols to their corresponding aldehydes and ketones in heterogeneous mixtures.The experiments were done moderately at mild condition and high yields in suitable times were obtained.

  18. A General Silica-Templating Synthesis of Alkaline Mesoporous Carbon Catalysts for Highly Efficient H2S Oxidation at Room Temperature.

    Science.gov (United States)

    Zhang, Zixiao; Jiang, Wuyou; Long, Donghui; Wang, Jitong; Qiao, Wenming; Ling, Licheng

    2017-01-25

    A general synthesis of alkaline mesoporous carbons (AMCs) is developed based on a simplified silica-templating method for room-temperature catalytic oxidation of H2S. The key to the success relies on dissolving the silica templates to create the interconnected mesoporous structure as well as leaving parts of the alkaline products in the pores; both of them are prerequisites for H2S oxidation. By adjusting the alkaline etching degree and organic/inorganic ratio, the porosity and basicity of the AMC could be simultaneously tuned, allowing the AMCs direct use for H2S catalytic oxidation with an unprecedented removal capacities of 4.49 ± 0.12 g/g. Such excellent catalytic performance should be attributed to the developed pore structure that stores the product sulfur and the strong basicity that promotes the dissociation of H2S into HS(-) ions. Moreover, this simplified silica-templating method could be easily extended to the preparation of various silica templated mesoporous carbon catalysts. All these AMCs demonstrate a successful combination of low cost with high performance, which may well be the answer for the technical development of industrial H2S removal.

  19. Kinetics and mechanism of oxidation of L-leucine by alkaline diperiodatocuprate(III)—A free radical intervention, deamination and decarboxylation

    Indian Academy of Sciences (India)

    Keerti M Naik; Sharanappa T Nandibewoor

    2012-07-01

    The kinetics of oxidation of L-leucine by diperiodatocuprate (III) (DPC) in aqueous alkaline medium at a constant ionic strength of 0.10mol dm-3 was studied spectrophotometrically. The reaction between L-leucine and DPC in alkaline medium exhibits 1:4 stoichiometry (L-leucine: DPC). The reaction is of first order in [DPC] and has less than unit order in both [L-leucine] and [alkali]. However, the order in [Lleucine] and [alkali] changes from first order to zero order as their concentration increase. Intervention of free radicals was observed in the reaction. Increase in periodate concentration decreased the rate. The oxidation reaction in alkaline medium has been shown to proceed via a monoperiodatocuprate (III) - L-leucine complex, which decomposed slowly in a rate-determining step followed by other fast steps to give the products. The main oxidative products were identified by spot test and GC-MS. The reaction constants involved in the different steps of the mechanism were calculated.

  20. Large-Scale Mercury Control Technology Testing for Lignite-Fired Utilities - Oxidation Systems for Wet FGD

    Energy Technology Data Exchange (ETDEWEB)

    Steven A. Benson; Michael J. Holmes; Donald P. McCollor; Jill M. Mackenzie; Charlene R. Crocker; Lingbu Kong; Kevin C. Galbreath

    2007-03-31

    Mercury (Hg) control technologies were evaluated at Minnkota Power Cooperative's Milton R. Young (MRY) Station Unit 2, a 450-MW lignite-fired cyclone unit near Center, North Dakota, and TXU Energy's Monticello Steam Electric Station (MoSES) Unit 3, a 793-MW lignite--Powder River Basin (PRB) subbituminous coal-fired unit near Mt. Pleasant, Texas. A cold-side electrostatic precipitator (ESP) and wet flue gas desulfurization (FGD) scrubber are used at MRY and MoSES for controlling particulate and sulfur dioxide (SO{sub 2}) emissions, respectively. Several approaches for significantly and cost-effectively oxidizing elemental mercury (Hg{sup 0}) in lignite combustion flue gases, followed by capture in an ESP and/or FGD scrubber were evaluated. The project team involved in performing the technical aspects of the project included Babcock & Wilcox, the Energy & Environmental Research Center (EERC), the Electric Power Research Institute, and URS Corporation. Calcium bromide (CaBr{sub 2}), calcium chloride (CaCl{sub 2}), magnesium chloride (MgCl{sub 2}), and a proprietary sorbent enhancement additive (SEA), hereafter referred to as SEA2, were added to the lignite feeds to enhance Hg capture in the ESP and/or wet FGD. In addition, powdered activated carbon (PAC) was injected upstream of the ESP at MRY Unit 2. The work involved establishing Hg concentrations and removal rates across existing ESP and FGD units, determining costs associated with a given Hg removal efficiency, quantifying the balance-of-plant impacts of the control technologies, and facilitating technology commercialization. The primary project goal was to achieve ESP-FGD Hg removal efficiencies of {ge}55% at MRY and MoSES for about a month.

  1. Microbial responses and nitrous oxide emissions during wetting and drying of organically and conventionally managed soil under tomatoes

    Science.gov (United States)

    Burger, M.; Jackson, L.E.; Lundquist, E.J.; Louie, D.T.; Miller, R.L.; Rolston, D.E.; Scow, K.M.

    2005-01-01

    The types and amounts of carbon (C) and nitrogen (N) inputs, as well as irrigation management are likely to influence gaseous emissions and microbial ecology of agricultural soil. Carbon dioxide (CO2) and nitrous oxide (N2O) efflux, with and without acetylene inhibition, inorganic N, and microbial biomass C were measured after irrigation or simulated rainfall in two agricultural fields under tomatoes (Lycopersicon esculentum). The two fields, located in the California Central Valley, had either a history of high organic matter (OM) inputs ("organic" management) or one of low OM and inorganic fertilizer inputs ("conventional" management). In microcosms, where short-term microbial responses to wetting and drying were studied, the highest CO2 efflux took place at about 60% water-filled pore space (WFPS). At this moisture level, phospholipid fatty acids (PLFA) indicative of microbial nutrient availability were elevated and a PLFA stress indicator was depressed, suggesting peak microbial activity. The highest N 2O efflux in the organically managed soil (0.94 mg N2O-N m-2 h-1) occurred after manure and legume cover crop incorporation, and in the conventionally managed soil (2.12 mg N2O-N m-2 h-1) after inorganic N fertilizer inputs. Elevated N2O emissions occurred at a WFPS >60% and lasted <2 days after wetting, probably because the top layer (0-150 mm) of this silt loam soil dried quickly. Therefore, in these cropping systems, irrigation management might control the duration of elevated N2O efflux, even when C and inorganic N availability are high, whereas inorganic N concentrations should be kept low during times when soil moisture cannot be controlled.

  2. Study of wet etching thin films of indium tin oxide in oxalic acid by monitoring the resistance

    Energy Technology Data Exchange (ETDEWEB)

    Mammana, Suelene S., E-mail: ssmammana@abinfo.com.br [Brazilian Association for Informatics - ABINFO, Rua Deusdete Martins Gomes 163, CEP 13084-723, Campinas, SP (Brazil); Greatti, Alessandra; Luiz, Francis H.; Costa, Francisca I. da; Mammana, Alaide P. [Brazilian Association for Informatics - ABINFO, Rua Deusdete Martins Gomes 163, CEP 13084-723, Campinas, SP (Brazil); Calligaris, Guilherme A.; Cardoso, Lisandro P. [Institute of Physics Gleb Wataghin, State University of Campinas-UNICAMP, CEP 13083-859, Campinas, SP (Brazil); Mammana, Carlos I.Z.; Engelsen, Daniel den [Brazilian Association for Informatics - ABINFO, Rua Deusdete Martins Gomes 163, CEP 13084-723, Campinas, SP (Brazil)

    2014-09-30

    We describe a study on wet etching of thin films of indium tin oxide (ITO) using a simple method by monitoring the resistance of the thin film in aqueous solutions of oxalic acid and hydrochloric acid. Generally three different regimes can be distinguished during etching ITO in acids: (1) initial etching, which is slow, (2) a fast etching phase and (3) slow etching stage at the end. These regimes are explained in terms of a porosity–roughness model. This porosity model has been confirmed largely by X-ray reflection measurements at grazing incidence, roughness measurements and scanning electron microscopy (SEM). A reliable method for monitoring the resistance during etching has been developed. This method is based on a 2-strips measuring jig with a very low series contact resistance. The activation energy of the etch rate of ITO films was found to be 80 ± 5 kJ/mol for oxalic acid and 56 ± 5 kJ/mol for HCl. SEM analyses in the final stage of the etching process indicate an enrichment of Sn in the residual film material. These observations are explained in terms of preferential etching of In{sub 2}O{sub 3}. X-ray analyses showed that the density of the ITO film decreased by etching. By adding ferric chloride to the oxalic acid solution we could accelerate the etch rate substantially. - Highlights: • Etching of indium tin oxide thin films by monitoring the resistance. • Oxalic acid has 2–3 times lower etch rate than concentrated HCl. • The etch rate in oxalic acid can be accelerated substantially by adding FeCl{sub 3}. • The proposed etching model for indium tin oxide was confirmed by X-ray analysis and scanning electron microscopy. • Energy Dispersive X-ray Spectroscopy analyses showed preferential etching of In{sub 2}O{sub 3}, enriching the film with SnO{sub 2}.

  3. Chemical and toxicological evaluation of an emerging pollutant (enrofloxacin) by catalytic wet air oxidation and ozonation in aqueous solution.

    Science.gov (United States)

    Li, Yan; Zhang, Feifang; Liang, Xinmiao; Yediler, Ayfer

    2013-01-01

    This study evaluates the degradation efficiency of enrofloxacin (ENR) by catalytic wet air oxidation (CWAO) and ozonation. Results obtained by CWAO experiments show that 99.5% degradation, 37.0% chemical oxidation demand (COD) removal and 51.0% total organic carbon (TOC) conversion were obtained when 100 mol% FeCl(3) and 25 mol% NaNO(2) at 150 °C under 0.5 MPa oxygen pressure after 120 min are used. The degradation products are identified by liquid chromatography-tandem mass spectrometry (LC-MS/MS), gas chromatography-mass spectrometry (GC-MS) and ion chromatography (IC). The oxidation end products, F(-), NO(3)(-) and NH(4)(+) were determined by IC. The BOD(5)/COD ratio as a measure of the biodegradability of the parent compound increased from 0.01 to 0.12 after 120 min of reaction time, indicating an improved biodegradability of the parent compound. The inhibition of bioluminescence of the marine bacteria V. fischeri decreased from 43% to 12% demonstrating a loss in toxicity of ENR during CWAO. Ozonation of 0.2 mM ENR was carried out with an ozone concentration of 7.3 g m(-3) at pH 7. ENR decomposition with a degradation rate of 87% was obtained corresponding to the reaction time. Moderate changes in COD (18%) and TOC (17%) removal has been observed. The bioluminescence inhibition increased from 8% to 50%, due to the generation of toxic degradation products during ozonation. In comparison to the widely use of well developed method of ozonation CWAO exhibits better performance in terms of COD, TOC removals and generates less toxic products.

  4. Removal of salicylic acid on perovskite-type oxide LaFeO3 catalyst in catalytic wet air oxidation process.

    Science.gov (United States)

    Yang, Min; Xu, Aihua; Du, Hongzhang; Sun, Chenglin; Li, Can

    2007-01-02

    It has been found that salicylic acid can be removal effectively at the lower temperature of 140 degrees C on perovskite-type oxide LaFeO3 catalyst in the catalytic wet air oxidation (CWAO) process. Under the same condition, the activities for the CWAO of phenol, benzoic acid and sulfonic salicylic acid have been also investigated. The results indicated that, with compared to the very poor activities for phenol and benzoic acid, the activities for salicylic acid and sulfonic salicylic acid were very high, which are attributed to their same intramolecular H-bonding structures. With the role of hard acidity of intramolecular H-bonding, salicylic acid and sulfonic salicylic acid can be adsorbed effectively on the basic center of LaFeO3 catalyst and are easy to take place the total oxidation reaction. However, at temperatures higher than 140 degrees C, the intramolecular H-bonding structure of salicylic acid was destroyed and the activities at 160 and 180 degrees C decreased greatly, which confirms further the key role of intramolecular H-bonding in the CWAO. Moreover, the LaFeO3 catalyst also indicated a superior stability of activity and structure in CWAO of salicylic acid.

  5. Oxidative study of gabapentin by alkaline hexacyanoferrate(III) in room temperature in presence of catalytic amount of Ru(III) a mechanistic approach

    Science.gov (United States)

    Jose, Timy P.; Angadi, Mahantesh A.; Salunke, Manjalee S.; Tuwar, Suresh M.

    2008-12-01

    The kinetics of oxidation of gabapentin by hexacyanoferrate(III) in aqueous alkaline medium at a constant ionic strength of 0.5 mol dm -3 was studied spectrophotometrically. The reaction is of first order in [HCF(III)] and of less than unit order in [alkali]. The reaction rate is independent upon [gabapentin]. Effects of added products, ionic strength and dielectric constant of the reaction medium have been investigated. Oxidative product of gabapentin was identified. A suitable mechanism has been proposed. The reaction constants involved in the different steps of mechanism are calculated. The activation parameters of the mechanism are computed and discussed .

  6. Electrochemical quartz crystal microbalance study on Au-supported Pt adlayers for electrocatalytic oxidation of methanol in alkaline solution

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    Underpotential deposition(UPD) of Cu on an Au electrode followed by redox replacement reaction(RRR) of CuUPD with a Pt source(H2PtCl6 or K2PtCl4) yielded Au-supported Pt adlayers(for short,Pt(CuUPD-Pt4+)n/Au for H2PtCl6,or Pt(CuUPD-Pt2+)n/Au for K2PtCl4,where n denotes the number of UPD-redox replacement cycles).The electrochemical quartz crystal microbalance(EQCM) technique was used for the first time to quantitatively study the fabricated electrodes and estimate their mass-normalized specific electrocatalytic activity(SECA) for methanol oxidation in alkaline solution.In comparison with Pt(CuUPD-Pt2+)n/Au,Pt(CuUPD-Pt4+)n/Au exhibited a higher electrocatalytic activity,and the maximum SECA was obtained to be as high as 35.7 mA ?g?1 at Pt(CuUPD-Pt4+)3/Au.The layer-by-layer architecture of Pt atoms on Au is briefly discussed based on the EQCM-revealed redox replacement efficiency,and the calculated distribution percentages of bare Au sites agree with the experimental results deduced from the charge under the AuOx-reduction peaks.The EQCM is highly recommended as an efficient technique to quantitatively examine various electrode-supported catalyst adlayers,and the highly efficient catalyst adlayers of noble metals are promising in electrocatalysis relevant to biological,energy and environmental sciences and technologies.

  7. Ab Initio Quantum Mechanical Study of the Structure and Stability of the Alkaline Earth Metal Oxides and Peroxides

    Science.gov (United States)

    Königstein, Markus; Catlow, C. Richard A.

    1998-10-01

    We report a detailed computationally study of the stability of the alkaline earth metal peroxidesMO2(M=Ba, Sr, Ca, Mg, Be) with respect to decomposition into the corresponding oxidesMOand molecular oxygen using Hartree-Fock and density functional theory (DFT) techniques. A comparison between calculated and experimental binding energies indicates that the DFT method is most suitable for a correct description of the peroxide bond. The DFT reaction energies for the peroxide decompositionMO2→MO+{1}/{2}O2show that only BaO2and SrO2are thermodynamically stable compounds, while CaO2(in the calcium carbide structure), MgO2, and BeO2(in the pyrite structure) are energetically unstable with reaction energies of -24.7, -26.8, and -128.7kJ/mol, respectively, and are therefore unlikely to exist as pure compounds. The published calcium carbide structure for CaO2is probably incorrect, at least for pure calcium peroxide, since apart from the thermodynamical instability the compound is more stable in the pyrite structure by 25.5 kJ/mol. Our analysis suggests that the water and/or hydrogen peroxide content of experimentally prepared MgO2samples is necessary for the stabilization of the structure, while BeO2is clearly unstable under ambient conditions. We studied also the effect of the zero point energies and the entropies on the decomposition free energies and, for this purpose, performed atomistic lattice simulations based on interatomic potentials, which we derived from ourab initiodata; the results indicate a negligible effect of the zero point energies, while the entropy terms favor the decomposition reaction by ca. 20 kJ/mol at 298.15 K.

  8. Ab initio quantum mechanical study of the structure and stability of the alkaline earth metal oxides and peroxides

    Energy Technology Data Exchange (ETDEWEB)

    Koenigstein, M.; Catlow, C.R.A. [Royal Institution of Great Britain, London (United Kingdom). Davy Faraday Research Lab.

    1998-10-01

    The authors report a detailed computational study of the stability of the alkaline earth metal peroxides MO{sub 2} (M = Ba, Sr, Ca, Mg, Be) with respect to decomposition into the corresponding oxides Mo and molecular oxygen using Hartree-Fock and density functional theory (DFT) techniques. A comparison between calculated and experimental binding energies indicates that the DFT method is most suitable for a correct description of the peroxide bond. The DFT reaction energies for the peroxide decomposition MO{sub 2} {yields} MO + {1/2}O{sub 2} show that only BaO{sub 2} and SrO{sub 2} are thermodynamically stable compounds, while CaO{sub 2} (in the calcium carbide structure), MgO{sub 2}, and BeO{sub 2} (in the pyrite structure) are energetically unstable with reaction energies of {minus}24.7, {minus}26.8, and {minus}128.7 kJ/mol, respectively, and are therefore unlikely to exist as pure compounds. The published calcium carbide structure for CaO{sub 2} is probably incorrect, at least for pure calcium peroxide, since apart from the thermodynamical instability the compound is more stable in the pyrite structure by 25.5 kJ/mol. The analysis suggests that the water and/or hydrogen peroxide content of experimentally prepared MgO{sub 2} samples is necessary for the stabilization of the structure, while BeO{sub 2} is clearly unstable under ambient conditions. The authors studied also the effect of the zero point energies and the entropies on the decomposition free energies and, for this purpose, performed atomistic lattice simulations based on interatomic potentials, which they derived from their ab initio data; the results indicate a negligible effect of the zero point energies, while the entropy terms favor the decomposition reaction by ca. 20 kJ/mol at 298.15 K.

  9. Enhancement of dispersion and bonding of graphene-polymer through wet transfer of functionalized graphene oxide

    Directory of Open Access Journals (Sweden)

    F. Sharif

    2012-12-01

    Full Text Available Dispersion of nanomaterials in polymeric matrices plays an important role in determining the final properties of the composites. Dispersion in nano scale, and especially in single layers, provides best opportunity for bonding. In this study, we propose that by proper functionalization and mixing strategy of graphene its dispersion, and bonding to the polymeric matrix can be improved. We then apply this strategy to graphene-epoxy system by amino functionalization of graphene oxide (GO. The process included two phase extraction, and resulted in better dispersion and higher loading of graphene in epoxy matrix. Rheological evaluation of different graphene-epoxy dispersions showed a rheological percolation threshold of 0.2 vol% which is an indication of highly dispersed nanosheets. Observation of the samples by optical microscopy, scanning electron microscopy (SEM, and atomic force microscopy (AFM, showed dispersion homogeneity of the sheets at micro and nano scales. Study of graphene-epoxy composites showed good bonding between graphene and epoxy. Mechanical properties of the samples were consistent with theoretical predictions for ideal composites indicating molecular level dispersion and good bonding between nanosheets and epoxy matrix.

  10. Wet oxidation of glycerol into fine organic acids: catalyst selection and kinetic evaluation

    Directory of Open Access Journals (Sweden)

    J. E. N. Brainer

    2014-12-01

    Full Text Available The liquid phase oxidation of glycerol was performed producing fine organic acids. Catalysts based on Pt, Pd and Bi supported on activated carbon were employed to perform the conversion of glycerol into organic acids at 313 K, 323 K and 333 K, under atmospheric pressure (1.0 bar, in a mechanically agitated slurry reactor (MASR. The experimental results indicated glycerol conversions of 98% with production of glyceric, tartronic and glycolic acids, and dihydroxyacetone. A yield of glyceric acid of 69.8%, and a selectivity of this compound of 70.6% were reached after 4 h of operation. Surface mechanisms were proposed and rate equations were formulated to represent the kinetic behavior of the process. Selective formation of glyceric acid was observed, and the kinetic parameter values indicated the lowest activation energy (38.5 kJ/mol for its production reaction step, and the highest value of the adsorption equilibrium constant of the reactant glycerol (10-4 dm³/mol.

  11. Treatment of municipal landfill leachate by catalytic wet air oxidation: Assessment of the role of operating parameters by factorial design.

    Science.gov (United States)

    Anglada, Angela; Urtiaga, Ane; Ortiz, Inmaculada; Mantzavinos, Dionissios; Diamadopoulos, Evan

    2011-08-01

    The wet air oxidation (WAO) of municipal landfill leachate catalyzed by cupric ions and promoted by hydrogen peroxide was investigated. The effect of operating conditions such as WAO treatment time (15-30min), temperature (160-200°C), Cu(2+) concentration (250-750mgL(-1)) and H(2)O(2) concentration (0-1500mgL(-1)) on chemical oxygen demand (COD) removal was investigated by factorial design considering a two-stage, sequential process comprising the heating-up of the reactor and the actual WAO. The leachate, at an initial COD of 4920mgL(-1), was acidified to pH 3 leading to 31% COD decrease presumably due to the coagulation/precipitation of colloidal and other organic matter. During the 45min long heating-up period of the WAO reactor under an inert atmosphere, COD removal values up to 35% (based on the initial COD value) were recorded as a result of the catalytic decomposition of H(2)O(2) to reactive hydroxyl radicals. WAO at 2.5MPa oxygen partial pressure advanced treatment further; for example, 22min of oxidation at 200°C, 250mgL(-1) Cu(2+) and 0-1500mgL(-1) H(2)O(2) resulted in an overall (i.e. including acidification and heating-up) COD reduction of 78%. Amongst the operating variables in question, temperature had the strongest influence on both the heating-up and WAO stages, while H(2)O(2) concentration strongly affected the former and reaction time the latter. Nonetheless, the effects of temperature and H(2)O(2) concentration were found to depend on the concentration levels of catalyst as suggested by the significance of their 3rd order interaction term.

  12. Preparation and Photocatalytic Activity of Potassium- Incorporated Titanium Oxide Nanostructures Produced by the Wet Corrosion Process Using Various Titanium Alloys

    Directory of Open Access Journals (Sweden)

    So Yoon Lee

    2015-08-01

    Full Text Available Nanostructured potassium-incorporated Ti-based oxides have attracted much attention because the incorporated potassium can influence their structural and physico-chemical properties. With the aim of tuning the structural and physical properties, we have demonstrated the wet corrosion process (WCP as a simple method for nanostructure fabrication using various Ti-based materials, namely Ti–6Al–4V alloy (TAV, Ti–Ni (TN alloy and pure Ti, which have 90%, 50% and 100% initial Ti content, respectively. We have systematically investigated the relationship between the Ti content in the initial metal and the precise condition of WCP to control the structural and physical properties of the resulting nanostructures. The WCP treatment involved various concentrations of KOH solutions. The precise conditions for producing K-incorporated nanostructured titanium oxide films (nTOFs were strongly dependent on the Ti content of the initial metal. Ti and TAV yielded one-dimensional nanowires of K-incorporated nTOFs after treatment with 10 mol/L-KOH solution, whereas TN required a higher concentration (20 mol/L-KOH solution to produce comparable nanostructures. The obtained nanostructures revealed a blue-shift in UV absorption spectra due to the quantum confinement effects. A significant enhancement of the photocatalytic activity was observed via the chromomeric change and the intermediate formation of methylene blue molecules under UV irradiation. This study demonstrates the WCP as a simple, versatile and scalable method for the production of nanostructured K-incorporated nTOFs to be used as high-performance photocatalysts for environmental and energy applications.

  13. Degradation of cellulose at the wet-dry interface. II. Study of oxidation reactions and effect of antioxidants.

    Science.gov (United States)

    Jeong, Myung-Joon; Dupont, Anne-Laurence; de la Rie, E René

    2014-01-30

    To better understand the degradation of cellulose upon the formation of a tideline at the wet-dry interface when paper is suspended in water, the production of chemical species involved in oxidation reactions was studied. The quantitation of hydroperoxides and hydroxyl radicals was carried out in reverse phase chromatography using triphenylphosphine and terephthalic acid, respectively, as chemical probes. Both reactive oxygen species were found in the tideline immediately after its formation, in the range of micromoles and nanomoles per gram of paper, respectively. The results indicate that hydroxyl radicals form for the most part in paper before the tideline experiment, whereas hydroperoxides appear to be produced primarily during tideline formation. Iron sulfate impregnation of the paper raised the production of hydroperoxides. After hygrothermal aging in sealed vials the hydroxyl radical content in paper increased significantly. When aged together in the same vial, tideline samples strongly influenced the degradation of samples from other areas of the paper (multi-sample aging). Different types of antioxidants were added to the paper before the tideline experiment to investigate their effect on the oxidation reactions taking place. In samples treated with iron sulfate or artificially aged, the addition of Irgafos 168 (tris(2,4-ditert-butylphenyl) phosphate) and Tinuvin 292 (bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate) reduced the concentration of hydroperoxides and hydroxyl radicals, respectively. Tinuvin 292 was also found to considerably lower the rate of cellulose chain scission reactions during hygrothermal aging of the paper.

  14. Active carbon-ceramic sphere as support of ruthenium catalysts for catalytic wet air oxidation (CWAO) of resin effluent.

    Science.gov (United States)

    Liu, Wei-Min; Hu, Yi-Qiang; Tu, Shan-Tung

    2010-07-15

    Active carbon-ceramic sphere as support of ruthenium catalysts were evaluated through the catalytic wet air oxidation (CWAO) of resin effluent in a packed-bed reactor. Active carbon-ceramic sphere and ruthenium catalysts were characterized by N(2) adsorption and chemisorption measurements. BET surface area and total pore volume of active carbon (AC) in the active carbon-ceramic sphere increase with increasing KOH-to-carbon ratio, and AC in the sample KC-120 possesses values as high as 1100 m(2) g(-1) and 0.69 cm(3) g(-1) (carbon percentage: 4.73 wt.%), especially. Active carbon-ceramic sphere supported ruthenium catalysts were prepared using the RuCl(3) solution impregnation onto these supports, the ruthenium loading was fixed at 1-5 wt.% of AC in the support. The catalytic activity varies according to the following order: Ru/KC-120>Ru/KC-80>Ru/KC-60>KC-120>without catalysts. It is found that the 3 wt.% Ru/KC-120 catalyst displays highest stability in the CWAO of resin effluent during 30 days. Chemical oxygen demand (COD) and phenol removal were about 92% and 96%, respectively at the reaction temperature of 200 degrees C, oxygen pressure of 1.5 MPa, the water flow rate of 0.75 L h(-1) and the oxygen flow rate of 13.5 L h(-1).

  15. Al 2O 3 supported Ru catalysts prepared by thermolysis of Ru 3(CO) 12 for catalytic wet air oxidation

    Science.gov (United States)

    Yu, Chaoying; Zhao, Peiqing; Chen, Gexin; Hu, Bin

    2011-06-01

    Low loading catalysts Ru/γ-Al 2O 3 and Ru-Ce/γ-Al 2O 3 were prepared by thermolysis of Ru 3(CO) 12 on γ-Al 2O 3. The catalysts were characterized by XPS, XRD and SEM. Two new Ru species (Ru A and Ru B) were detected during the Ru 3(CO) 12 decomposition process due to chemical interaction with the active OH groups on the surface of Al 2O 3 support, and the reduction of them can lead to more dispersed metallic phases. The sample was completely decomposed at 673 K in H 2, and RuO 2 was formed with minor amounts of Ru 0. When the temperature was increased to 773 K to heat the sample, the ratio of Ru 0 to RuO 2 increased. However, after the addition of CeO 2, only RuO 2 was detected on surface. The catalysts exhibited high activities in Catalytic Wet Air Oxidation (CWAO) of different organic compounds at high concentration such as isopropyl alcohol, phenol, acetic acids and N,N-dimethylformamide, which is attributed to the better dispersion of Ru particles and the addition of CeO 2 further enhanced number of effectively active sites on the cluster-derived catalyst surface.

  16. Low-pressure catalytic wet-air oxidation of a high-strength industrial wastewater using Fenton's reagent.

    Science.gov (United States)

    Biçaksiz, Zeliha; Aytimur, Gülin; Atalay, Süheyda

    2008-06-01

    Wastewater from the Afyon Alkaloids Factory (Afyon, Turkey) was subjected to low-pressure catalytic wet-air oxidation (CWAO) using Fenton's reagent, and the optimal reaction conditions were investigated. The CWAO using Fenton's reagent was applied to the factory effluent, diluted factory effluent, and aerobically pretreated wastewater. To find the optimum quantities of reagents, ferrous iron (Fe(+2))-to-substrate ratios of 1:10, 1:25, and 1:50 and hydrogen peroxide (H2O2)-to-Fe(+2) ratios of 1, 5, and 10 were investigated, and the treatment was carried out at different temperatures. High chemical oxygen demand (COD) removals were obtained at 50 degrees C, with the Fe(+2)-to-substrate ratio range between 1:10 and 1:25. The change in H2O2-to-Fe(+2) ratios did not cause any considerable effect. Also, the percentages of COD removals were nearly the same, so the ratio H2O2:Fe(+2):1 is recommended. Aerobic pretreatment seems to be effective. On the other hand, no enhancement was observed in the case of the diluted wastewater.

  17. Resting Study of Tracer Experiment on Catalytic Wet Oxidation Reactor under Micro-gravity and Earth Gravity Conditions

    Institute of Scientific and Technical Information of China (English)

    YANG Ji; JIA Jin-ping

    2005-01-01

    The International Space Station(ISS) employs catalytic wet oxidation carried out in a Volatile Reactor Assembly (VRA) for water recycling. Previous earth gravity experiments show that the VRA is very effective at removing polar,low molecular weight organics. To compare the reactor performance under micro-gravity and Earth gravity conditions,a tracer study was performed on a space shuttle in 1999 by using 0. 2% potassium carbonate as the chemical tracer.In this paper, the experimental data were analyzed and it is indicated that the reactor can be considered as a plug flow one under both micro-gravity and earth gravity experimental conditions. It has also been proved that dispersion is not important in the VRA reactor under the experimental conditions. Tracer retardation was observed in the experiments and it is most likely caused by catalyst adsorption. It is concluded that the following reasons may also have influence on the retardation of mean residence time: (1) the liquid can be held by appurtenances, which will retard the mean residence time; (2) the pores can hold the tracer, which can also retard the mean residence time.

  18. Evaluation of wet air oxidation variables for removal of organophosphorus pesticide malathion using Box-Behnken design.

    Science.gov (United States)

    Isgoren, Melike; Gengec, Erhan; Veli, Sevil

    2017-02-01

    This paper deals with finding optimum reaction conditions for wet air oxidation (WAO) of malathion aqueous solution, by Response Surface Methodology. Reaction conditions, which affect the removal efficiencies most during the non-catalytic WAO system, are: temperature (60-120 °C), applied pressure (20-40 bar), the pH value (3-7), and reaction time (0-120 min). Those were chosen as independent parameters of the model. The interactions between parameters were evaluated by Box-Behnken and the quadratic model fitted very well with the experimental data (29 runs). A higher value of R(2) and adjusted R(2) (>0.91) demonstrated that the model could explain the results successfully. As a result, optimum removal efficiency (97.8%) was obtained at pH 5, 20 bars of pressure, 116 °C, and 96 min. These results showed that Box-Behnken is a suitable design to optimize operating conditions and removal efficiency for non-catalytic WAO process. The EC20 value of raw wastewater was measured as 35.40% for malathion (20 mg/L). After the treatment, no toxicity was observed at the optimum reaction conditions. The results show that the WAO is an efficient treatment system for malathion degradation and has the ability of converting malathion to the non-toxic forms.

  19. Wet air oxidation of resorcinol as a model treatment for refractory organics in wastewaters from the wood processing industry.

    Science.gov (United States)

    Weber, Bernd; Chavez, Alma; Morales-Mejia, Julio; Eichenauer, Sabrina; Stadlbauer, Ernst A; Almanza, Rafael

    2015-09-15

    Wastewater treatment systems are important tools to enhance sustainability in terms of reducing environmental impact and complying with sanitary requirements. This work addresses the wet air oxidation (WAO) process for pre-treatment of phenolic wastewater effluents. The aim was to increase biodegradability prior to a subsequent anaerobic stage. In WAO laboratory experiments using a micro-autoclave, the model compound resorcinol was degraded under different oxygen availability regims within the temperature range 150 °C-270 °C. The activation energy was determined to be 51.5 kJ/mol. Analysis of the products revealed that after 3 h of reaction at 230 °C, 97.5% degradation of resorcinol was achieved. At 250 °C and the same reaction time complete removal of resorcinol was observed. In this case the total organic carbon content was reduced down to 29%, from 118.0 mg/L down to 34.4 mg/L. Under these process conditions, the pollutant was only partially mineralized and the ratio of the biological oxygen demand relative to the chemical oxygen demand, which is 0.07 for resorcinol, was increased to a value exceeding 0.5. The main by-product acetic acid, which is a preferred compound for methanogenic bacteria, was found to account for 33% of the total organic carbon.

  20. Energy balance and cost-benefit analysis of biogas production from perennial energy crops pretreated by wet oxidation.

    Science.gov (United States)

    Uellendahl, H; Wang, G; Møller, H B; Jørgensen, U; Skiadas, I V; Gavala, H N; Ahring, B K

    2008-01-01

    Perennial crops need far less energy to plant, require less fertilizer and pesticides, and show a lower negative environmental impact compared with annual crops like for example corn. This makes the cultivation of perennial crops as energy crops more sustainable than the use of annual crops. The conversion into biogas in anaerobic digestion plants shows however much lower specific methane yields for the raw perennial crops like miscanthus and willow due to their lignocellulosic structure. Without pretreatment the net energy gain is therefore lower for the perennials than for corn. When applying wet oxidation to the perennial crops, however, the specific methane yield increases significantly and the ratio of energy output to input and of costs to benefit for the whole chain of biomass supply and conversion into biogas becomes higher than for corn. This will make the use of perennial crops as energy crops competitive to the use of corn and this combination will make the production of biogas from energy crops more sustainable.

  1. Research on Synergy of Combining Electrochemical Oxidation and Catalytic Wet Oxidation%电场效应与催化湿式氧化协同作用研究

    Institute of Scientific and Technical Information of China (English)

    王华; 李光明; 张芳; 黄菊文

    2009-01-01

    A new catalytic wet oxidation fixed-bed reactor combined with three-dimensional electric-field was developed to investigate catalytic wet oxidation, electrochemical oxidation and electroassisted catalytic wet oxidation of the solution containing phenol in the presence of a catalyst Mn-Sn-Sb-3/γ-Al_2O_3 . Good eleetroassisted catalytic wet oxidation efficiency was obtained in the setup for the combination system even at mild conditions ( T = 130℃, po_2 =1.0 MPa) that the phenol conversion and TOC reduction were up to 94.0% and 88.4% after 27 min treatment, respectively. The result also shows that the rate constants of electroassisted catalytic wet oxidation are much higher than that of not only both catalytic wet oxidation and electrochemical oxidation process alone but also additive efficiencies of catalytic wet oxidation and electrochemical oxidation processes, which indicates an apparent synergetic effect between CWO and ECO processes.%在自行研制开发的一套固定床和复合三维电场一体化连续式催化湿式氧化反应器中,采用浸渍法制备的Mn-Sn-Sb-3/γAl_2O_3催化剂,实验研究了苯酚催化湿式氧化、电催化氧化以及电场效应下的催化湿式氧化过程的行为.结果表明,一体化反应器在较低反应温度(T=130℃)和氧分压(Po_2=1.0 MPa)下即可获得相当满意的处理效果,空时仅为27min时苯酚和TOC的去除率就分别可达到94.0%和88.4%.电场效应下的催化湿式氧化协同降解苯酚的反应速率常数大于单独电催化或催化湿式氧化降解苯酚的反应速率常数,而且还大大超过两者之和,电催化氧化对催化湿式氧化工艺存在明显的协同增效作用.

  2. Catalytic Oxidative Conversion from Naphthol to 2-Hydroxy-1, 4-naphthoquinone over Iron Porphyrin Catalysts by Molecular Oxygen in an Alkaline 2-Propanol Solution

    Institute of Scientific and Technical Information of China (English)

    YANG Ke-er; TONG Shan-ling; YAN Yan; KANG En-hua; XIAO Feng-shou; LI Qing; CHANG Xin; FANG Chi-guang

    2005-01-01

    In an alkaline 2-propanol solution with 5,10,15,20-tetra(4-methoxyl phenyl) porphyrin iron chloride(TOMPPFeCl) as a catalyst and oxygen as a cheap green oxidant, 2-naphthol was conversed to 2-hydroxy-1,4-naphthoquinone(HNQ) with a yield of 62.17% and a selectivity of 100%, and the conversion number of TMOPPFeCl catalyst was 8.32/min. The catalytic oxidation products were characterized by means of UV-Vis, IR, GC-MS, 1H NMR and melting point determination. In this catalytic oxidation, the catalytic activity of TMOPPFeCl was researched in detail and the reacting conditions were optimized. A possible reaction mechanism is summarized based on in situ EPR determination.

  3. Reuse of a dyehouse effluent after being treated with the combined catalytic wet peroxide oxidation process and the aerated constructed wetland.

    Science.gov (United States)

    Lee, D K; Kim, S C; Yoon, J H

    2007-01-01

    A catalytic wet peroxide oxidation process was combined with the aerated constructed wetland in order to treat the raw dyehouse wastewater to in acceptable level for reuse as washing process water. More than 90% of BOD and CODs could be removed with the wet peroxide oxidation reactor and the remaining pollutants in the treated water were transformed into biodegradable ones which could have been successfully treated at the following aerated constructed wetland. The highest values of BOD5, CODMn, CODCr, SS and T-N in the treated water were 1.6, 1.8, 2.1, 0.5 and 12.8 mg/L, respectively. These values were low enough for the treated water to be reused at the washing process.

  4. Ethanol electro-oxidation in alkaline medium using Pd/MWCNT and PdAuSn/MWCNT electrocatalysts prepared by electron beam irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Geraldes, Adriana Napoleao; Silva, Dionisio Furtunato da; Andrade e Silva, Leonardo Gondin de; Spinace, Estevam Vitorio; Oliveira Neto, Almir, E-mail: drinager@ig.com.br, E-mail: dfsilva@ipen.br [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil); Santos, Mauro Coelho dos [Universidade Federal do ABC (LEMN/CCNH/UFABC), Santo Andre, SP (Brazil)

    2015-07-01

    Environmental problems and the world growing demand for energy has mobilized the scientific community in finding of clean and renewable energy sources. In this context, fuel cells appear as appropriate technology for generating electricity through alcohols electro-oxidation. Multi Wall Carbon Nanotubes (MWCNT)-supported Pd and trimetallic PdAuSn (Pd:Au:Sn 50:10:40 atomic ratio) electrocatalysts were prepared using electron beam irradiation. The obtained materials were characterized by VC, Chronoamperometry, EDX, TEM and XRD. The catalytic activities of electrocatalysts toward ethanol electro-oxidation were evaluated in alkaline medium in a single alkaline direct ethanol fuel cell (ADEFC) in a range temperature 60 to 90 deg C. The best performances were obtained at 85 deg C: 33 mW.cm{sup -2} and 31 mW.cm{sup -2} for Pd/ MWCNT and PdAuSn/MWCNT electrocatalysts, respectively. X-ray diffractograms of electrocatalysts showed the presence of Pd-rich (fcc) and Au-rich (fcc) phases. Cyclic voltammetry and chronoamperometry experiments showed that PdAuSn/MWCNT electrocatalyst demonstrated similar activity toward ethanol electro-oxidation at room temperature, compared to electrocatalyst Pd/MWCNT. (author)

  5. FeS anchored reduced graphene oxide nanosheets as advanced anode material with superior high-rate performance for alkaline secondary batteries

    Science.gov (United States)

    Shangguan, Enbo; Guo, Litan; Li, Fei; Wang, Qin; Li, Jing; Li, Quanmin; Chang, Zhaorong; Yuan, Xiao-Zi

    2016-09-01

    A new nanocomposite formulation of the iron-based anode for alkaline secondary batteries is proposed. For the first time, FeS nanoparticles anchored on reduced graphene oxide (RGO) nanosheets are synthesized via a facile, environmentally friendly direct-precipitation approach. In this nanocomposite, FeS nanoparticles are anchored uniformly and tightly on the surface of RGO nanosheets. As an alkaline battery anode, the FeS@RGO electrode delivers a superior high-rate charge/discharge capability and outstanding cycling stability, even at a condition without any conductive additives and a high electrode loading of ∼40 mg cm-2. At high charge/discharge rates of 5C, 10C and 20C (6000 mA g-1), the FeS@RGO electrode presents a specific capacity of ∼288, 258 and 220 mAh g-1, respectively. Moreover, the FeS@RGO electrode exhibits an admirable long cycling stability with a superior capacity retention of 87.6% for 300 cycles at a charge/discharge rate of 2C. The excellent electrochemical properties of the FeS@RGO electrode can be stemmed from the high specific surface area, peculiar electric conductivity and robust sheet-anchored structure of the FeS@RGO nanocomposite. By virtue of its superior fast charge/discharge properties, the FeS@RGO nanocomposite is suitable as an advanced anode material for high-performance alkaline secondary batteries.

  6. Catalytic wet oxidation of dyehouse effluents with Cu/Al{sub 2}O{sub 3} and Al-Cu pillared clays

    Energy Technology Data Exchange (ETDEWEB)

    Lee, D.K.; Kim, S.C.; Kim, D.S.; Lee, G.S.; Yoon, S.B. [Dept. of Chemical Engineering/Environmental Protection, Environment and Regional Development Inst., Gyeongsang National Univ., Gyeongnam (Korea)

    2003-07-01

    Catalytic wet oxidation of real dyehouse effluents was performed in a batch reactor and a continuous flow pilot plant scale reactor by using Cu/Al{sub 2}O{sub 3} and Al-Cu-PILC catalysts. Hydrogen peroxide was used as the oxidant. The removal of TOC and color was strongly related to the consumption of H{sub 2}O{sub 2} and the subsequent formation of HO-. Copper components in the catalysts, especially in the Al-Cu-PILCs, showed successful activity toward complete removal of TOC and color. In addition the Al-Cu-PILC catalysts were extremely stable against copper leaching. (orig.)

  7. One-pot wet-chemical co-reduction synthesis of bimetallic gold-platinum nanochains supported on reduced graphene oxide with enhanced electrocatalytic activity

    Science.gov (United States)

    Chen, De-Jun; Zhang, Qian-Li; Feng, Jin-Xia; Ju, Ke-Jian; Wang, Ai-Jun; Wei, Jie; Feng, Jiu-Ju

    2015-08-01

    In this work, a simple, rapid and facile one-pot wet-chemical co-reduction method is developed for synthesis of bimetallic Au-Pt alloyed nanochains supported on reduced graphene oxide (Au-Pt NCs/RGO), in which caffeine is acted as a capping agent and a structure-directing agent, while no any seed, template, surfactant or polymer involved. The as-prepared nanocomposites display enlarged electrochemical active surface area, significantly enhanced catalytic activity and better stability for methanol and ethylene glycol oxidation, compared with commercial Pt-C (Pt 50 wt%), PtRu-C (Pt 30 wt% and Ru 15 wt%) and Pt black.

  8. Treatment of ammonia by catalytic wet oxidation process over platinum-rhodium bimetallic catalyst in a trickle-bed reactor: effect of pH.

    Science.gov (United States)

    Hung, Chang-Mao; Lin, Wei-Bang; Ho, Ching-Lin; Shen, Yun-Hwei; Hsia, Shao-Yi

    2010-08-01

    This work adopted aqueous solutions of ammonia for use in catalytic liquid-phase reduction in a trickle-bed reactor with a platinum-rhodium bimetallic catalyst, prepared by the co-precipitation of chloroplatinic acid (H2PtCl6) and rhodium nitrate [Rh(NO3)3]. The experimental results demonstrated that a minimal amount of ammonia was removed from the solution by wet oxidation in the absence of any catalyst, while approximately 97.0% of the ammonia was removed by wet oxidation over the platinum-rhodium bimetallic catalyst at 230 degrees C with an oxygen partial pressure of 2.0 MPa. The oxidation of ammonia has been studied as a function of pH, and the main reaction products were determined. A synergistic effect is manifest in the platinum-rhodium bimetallic structure, in which the material has the greatest capacity to reduce ammonia. The reaction pathway linked the oxidizing ammonia to nitric oxide, nitrogen, and water.

  9. Protection effect of a SiO2 layer in Al0.85Ga0.15As wet oxidation

    Institute of Scientific and Technical Information of China (English)

    Zhou Wenfei; Ye Xiaoling; Xu Bo; Zhang Shizhu; Wang Zhanguo

    2012-01-01

    The Al0.85Ga0.15As layers buried below the GaAs core layer with and without the SiO2 layer were successfully oxidized in a wet ambient environment.The experimental results show that the SiO2 layer has little impact on the lateral-wet-oxidation rate of the Al0.85Ga0.15As layer.The contrast of the SEM image of the oxidized regions and the absence of As-related Raman peaks for samples with the SiO2 layer arise from the removal of As ingredients with the largest atomic number,which leads to improvements in the thermal stability of the oxidized layer.The PL intensities of samples with the SiO2 layer are much stronger than those without the SiO2 layer.The PL emission peak is almost unshifted with a slight broadening under the protection of the SiO2 layer.This is attributed to the SiO2 layer preventing oxidation damage to the GaAs capping layer.

  10. Application of a wet oxidation method for the quantification of ³H and ¹⁴C in low-level radwastes.

    Science.gov (United States)

    Ahn, H J; Song, B C; Sohn, S C; Lee, M H; Song, K; Jee, K Y

    2013-11-01

    Wet oxidation methods are utilized to separate and quantify (3)H and (14)C radionuclides in inorganic and organic radwastes generated at nuclear facilities. Because (3)H and (14)C are pure beta emitters with half-lives of 12.3 and 5,730 years, respectively, these radionuclides should be chemically separated from other radionuclides present in radwastes for accurate quantification. In particular, a collection technique for (14)C radionuclide in radwastes is needed because it is converted into (14)CO2 gas by an oxidation reaction. To confirm the recoveries of (3)H and (14)C, various standard radioactive sources were used to verify the proposed method. Because the majority of (3)H radionuclides are distributed in tritiated water (HTO), only tritiated water was used as a standard for (3)H radionuclides. Additionally, (14)C-labeled methanol ((14)CH3OH), lauric acid ((14)CH3(CH2)10COOH), sodium bicarbonate (NaH(14)CO3), and toluene (C6H5(14)CH3) were used as (14)C standards. The compounds were oxidized with chemical oxidants and then separated. The individual species were mixed with a scintillation cocktail and counted using a liquid scintillation counter. The recoveries of (14)C and (3)H were 82-97% and 98%, respectively. The wet oxidation method will be applied to RI wastes for clearance.

  11. Post-treatment of biologically treated wastewater containing organic contaminants using a sequence of H2O2 based advanced oxidation processes: photolysis and catalytic wet oxidation.

    Science.gov (United States)

    Rueda-Márquez, J J; Sillanpää, M; Pocostales, P; Acevedo, A; Manzano, M A

    2015-03-15

    In this paper the feasibility of a multi-barrier treatment (MBT) for the regeneration of synthetic industrial wastewater (SIWW) was evaluated. Industrial pollutants (orange II, phenol, 4-chlorophenol and phenanthrene) were added to the effluent of municipal wastewater treatment plant. The proposed MBT begins with a microfiltration membrane pretreatment (MF), followed by hydrogen peroxide photolysis (H2O2/UVC) and finishing, as a polishing step, with catalytic wet peroxide oxidation (CWPO) using granular activated carbon (GAC) at ambient conditions. During the microfiltration step (0.7 μm) the decrease of suspended solids concentration, turbidity and Escherichia coli in treated water were 88, 94 and 99%, respectively. Also, the effluent's transmittance (254 nm) was increased by 14.7%. Removal of more than 99.9% of all added pollutants, mineralization of 63% of organic compounds and complete disinfection of total coliforms were reached during the H2O2/UVC treatment step (H2O2:TOC w/w ratio = 5 and an UVC average dose accumulated by wastewater 8.80 WUVC s cm(-2)). The power and efficiency of the lamp, the water transmittance and photoreactor geometry are taken into account and a new equation to estimate the accumulated dose in water is suggested. Remaining organic pollutants with a higher oxidation state of carbon atoms (+0.47) and toxic concentration of residual H2O2 were present in the effluent of the H2O2/UVC process. After 2.3 min of contact time with GAC at CWPO step, 90 and 100% of total organic carbon and residual H2O2 were removed, respectively. Also, the wastewater toxicity was studied using Vibrio fischeri and Sparus aurata larvae. The MBT operational and maintenance costs (O&M) was estimated to be 0.59 € m(-3).

  12. Structure-guided systems-level engineering of oxidation-prone methionine residues in catalytic domain of an alkaline α-amylase from Alkalimonas amylolytica for significant improvement of both oxidative stability and catalytic efficiency.

    Directory of Open Access Journals (Sweden)

    Haiquan Yang

    Full Text Available High oxidative stability and catalytic efficiency are required for the alkaline α-amylases to keep the enzymatic performance under the harsh conditions in detergent industries. In this work, we attempted to significantly improve both the oxidative stability and catalytic efficiency of an alkaline α-amylase from Alkalimonas amylolytica by engineering the five oxidation-prone methionine residues around the catalytic domain via a systematic approach. Specifically, based on the tertiary structure analysis, five methionines (Met 145, Met 214, Met 229, Met 247 and Met 317 were individually substituted with oxidation-resistant threonine, isoleucine and alaline, respectively. Among the created 15 mutants, 7 mutants M145A, M145I, M214A, M229A, M229T, M247T and M317I showed significantly enhanced oxidative stability or catalytic efficiency. In previous work, we found that the replacement of M247 with leucine could significantly improve the oxidative stability. Thus, these 8 positive mutants (M145A, M145I, M214A, M229A, M229T, M247T, M247L and M317I were used to conduct the second round of combinational mutations. Among the constructed 85 mutants (25 two-point mutants, 36 three-point mutants, 16 four-point mutants and 8 five-point mutants, the mutant M145I-214A-229T-247T-317I showed a 5.4-fold increase in oxidative stability and a 3.0-fold increase in catalytic efficiency. Interestingly, the specific activity, alkaline stability and thermal stability of this mutant were also increased. The increase of salt bridge and hydrogen bonds around the catalytic domain contributed to the significantly improved catalytic efficiency and stability, as revealed by the three-dimensional structure model of wild-type alkaline α-amylase and its mutant M145I-214A-229T-247T-317I. With the significantly improved oxidative stability and catalytic efficiency, the mutant M145I-214A-229T-247T-317I has a great potential as a detergent additive, and this structure-guided systems

  13. Structure-guided systems-level engineering of oxidation-prone methionine residues in catalytic domain of an alkaline α-amylase from Alkalimonas amylolytica for significant improvement of both oxidative stability and catalytic efficiency.

    Science.gov (United States)

    Yang, Haiquan; Liu, Long; Shin, Hyun-dong; Li, Jianghua; Du, Guocheng; Chen, Jian

    2013-01-01

    High oxidative stability and catalytic efficiency are required for the alkaline α-amylases to keep the enzymatic performance under the harsh conditions in detergent industries. In this work, we attempted to significantly improve both the oxidative stability and catalytic efficiency of an alkaline α-amylase from Alkalimonas amylolytica by engineering the five oxidation-prone methionine residues around the catalytic domain via a systematic approach. Specifically, based on the tertiary structure analysis, five methionines (Met 145, Met 214, Met 229, Met 247 and Met 317) were individually substituted with oxidation-resistant threonine, isoleucine and alaline, respectively. Among the created 15 mutants, 7 mutants M145A, M145I, M214A, M229A, M229T, M247T and M317I showed significantly enhanced oxidative stability or catalytic efficiency. In previous work, we found that the replacement of M247 with leucine could significantly improve the oxidative stability. Thus, these 8 positive mutants (M145A, M145I, M214A, M229A, M229T, M247T, M247L and M317I) were used to conduct the second round of combinational mutations. Among the constructed 85 mutants (25 two-point mutants, 36 three-point mutants, 16 four-point mutants and 8 five-point mutants), the mutant M145I-214A-229T-247T-317I showed a 5.4-fold increase in oxidative stability and a 3.0-fold increase in catalytic efficiency. Interestingly, the specific activity, alkaline stability and thermal stability of this mutant were also increased. The increase of salt bridge and hydrogen bonds around the catalytic domain contributed to the significantly improved catalytic efficiency and stability, as revealed by the three-dimensional structure model of wild-type alkaline α-amylase and its mutant M145I-214A-229T-247T-317I. With the significantly improved oxidative stability and catalytic efficiency, the mutant M145I-214A-229T-247T-317I has a great potential as a detergent additive, and this structure-guided systems engineering

  14. A study of substituent effect on the oxidative strengths of sodium salts of N-bromo-arylsulphonamides: Kinetics and mechanism of oxidation of D-fructose and D-glucose in alkaline medium

    Indian Academy of Sciences (India)

    K M Usha; B Thimme Gowda

    2006-07-01

    N-Bromo-arylsulphonamides of different oxidizing strengths are used for studying the kinetics of oxidation of D-fructose and D-glucose in aqueous alkaline medium. The results are analysed and compared with those from the sodium salts of N-bromo-benzenesulphonamide and N-bromo-4-methylbenzenesulphonamide. The reactions show zero-order kinetics in [oxidant], fractional order in [Fru/Glu] and nearly first order in [OH-]. Rates of oxidation of fructose are higher than those for glucose with the same oxidant. Similarly, values for glucose oxidations are higher than those for fructose. The results are explained by a suitable mechanism and the related rate law is deduced. The effective oxidising species in the reactions of N-bromo-arylsulphonamides is Br+. The oxidative strengths of the latter therefore depend on the ease with which Br+ is released from them. The ease with which Br+ is released from Nbromo- arylsulphonamides depends on the electron density on the nitrogen atom of the sulphonamide group, which in turn depends on the nature of the substituent on the benzene ring. The validity of the Hammett equation has also been tested for oxidation of both fructose and glucose. Enthalpies and entropies of activations of the oxidations by all the N-bromo-arylsulphonamides correlate well. The effect of substitution on and log of the oxidations is also considered.

  15. Well-dispersed NiO nanoparticles supported on nitrogen-doped carbon nanotube for methanol electrocatalytic oxidation in alkaline media

    Science.gov (United States)

    Wang, Pengcheng; Zhou, Yingke; Hu, Min; Chen, Jian

    2017-01-01

    Nitrogen-doped carbon nanotube supporting NiO nanoparticles were synthesized by a chemical precipitation process coupled with subsequent calcination. The morphology and structure of the composites were characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS), and the electrochemical performance was evaluated using cyclic voltammetry and chronoamperometric technique. The effects of nitrogen doping, calcination temperature and content of NiO nanoparticles on the electrocatalytic activity toward methanol oxidation were systematically studied. The results show that the uniformly dispersed ultrafine NiO nanoparticles supported on nitrogen-doped carbon nanotube are obtained after calcination at 400 °C. The optimized composite catalysts present high electrocatalytic activity, fast charge-transfer process, excellent accessibility and stability for methanol oxidation reaction, which are promising for application in the alkaline direct methanol fuel cells.

  16. 3-Methyltrimethylammonium poly(2,6-dimethyl-1,4-phenylene oxide) based anion exchange membrane for alkaline polymer electrolyte fuel cells

    Indian Academy of Sciences (India)

    K Hari Gopi; S Gouse Peera; S D Bhat; P Sridhar; S Pitchumani

    2014-06-01

    Hydroxyl ion (OH–) conducting anion exchange membranes based on modified poly (phenylene oxide) are fabricated for their application in alkaline polymer electrolyte fuel cells (APEFCs). In the present study, chloromethylation of poly(phenylene oxide) (PPO) is performed by aryl substitution rather than benzyl substitution and homogeneously quaternized to form an anion exchange membrane (AEM). 1H NMR and FT–IR studies reveal successful incorporation of the above groups in the polymer backbone. The membrane is characterized for its ion exchange capacity and water uptake. The membrane formed by these processes show good ionic conductivity and when used in fuel cell exhibited an enhanced performance in comparison with the state-of-the-art commercial AHA membrane. A peak power density of 111 mW/cm2 at a load current density of 250 mA/cm2 is obtained for PPO based membrane in APEFCs at 30 °C.

  17. Small-Angle Neutron Scattering and Electron Microscopy Study of the Wet and Dry High-Temperature Oxidation of Alumina- and Chromia- Forming Stainless Steels

    Energy Technology Data Exchange (ETDEWEB)

    Rother, Gernot [ORNL; Keiser, James R [ORNL; Brady, Michael P [ORNL; Unocic, Kinga A [ORNL; Anovitz, Lawrence {Larry} M [ORNL; Littrell, Ken [ORNL; Meisner, Roberta Ann [ORNL; Santella, Michael L [ORNL; Wesolowski, David J [ORNL; Cole, David R [ORNL

    2012-01-01

    Foils of T347 stainless steel and a developmental alumina-forming austenitic (AFA) stainless steel were oxidized at 800 C in dry air, air with 10% H2O, and air with 10% D2O. The T347 foils exhibited a transition to rapid Fe-base oxide formation between 24 and 72 h of exposure in H2O and D2O, but exhibited protective Cr-rich oxide formation in dry air. In contrast, only thin, protective Al-rich oxide surfaces were observed for the AFA alloy foils under all conditions studied. Changes in the small angle neutron scattering (SANS) signal were observed for the T347 stainless steel as a function of oxidation time in dry air, attributed to oxide grain growth and porosity formation/partial scale detachment associated with spinel phase at the scale/gas interface. For the AFA alloy, only minor changes in scattering as a result of oxidation time were observed. For both T347 and AFA, similar scattering was observed in dry and wet air (H2O and D2O) exposure. This finding indicates that water vapor exposure did not induce significant morphological changes in the oxide scales (such as increased porosity) in the 5-300 nm size regime accessed by SANS.

  18. [Use of coulometric titration for elucidating the mechanism of the oxidation of 6-APA alkaline breakdown products by halogens].

    Science.gov (United States)

    Kharlamov, V T; Inkin, A A; Ermolina, G E

    1975-02-01

    Penaldinic acid and penicillamine were formed on alkali decomposition (1 N NaOH) of 6-APA for 20 minutes at room temperature, penicillamine being completely oxidized to disulphide by the air oxygen. Coulometric titration of the alkali decomposition products showed that generated chlorine in 0.5 N HCl solution or bromine in a week acid solution of KBr oxidized them with participation of 7 electrones. Generated iodine did not practically oxidize the 6-APA decomposition products during the coulometric titration.

  19. High performance nano-Ni/Graphite electrode for electro-oxidation in direct alkaline ethanol fuel cells

    Science.gov (United States)

    Soliman, Ahmed B.; Abdel-Samad, Hesham S.; Abdel Rehim, Sayed S.; Ahmed, Mohamed A.; Hassan, Hamdy H.

    2016-09-01

    Ni/Graphite electrocatalysts (Ni/G) are successfully prepared through electrodeposition of Ni from acidic (pH = 0.8) and feebly acidic (pH = 5.5) aqueous Ni (II) baths. The efficiencies of such electrodes are investigated as anodes for direct alkaline ethanol fuel cells through their ethanol electrooxidation cyclic voltammetric (CV) response in alkaline medium. A direct proportionality between the amount of the electrodeposited Ni and its CV response is found. The amounts of the deposited Ni from the two baths are recorded using the Electrochemical Quartz Crystal Microbalance (eQCM). The Ni/G electrodes prepared from the feebly acidic bath show a higher electrocatalytic response than those prepared from the acidic bath. Surface morphology of the Ni particles electrodeposited from feebly acidic bath appears in a nano-scale dimension. Various electrochemical experiments are conducted to confirm that the Ni/G ethanol electrooxidation CV response greatly depends on the pH rather than nickel ion concentration of the deposition bath. The eQCM technique is used to detect the crystalline phases of nickel as α-Ni(OH)2/γ-NiOOH and β-Ni(OH)2/β-NiOOH and their in-situ inter-transformations during the potentiodynamic polarization.

  20. Application of sludge-based carbonaceous materials in a hybrid water treatment process based on adsorption and catalytic wet air oxidation.

    Science.gov (United States)

    Julcour Lebigue, Carine; Andriantsiferana, Caroline; N'Guessan Krou; Ayral, Catherine; Mohamed, Elham; Wilhelm, Anne-Marie; Delmas, Henri; Le Coq, Laurence; Gerente, Claire; Smith, Karl M; Pullket, Suangusa; Fowler, Geoffrey D; Graham, Nigel J D

    2010-12-01

    This paper describes a preliminary evaluation of the performance of carbonaceous materials prepared from sewage sludges (SBCMs) in a hybrid water treatment process based on adsorption and catalytic wet air oxidation; phenol was used as the model pollutant. Three different sewage sludges were treated by either carbonisation or steam activation, and the physico-chemical properties of the resultant carbonaceous materials (e.g. hardness, BET surface area, ash and elemental content, surface chemistry) were evaluated and compared with a commercial reference activated carbon (PICA F22). The adsorption capacity for phenol of the SBCMs was greater than suggested by their BET surface area, but less than F22; a steam activated, dewatered raw sludge (SA_DRAW) had the greatest adsorption capacity of the SBCMs in the investigated range of concentrations (oxidation tests, the SBCMs demonstrated catalytic behaviour arising from their substrate adsorptivity and metal content. Recycling of SA_DRAW in successive oxidations led to significant structural attrition and a hardened SA_DRAW was evaluated, but found to be unsatisfactory during the oxidation step. In a combined adsorption-oxidation sequence, both the PICA carbon and a selected SBCM showed deterioration in phenol adsorption after oxidative regeneration, but a steady state performance was reached after 2 or 3 cycles.

  1. Total catalytic wet oxidation of phenol and its chlorinated derivates with MnO2/CeO2 catalyst in a slurry

    Directory of Open Access Journals (Sweden)

    A. J. Luna

    2009-09-01

    Full Text Available In the present work, a synthetic effluent of phenol was treated by means of a total oxidation process-Catalyzed Wet Oxidation (CWO. A mixed oxide of Mn-Ce (7:3, the catalyst, was synthesized by co-precipitation from an aqueous solution of MnCl2 and CeCl3 in a basic medium. The mixed oxide, MnO2/CeO2, was characterized and used in the oxidation of phenol in a slurry reactor in the temperature range of 80-130ºC and pressure of 2.04-4.76 MPa. A phenol solution containing 2.4-dichlorophenol and 2.4-dichlorophenoxyacetic acid was also degraded with good results. A lumped kinetic model, with two parallel reaction steps, fits precisely with the integrated equation and the experimental data. The kinetic parameters obtained are in agreement with the Arrhenius equation. The activation energies were determined to be 38.4 for the total oxidation and 53.4 kJ/mol for the organic acids formed.

  2. Total catalytic wet oxidation of phenol and its chlorinated derivates with MnO{sub 2}/CeO{sub 2} catalyst in a slurry

    Energy Technology Data Exchange (ETDEWEB)

    Luna, A.J. [Instituto Nacional de Propriedade Industrial (INPI), Rio de Janeiro, RJ (Brazil)], e-mail: airtonj@inpi.gov.br; Rojas, L.O.A.; Sousa, J.F. de [Universidade Federal do Rio Grande do Norte (UFRN), Natal, RN (Brazil). Dept. of Chemical Engineering; Melo, D.M.A. [Universidade Federal do Rio Grande do Norte (UFRN), Natal, RN (Brazil). Dept. of Chemistry; Benachour, M. [Universidade Federal de Pernambuco (UFPE)Recife, PE (Brazil). Dept. of Chemical Engineering

    2009-07-15

    In the present work, a synthetic effluent of phenol was treated by means of a total oxidation process - Catalyzed Wet Oxidation (CWO). A mixed oxide of Mn-Ce (7:3), the catalyst, was synthesized by co-precipitation from an aqueous solution of MnCl{sub 2} and CeCl{sub 3} in a basic medium. The mixed oxide, MnO{sub 2}/CeO{sub 2}, was characterized and used in the oxidation of phenol in a slurry reactor in the temperature range of 80-130 deg C and pressure of 2.04-4.76 MPa. A phenol solution containing 2.4-dichlorophenol and 2.4- dichlorophenoxyacetic acid was also degraded with good results. A lumped kinetic model, with two parallel reaction steps, fits precisely with the integrated equation and the experimental data. The kinetic parameters obtained are in agreement with the Arrhenius equation. The activation energies were determined to be 38.4 for the total oxidation and 53.4 kJ/mol for the organic acids formed. (author)

  3. Long-time constant-capacitance DLTS investigations of 6H SiC/MOS structures: comparison of dry and wet oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Bassler, M.; Pensl, G. [Erlangen-Nuernberg Univ., Erlangen (Germany). Inst. fuer Angewandte Physik

    1999-07-30

    A long-time constant-capacitance deep level transient spectroscopy (LT-CC-DLTS) method has been established to investigate the energy distribution D{sub it} and the capture-cross-section {sigma}{sub n/p} of states at the interface of 6H SiC/MOS structures. A comparison of dry and wet oxidation (1120 C) reveals a change in the distribution of interface states and a different magnitude of capture-cross-sections indicating that the interface states consist of at least two types of defects. (orig.)

  4. Carbon Supported Oxide-Rich Pd-Cu Bimetallic Electrocatalysts for Ethanol Electrooxidation in Alkaline Media Enhanced by Cu/CuOx

    Directory of Open Access Journals (Sweden)

    Zengfeng Guo

    2016-04-01

    Full Text Available Different proportions of oxide-rich PdCu/C nanoparticle catalysts were prepared by the NaBH4 reduction method, and their compositions were tuned by the molar ratios of the metal precursors. Among them, oxide-rich Pd0.9Cu0.1/C (Pd:Cu = 9:1, metal atomic ratio exhibits the highest electrocatalytic activity for ethanol oxidation reaction (EOR in alkaline media. X-ray photoelectron spectroscopy (XPS and high resolution transmission electron microscopy (HRTEM confirmed the existence of both Cu and CuOx in the as-prepared Pd0.9Cu0.1/C. About 74% of the Cu atoms are in their oxide form (CuO or Cu2O. Besides the synergistic effect of Cu, CuOx existed in the Pd-Cu bimetallic nanoparticles works as a promoter for the EOR. The decreased Pd 3d electron density disclosed by XPS is ascribed to the formation of CuOx and the spill-over of oxygen-containing species from CuOx to Pd. The low Pd 3d electron density will decrease the adsorption of CH3COads intermediates. As a result, the electrocatalytic activity is enhanced. The onset potential of oxide-rich Pd0.9Cu0.1/C is negative shifted 150 mV compared to Pd/C. The oxide-rich Pd0.9Cu0.1/C also exhibited high stability, which indicated that it is a candidate for the anode of direct ethanol fuel cells (DEFCs.

  5. Monitoring, field experiments, and geochemical modeling of Fe(II) oxidation kinetics in a stream dominated by net-alkaline coal-mine drainage, Pennsylvania, USA

    Science.gov (United States)

    Cravotta, Charles A.

    2015-01-01

    Watershed-scale monitoring, field aeration experiments, and geochemical equilibrium and kinetic modeling were conducted to evaluate interdependent changes in pH, dissolved CO2, O2, and Fe(II) concentrations that typically take place downstream of net-alkaline, circumneutral coal-mine drainage (CMD) outfalls and during aerobic treatment of such CMD. The kinetic modeling approach, using PHREEQC, accurately simulates observed variations in pH, Fe(II) oxidation, alkalinity consumption, and associated dissolved gas concentrations during transport downstream of the CMD outfalls (natural attenuation) and during 6-h batch aeration tests on the CMD using bubble diffusers (enhanced attenuation). The batch aeration experiments demonstrated that aeration promoted CO2 outgassing, thereby increasing pH and the rate of Fe(II) oxidation. The rate of Fe(II) oxidation was accurately estimated by the abiotic homogeneous oxidation rate law −d[Fe(II)]/dt = k1·[O2]·[H+]−2·[Fe(II)] that indicates an increase in pH by 1 unit at pH 5–8 and at constant dissolved O2 (DO) concentration results in a 100-fold increase in the rate of Fe(II) oxidation. Adjusting for sample temperature, a narrow range of values for the apparent homogeneous Fe(II) oxidation rate constant (k1′) of 0.5–1.7 times the reference value of k1 = 3 × 10−12 mol/L/min (for pH 5–8 and 20 °C), reported by Stumm and Morgan (1996), was indicated by the calibrated models for the 5-km stream reach below the CMD outfalls and the aerated CMD. The rates of CO2 outgassing and O2ingassing in the model were estimated with first-order asymptotic functions, whereby the driving force is the gradient of the dissolved gas concentration relative to equilibrium with the ambient atmosphere. Although the progressive increase in DO concentration to saturation could be accurately modeled as a kinetic function for the conditions evaluated, the simulation of DO as an instantaneous equilibrium process did not affect the

  6. Preparation of Pt Au/C and Pt Au Bi/C electrocatalysts using electron beam irradiation for ethanol electro-oxidation in alkaline medium

    Energy Technology Data Exchange (ETDEWEB)

    Silva, Dionisio F.; Geraldes, Adriana N.; Cardoso, Elisangela S.Z.; Gomes, Thiago B.; Linardi, Marcelo; Oliveira Neto, Almir; Spinace, Estevam V., E-mail: dfsilva@ipen.b [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil)

    2011-07-01

    Pt Au/C (50:50) and PtAuBi/C electrocatalysts with Pt:Au:Bi atomic ratios of 50:40:10, 50:30:20 and 50:10:40 were prepared in water/2-propanol using electron beam irradiation. The materials were characterized by X-ray diffraction (XRD) and the electro-oxidation of ethanol was studied by chronoamperometry at room temperature. The X-ray diffraction measurements for all electrocatalysts prepared showed four peaks, which are associated with the planes of the face-centered cubic (fcc) structure characteristic of Pt and Pt alloys. For PtAuBi/C it was also observed the presence of a mixture of BiPt alloys and bismuth phases. The average crystallite sizes for Pt/C, PtAu/C, PtAuBi/C (50:40:10), PtAuBi/C (50:30:20) and PtAuBi/C (50:10:40) were in the range of 2.0 - 4.0 nm. The activity of the electrocatalysts for ethanol oxidation in alkaline medium showed that PtAuBi/C (50:40:10) had a higher performance for ethanol oxidation compared to others electrocatalysts prepared. (author)

  7. Kinetic study of wet oxidation of Si0.5Ge0.5 alloy by Rutherford backscattering spectroscopy

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    The oxidation of Si0. sGeo.5 alloy has been investigated at the temperatures of 800℃ and 900 ℃. Rutherford backscattering spectroscopy has been employed to determine the composition and thickness of the oxide layers. Only Sio.5Geo. 5O2 layer formed during the oxidation at 800℃, whilst three layers, Si0.5Ge0.5O2, SiO2 and Ge, are existed after the oxidation at 900℃. Experimental results are interpreted by adding a germanium flux F4 in Deal-Grove oxidation model of Silicon.

  8. Catalytic wet air oxidation of bisphenol A solution in a batch-recycle trickle-bed reactor over titanate nanotube-based catalysts.

    Science.gov (United States)

    Kaplan, Renata; Erjavec, Boštjan; Senila, Marin; Pintar, Albin

    2014-10-01

    Catalytic wet air oxidation (CWAO) is classified as an advanced oxidation process, which proved to be highly efficient for the removal of emerging organic pollutant bisphenol A (BPA) from water. In this study, BPA was successfully removed in a batch-recycle trickle-bed reactor over bare titanate nanotube-based catalysts at very short space time of 0.6 min gCAT g(-1). The as-prepared titanate nanotubes, which underwent heat treatment at 600 °C, showed high activity for the removal of aqueous BPA. Liquid-phase recycling (5- or 10-fold recycle) enabled complete BPA conversion already at 200 °C, together with high conversion of total organic carbon (TOC), i.e., 73 and 98 %, respectively. The catalyst was chemically stable in the given range of operating conditions for 189 h on stream.

  9. Methods of analysis by the U.S. Geological Survey National Water Quality Laboratory : determination of nonpurgeable suspended organic carbon by wet-chemical oxidation and infrared spectrometry

    Science.gov (United States)

    Burkhardt, Mark R.; Kammer, James A.; Jha, Virendra K.; O'Mara-Lopez, Peggy G.; Woodworth, Mark T.

    1997-01-01

    Precision and accuracy results are described for the determination of nonpurgeable suspended organic carbon (SOC) by silver-filter filtration, wet-chemical oxidation, and infrared determination of hte resulting carbon dioxide (CO2) used at the U.S. Geological Survey's nationalWater Quality Laboratory. An aliquot of raw water isfiltered through a 0.45-micrometer silver filter. The trapped organic material is oxidized using phosphoric acid and potassium persulfate in a scaled glass ampule,and the rseulting CO2 is measured by an infrared CO2 detector. The amount of CO3 is proportional to the concentration of chemically oxidizable nonpurgeable organic carbon in the sample. The SOC method detection limit for routine analysis is 0.2 milligram per liter. The average percent recovery is 97.1 percent and the average standard deviation is 11 percent.

  10. Experimental research on influencing factors of wet removal of NO from coal-fired flue gas by UV/H2O2 advanced oxidation process

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    Wet removal of NO from coal-fired flue gas by UV/H2O2 Advanced Oxidation Process (AOP) were investigated in a self-designed UV-bubble reactor. Several main influencing factors (UV intensity, H2O2 initial concentration, initial pH value, solution temperature, NO initial concentration, liquid-gas ratio and O2 percentage content) on the NO removal efficiency were studied. The results showed that UV intensity, H2O2 initial concentration, NO initial concentration and liquid-gas ratio are the main influencing factors. In the best conditions, the highest NO removal efficiency by UV/H2O2 advanced oxidation process could reach 82.9%. Based on the experimental study, the influencing mechanism of the relevant influencing factors were discussed in depth.

  11. Degradation process analysis of the azo dyes by catalytic wet air oxidation with catalyst CuO/γ-Al2O3.

    Science.gov (United States)

    Hua, Li; Ma, Hongrui; Zhang, Lei

    2013-01-01

    Three azo dyes (Methyl Orange, Direct Brown and Direct Green) were treated by catalytic wet air oxidation (CWAO) with the catalysts CuO/γ-Al(2)O(3) prepared by consecutive impregnation. The relationship of decolorization extent, chemical oxygen demand (COD) removal extent and total organic carbon (TOC) in dye solution were investigated. The results indicated that the CuO/γ-Al(2)O(3) catalyst had excellent catalytic activity in treating azo dyes. Almost 99% of color and 70% of TOC were removed in 2h. The high removal extent of color and TOC indicated that the CWAO obtained perfect decomposition for pollutants. The degradation pathway of azo dyes was analyzed by UV-Vis, FTIR and MS. According to the examined results, the hydroxyl ((·)OH) radicals induced strong oxidizing effects in the target solution and destroyed the chromophoric groups of azo-benzene conjugated of the molecular structure. Considering characteristics of the dye structure, the azo bond (-N=N-) would first be attacked by the hydroxyl radical and other free radicals. With the continuous oxidization and the long reaction time at high temperature, these intermediates could be oxidized to the final oxidation products, such as water and carbon dioxide.

  12. Sulfate-dependent acetate oxidation under extremely natron-alkaline conditions by syntrophic associations from hypersaline soda lakes

    OpenAIRE

    Sorokin, D. Y.; Abbas, B; Tourova, T.P.; Bumazhkin, B. K.; Kolganova, T. V.; Muyzer, G

    2014-01-01

    So far, anaerobic sulfate-dependent acetate oxidation at high pH has only been demonstrated for a low-salt-tolerant syntrophic association of a clostridium ‘Candidatus Contubernalis alkalaceticum’ and its hydrogenotrophic sulfate-reducing partner Desulfonatronum cooperativum. Anaerobic enrichments at pH 10 inoculated with sediments from hypersaline soda lakes of the Kulunda Steppe (Altai, Russia) demonstrated the possibility of sulfate-dependent acetate oxidation at much higher salt concentra...

  13. 生化剩余污泥湿式氧化减量机理研究%MECHANISM OF BIOCHEMICAL EXCESS SLUDGE REDUCTION BY WET AIR OXIDATION

    Institute of Scientific and Technical Information of China (English)

    李本高; 孙友; 张超

    2014-01-01

    The improvement of sludge dewater ability is essential to the volume reduction of waste activated sludge (WAS). The wet air oxidation process is used for WAS degradation. It is found that the volatile suspended sludge is decomposed into small molecular organic compounds,such as soluble protein,carbohydrate,short-chain fatty acids and ammonia by wet air oxidation,which improves the sludge dewater ability significantly.%改善污泥脱水性能对大幅减少生化剩余污泥体积意义重大。采用湿式氧化方法对生化剩余污泥进行消解,可将污泥的主要污染物高分子挥发性悬浮物降解,使其转变为水溶性蛋白质、糖、有机酸及氨氮等小分子有机物,使污泥脱水性能得到显著改善而容易脱水。

  14. Mechanistic Investigations of Oxidation of Some Dipeptides by Sodium N-chloro-p-toluenesulfonamide in Alkaline Medium: A Kinetic Study

    Institute of Scientific and Technical Information of China (English)

    PUTTASWAMY; VAZ Nirmala; RAJENAHALLY VGOWDA Jagadeesh

    2008-01-01

    The kinetics of oxidation of five dipeptides (DPP) viz., glycylglycine (Gly-Gly), L-alanyl-L-alanine (Ala-Ala),L-valyl-L-valine (Val-Val), L-leucyl-L-leucine (Leu-Leu) and phenylglycyl-phenylglycine (Phg-Phg) by sodium N-chloro-p-toluenesuifonamide or chloramine-T (CAT) in NaOH medium was studied at 308 K. The reactions follow identical kinetics for all the dipeptides, being first-order dependence each on [CAT]o, [DPP]o and fractional-order on [OH-]. Addition of p-toluenesulfonamide or halide ions (CI- or Br-) has no significant effect on the rate of reaction. The reaction rate was found to increase with increase in ionic strength of the medium. The solvent isotope effect was studied using D2O. The activation parameters for the reaction were computed from Arrhenius plots. Equilibrium and decomposition constants were evaluated. The oxidation products of the dipeptides were identiffed as their corresponding aldehydes. An isokinetic relationship was observed with β=352 K, indicating that enthalpy factors control the reaction rate. CH3C6H4SO2NCl- of the oxidant has been postulated as the reactive oxidizing species. Under comparable experimental conditions, the rate of oxidation of the dipeptides increases in the order: Phg-Phg>Ala-Ala>Val-Val>Leu-Leu>Gly-Gly. The kinetics of oxidation of the dipeptides have also been compared with those of their corresponding monomer amino acids. The observed results have been explained by a plausible mechanism and the related rate law has been deduced.

  15. Oxygen evolution reaction characteristics of synthetic nickel-cobalt-oxide electrodes for alkaline anion-exchange membrane water electrolysis

    Science.gov (United States)

    Koo, Tae Woo; Park, ChanSu; Kim, Yang Do; Lee, Dooyong; Park, Sungkyun; Lee, Jae Ho; Choi, Sung Mook; Choi, Chul Young

    2015-11-01

    A polymer electrolyte membrane water electrolysis system can produce high-purity hydrogen gases in a highly efficient manner. However, the level of hydrogen gas production is still small. In addition, noble-metal catalysts for the reaction in acidic environments, as well as an additional drying step to remove water contained in the hydrogen, are required. Therefore, water electrolysis system with high efficiency and lower cost, an alkaline anion-exchange membrane system that can produce high-purity hydrogen without a noble-metal catalyst, is needed. Nano-size NiCo2O4 powders were prepared by using a sol-gel method to achieve an efficient and economical water electrolysis system. When the powder was calcined at 450 °C, the crystallinity and the cyclic voltammogram measurement showed the best values. In addition, the 15-wt.% polytetrafluoroethylene mixed NiCo2O4 powders exhibited the largest cyclic voltammetry active area and the highest oxygen evolution reaction activity with the appropriate stability.

  16. Full scale calcium bromide injection with subsequent mercury oxidation and removal within wet flue gas desulphurization system: Experience at a 700 MW coal-fired power facility

    Science.gov (United States)

    Berry, Mark Simpson

    The Environmental Protection Agency promulgated the Mercury and Air Toxics Standards rule, which requires that existing power plants reduce mercury emissions to meet an emission rate of 1.2 lb/TBtu on a 30-day rolling average and that new plants meet a 0.0002 lb/GWHr emission rate. This translates to mercury removals greater than 90% for existing units and greater than 99% for new units. Current state-of-the-art technology for the control of mercury emissions uses activated carbon injected upstream of a fabric filter, a costly proposition. For example, a fabric filter, if not already available, would require a 200M capital investment for a 700 MW size unit. A lower-cost option involves the injection of activated carbon into an existing cold-side electrostatic precipitator. Both options would incur the cost of activated carbon, upwards of 3M per year. The combination of selective catalytic reduction (SCR) reactors and wet flue gas desulphurization (wet FGD) systems have demonstrated the ability to substantially reduce mercury emissions, especially at units that burn coals containing sufficient halogens. Halogens are necessary for transforming elemental mercury to oxidized mercury, which is water-soluble. Plants burning halogen-deficient coals such as Power River Basin (PRB) coals currently have no alternative but to install activated carbon-based approaches to control mercury emissions. This research consisted of investigating calcium bromide addition onto PRB coal as a method of increasing flue gas halogen concentration. The treated coal was combusted in a 700 MW boiler and the subsequent treated flue gas was introduced into a wet FGD. Short-term parametric and an 83-day longer-term tests were completed to determine the ability of calcium bromine to oxidize mercury and to study the removal of the mercury in a wet FGD. The research goal was to show that calcium bromine addition to PRB coal was a viable approach for meeting the Mercury and Air Toxics Standards rule

  17. Factors influencing catalytic wet peroxide oxidation of maleic acid in aqueous phase over copper/micelle templated silica-3-aminopropyltrimethoxysilane catalyst.

    Science.gov (United States)

    Daniel, Lilian; Katima, Jamidu H Y

    2009-01-01

    Catalytic wet peroxide oxidation (CWPO) of initial maleic acid feed concentration (0.005 to 0.03 M) was carried out in a temperature range of 20-50 degrees Celsius, on micelle templated silica-3-aminopropyltrimethoxysilane (MTS-AMP) supported copper catalyst. The influence of various operating parameters such as initial feed concentration of maleic acid, temperature, catalyst loading and the stability of the catalyst were investigated. CWPO reactions were performed in a stirred batch reactor at an atmospheric pressure in the presence of H(2)O(2) as an oxidant. Total conversion of maleic acid into acetic acid was obtained under mild conditions (i.e. atmospheric pressure and 40 degrees Celsius). Blank experiments showed no measurable maleic acid conversion (i.e. only approximately 0.5% conversion of initial maleic acid), indicating that a significant oxidation reaction of maleic acid is enhanced by the presence of a catalyst. Copper on micelle templated silica-3-aminopropyltrimethoxysilane catalyst therefore was found to be suitable for aqueous phase oxidation of maleic acid with 100% of maleic acid conversion.

  18. Sulfate-dependent acetate oxidation under extremely natron-alkaline conditions by syntrophic associations from hypersaline soda lakes

    NARCIS (Netherlands)

    Sorokin, D.Y.; Abbas, B.; Tourova, T.P.; Bumazhkin, B.K.; Kolganova, T.V.; Muyzer, G.

    2014-01-01

    So far, anaerobic sulfate-dependent acetate oxidation at high pH has only been demonstrated for a low-salt-tolerant syntrophic association of a clostridium ‘Candidatus Contubernalis alkalaceticum’ and its hydrogenotrophic sulfate-reducing partner Desulfonatronum cooperativum. Anaerobic enrichments a

  19. Copper-poly(2-aminodiphenylamine) as a novel and low cost electrocatalyst for electrocatalytic oxidation of methanol in alkaline solution

    Energy Technology Data Exchange (ETDEWEB)

    Ojani, Reza, E-mail: fer-o@umz.ac.i [Electroanalytical Chemistry Research Laboratory, Faculty of Chemistry, University of Mazandaran, Babolsar (Iran, Islamic Republic of); Raoof, Jahan-Bakhsh; Ahmady-Khanghah, Yusef [Electroanalytical Chemistry Research Laboratory, Faculty of Chemistry, University of Mazandaran, Babolsar (Iran, Islamic Republic of)

    2011-03-30

    In the present work we demonstrate the carbon paste as a new electrode substrate for the electropolymerization of 2-aminodiphenylamine and fabrication of polymer film modified electrode. Then transition metal of copper is incorporated into the polymer by electrodepositing of Cu(II) from CuCl{sub 2} acidic solution using potentiostatic technique. The electrocatalytic oxidation of methanol was studies by cyclic voltammetry and chronoamperometry methods at the surface of obtained Cu/P(2ADPA)/MCPE. It has been found that in the course of an anodic potential sweep, the electro-oxidation of methanol follows the formation of Cu(III) and is catalyzed by this species through a mediated electron transfer mechanism. The obtained current density for this catalytic oxidation is very high which could be come from high surface area of caused by the P(2ADPA) modification. The effects of various parameters such as the copper loading, scan rate and methanol concentration on the electrocatalytic oxidation of methanol were also investigated at the surface of Cu/P(2ADPA)/MCPE. Finally, using a chronoamperometric method, the catalytic rate constant (k) for methanol was found to be 0.2 x 10{sup 5} cm{sup 3} mol{sup -1} s{sup -1} that the high k can be ascribed for the fast electron transfer process due to electrode modification.

  20. Synthesis of silver/nitrogen-doped reduced graphene oxide through a one-step thermal solid-state reaction for oxygen reduction in an alkaline medium

    Science.gov (United States)

    Soo, Li Ting; Loh, Kee Shyuan; Mohamad, Abu Bakar; Daud, Wan Ramli Wan; Wong, Wai Yin

    2016-08-01

    One of the obstacles to the commercialisation of fuel cells is the high cost of noble metals, such as platinum, that are used as electrocatalysts. Silver-incorporated nitrogen-doped reduced graphene oxide (Ag/N-rGO) has been synthesised through the simple annealing of metal salts with graphene oxide and melamine. The presence of silver and nitrogen atoms in Ag/N-rGO was confirmed by X-ray photoelectron spectroscopy (XPS) and energy dispersive spectroscopy (EDS) analysis. Both the XPS and EDS results showed a higher Ag loading on the N-rGO surface compared with the rGO surface. Transmission electron microscopy (TEM) images revealed a wide size distribution of Ag particles loaded on the N-rGO surface. Electrochemical results indicate that N-rGO is a better support for Ag than rGO. Cyclic voltammetry (CV) and linear sweep voltammetry (LSV) results indicate that Ag/N-rGO is a potential ORR catalyst candidate in alkaline as it exhibited an onset potential of -0.15 V vs. Ag/AgCl and a limiting diffusion current density of -4.38 mA cm-2 with four electron pathways. In addition, Ag/N-rGO also showed better methanol tolerance than Pt/C.

  1. Mechanistic aspects of Os(VIII) catalysed oxidation of loop diuretic drug furosemide by Ag(III) periodate complex in aqueous alkaline medium

    Indian Academy of Sciences (India)

    Shweta J Malode; Nagaraj P Shetti; Sharanappa T Nandibewoor

    2012-03-01

    The kinetics of oxidation of a loop diuretic drug furosemide (Fur) by diperiodatoargentate(III) (DPA) has been investigated in the presence of osmium(VIII) (Os(VIII)) used as homogeneous catalyst in alkaline medium at a constant ionic strength of 0.20mol dm-3 spectrophotometrically attached with HI-TECH SFA-12 stopped flow accessory. The stoichiometry was 1:2 (Fur:DPA). The order of the reaction with respect to [DPA] was unity while the order with respect to [Fur] was less than unity over the concentration range studied. The rate increased with an increase in [OH−] and decreased with an increase in [IO$^{−}_{4}$]. The order with respect to [Os(VIII)] was unity. The oxidation products were identified as 2-(4-carboxy-2-oxo-but-3-enylamino)-4-chloro-5-sulfamoyl-benzoic acid and Ag(I). A suitable mechanism was proposed. The reaction constants involved in the different steps of the reaction mechanism were calculated. Kinetic experiments suggest that [Ag(H2IO6)(H2O)2] is the reactive silver(III) species and [OsO4(OH)2]2− is the reactive Os(VIII) species.

  2. Graphene oxide electrocatalyst on MnO2 air cathode as an efficient electron pump for enhanced oxygen reduction in alkaline solution

    Science.gov (United States)

    Basirun, Wan Jeffrey; Sookhakian, Mehran; Baradaran, Saeid; Endut, Zulkarnain; Mahmoudian, Mohammad Reza; Ebadi, Mehdi; Yousefi, Ramin; Ghadimi, Hanieh; Ahmed, Sohail

    2015-03-01

    Graphene oxide (GO) was deposited on the surface of a MnO2 air cathode by thermal evaporation at 50°C from a GO colloidal suspension. Fourier transformed infrared spectroscopy and field emission scanning electron microscopy confirmed the presence of GO on the MnO2 air cathode (GO-MnO2). Voltammetry and chrono-amperometry showed increased currents for the oxygen reduction reaction (ORR) in 6 M KOH solution for GO-MnO2 compared to the MnO2 cathode. The GO-MnO2 was used as an air cathode in an alkaline tin-air cell and produced a maximum power density of 13 mW cm-2, in contrast to MnO2, which produced a maximum power density of 9.2 mW cm-2. The electrochemical impedance spectroscopy results suggest that the chemical step for the ORR is the rate determining step, as proposed earlier by different researchers. It is suggested that the presence of GO and electrochemically reduced graphene oxide (ERGO) on the MnO2 surface are responsible for the increased rate of this step, whereby GO and ERGO accelerate the process of electron donation to the MnO2 and to adsorbed oxygen atoms.

  3. Ni/MgAlO regeneration for catalytic wet air oxidation of an azo-dye in trickle-bed reaction

    Energy Technology Data Exchange (ETDEWEB)

    Vallet, Ana [Grupo de Catálisis y Procesos de Separación (CyPS), Departamento de Ingeniería Química, Facultad de Ciencias Químicas, Universidad Complutense de Madrid, Avda. Complutense s/n, 28040 Madrid (Spain); Ovejero, Gabriel, E-mail: govejero@quim.ucm.es [Grupo de Catálisis y Procesos de Separación (CyPS), Departamento de Ingeniería Química, Facultad de Ciencias Químicas, Universidad Complutense de Madrid, Avda. Complutense s/n, 28040 Madrid (Spain); Rodríguez, Araceli [Grupo de Catálisis y Procesos de Separación (CyPS), Departamento de Ingeniería Química, Facultad de Ciencias Químicas, Universidad Complutense de Madrid, Avda. Complutense s/n, 28040 Madrid (Spain); Peres, José A. [Centro de Química de Vila Real, Universidade de Trás-os-Montes e Alto Douro, Apartado 1013, 5001-801 Vila Real (Portugal); García, Juan, E-mail: juangcia@quim.ucm.es [Grupo de Catálisis y Procesos de Separación (CyPS), Departamento de Ingeniería Química, Facultad de Ciencias Químicas, Universidad Complutense de Madrid, Avda. Complutense s/n, 28040 Madrid (Spain)

    2013-01-15

    Highlights: ► Ni supported over hydrotalcite calcined precursors as catalyst. ► Catalytic wet air oxidation in trickle bed reactor for Chromotrope 2R removal. ► Dye removal depends on temperature, initial dye concentration and flow rate. ► The catalyst proved to bare-usable after in situ regeneration. -- Abstract: Active nickel catalysts (7 wt%) supported over Mg–Al mixed oxides have been recently developed and it has also been demonstrated that they are also highly selective in Catalytic Wet air Oxidation (CWAO) of dyes. CWAO of Chromotrope 2R (C2R) has been studied using a trickle bed reactor employing temperatures from 100 to 180 °C, liquid flow rates from 0.1 to 0.7 mL min{sup −1} and initial dye concentration from 10 to 50 ppm. Total pressure and air flow were 25 bar and 300 mL min{sup −1}, respectively. The catalyst showed a very stable activity up to 24 h on stream with an average TOC conversion of 82% at 150 °C and T{sub r} = 0.098 g{sub Ni} min mL{sup −1}. After the reaction, a 1.1 wt% C of carbonaceous deposit is formed onto the catalyst and a diminution of 30% of the surface area with respect of the fresh catalyst was observed. An increase in the space time gave higher TOC conversions up to T{sub r} = 0.098 g{sub Ni} min mL{sup −1}, attaining values of 80% at 180 °C. The performance of TOC and dye removal does not decrease after two regeneration cycles. In total, a 57 h effective reaction has been carried out with no loss of catalytic activity.

  4. Selective recovery of pure copper nanopowder from indium-tin-oxide etching wastewater by various wet chemical reduction process: Understanding their chemistry and comparisons of sustainable valorization processes.

    Science.gov (United States)

    Swain, Basudev; Mishra, Chinmayee; Hong, Hyun Seon; Cho, Sung-Soo

    2016-05-01

    Sustainable valorization processes for selective recovery of pure copper nanopowder from Indium-Tin-Oxide (ITO) etching wastewater by various wet chemical reduction processes, their chemistry has been investigated and compared. After the indium recovery by solvent extraction from ITO etching wastewater, the same is also an environmental challenge, needs to be treated before disposal. After the indium recovery, ITO etching wastewater contains 6.11kg/m(3) of copper and 1.35kg/m(3) of aluminum, pH of the solution is very low converging to 0 and contain a significant amount of chlorine in the media. In this study, pure copper nanopowder was recovered using various reducing reagents by wet chemical reduction and characterized. Different reducing agents like a metallic, an inorganic acid and an organic acid were used to understand reduction behavior of copper in the presence of aluminum in a strong chloride medium of the ITO etching wastewater. The effect of a polymer surfactant Polyvinylpyrrolidone (PVP), which was included to prevent aggregation, to provide dispersion stability and control the size of copper nanopowder was investigated and compared. The developed copper nanopowder recovery techniques are techno-economical feasible processes for commercial production of copper nanopowder in the range of 100-500nm size from the reported facilities through a one-pot synthesis. By all the process reported pure copper nanopowder can be recovered with>99% efficiency. After the copper recovery, copper concentration in the wastewater reduced to acceptable limit recommended by WHO for wastewater disposal. The process is not only beneficial for recycling of copper, but also helps to address environment challenged posed by ITO etching wastewater. From a complex wastewater, synthesis of pure copper nanopowder using various wet chemical reduction route and their comparison is the novelty of this recovery process.

  5. Development of nano indium tin oxide (ITO) grains by alkaline hydrolysis of In(III) and Sn(IV) salts

    Indian Academy of Sciences (India)

    Nimai Chand Pramanik; Prasanta Kumar Biswas

    2002-11-01

    Indium tin oxide (ITO) nano powders of different compositions (In : Sn = 90 : 10, 70 : 30 and 50 : 50) were prepared by heat treatment (300–450°C) of mixed hydroxides of In(III) and Sn(IV). The hydroxides were obtained by the reaction of aq. NH3 with mixed aq. solutions of In(NO3)3 and SnCl4. FTIR and TG/DTA studies revealed that powders existed as In(OH)3 H2O−SnO3H2 H2O in the solid state and then they transformed to In2O3–SnO2 via some metastable intermediates after 300°C. Cubic phase of In2O3 was identified by XRD for the oxides up to 30% of Sn. Particle size measurements of the solid dispersed in acetone and SEM study for microstructure showed that the oxides were in the nano range (55–75 nm) whereas the size range determined from Debye–Scherrer equation were 11–24 nm.

  6. Dynamic Wetting of CaO-Al2O3-SiO2-MgO Liquid Oxide on MgAl2O4 Spinel

    Science.gov (United States)

    Abdeyazdan, Hamed; Dogan, Neslihan; Rhamdhani, M. Akbar; Chapman, Michael W.; Monaghan, Brian J.

    2015-02-01

    Inclusion type and content in steel is critical in steelmaking, affecting both productivity through clogging, and downstream physical properties of the steel. They are normally removed from steel by reacting with a slag (liquid oxide) phase. For efficient inclusion removal, the inclusions must attach/bond with this liquid phase. The strength of the attachment can be in part characterized by the wettability of the liquid oxide on the inclusions. In this study, the dynamic wetting of liquid oxides of the CaO-Al2O3-SiO2-MgO system on a solid spinel (MgAl2O4) substrate with low porosity of 1.9 pct was measured at 1773 K (1500 °C) using a modified sessile drop technique. The dynamic contact angle between the liquid and solid spinel was determined for different CaO/Al2O3 mass percent ratios ranging from 0.98 to 1.55. Characteristic curves of wettability ( θ) vs time showed a rapid decrease in wetting in the first 10 seconds tending to a plateau value at extended times. A mathematical model for spreading behavior of liquid oxides by Choi and Lee was adopted and shown to provide a reasonable representation of the spreading behavior with time. The chemical interaction at the interface between spinel (MgAl2O4) and slag was analyzed by carrying out detailed thermodynamic evaluation and characterization using scanning electron microscopy/energy dispersive spectroscopy. There is evidence of liquid penetrating the substrate via pores and along grain boundaries, forming a penetration layer in the substrate. The depth of the penetration layer was found to be a function of substrate porosity and sample cooling rate. It decreased from ~350 µm for 6.7 pct-porous substrate to ~190 µm for substrate with porosity of 1.9 pct and from ~190 µm to ~50 µm for a slow-cooled liquid oxide-spinel substrate sample in the furnace to a rapidly cooled liquid cooled-spinel substrate sample, respectively.

  7. Preparation and characterization of electrocatalysts based on palladium for electro-oxidation of alcohols in alkaline medium; Preparacao e caracterizacao de eletrocatalisadores a base de paladio para oxidacao eletroquimica de alcoois em meio alcalino

    Energy Technology Data Exchange (ETDEWEB)

    Brandalise, Michele

    2012-07-01

    In this study Pd/C, Au/C, PdAu/C, PdAuPt/C, PdAuBi/C and PdAuIr/C electrocatalysts were prepared by the sodium borohydride reduction method for the electrochemical oxidation of methanol, ethanol and ethylene glycol. This methodology consists in mix an alkaline solution of sodium borohydride to a mixture containing water/isopropyl alcohol, metallic precursors and the Vulcan XC 72 carbon support. The electrocatalysts were characterized by energy dispersive X-ray (EDX), X-ray diffraction (XRD), transmission electron microscopy (TEM) and cyclic voltammetry. The electrochemical oxidation of the alcohols was studied by chronoamperometry using a thin porous coating technique. The mechanism of ethanol electro-oxidation was studied by Fourier Transformed Infrared (FTIR) in situ. The most effective electrocatalysts were tested in alkaline single cells directly fed with methanol, ethanol or ethylene glycol. Preliminary studies showed that the most suitable atomic composition for preparing the ternary catalysts is 50:45:05. Electrochemical data in alkaline medium show that the electrocatalysts PdAuPt/C (50:45:05) showed the better activity for methanol electro oxidation, while PdAuIr/C was the most active for ethanol oxidation and PdAuBi/C (50:45:05) was the most effective for ethylene glycol oxidation in alkaline medium. These results show that the addition of gold in the composition of electrocatalysts increases their catalytic activities. The spectroelectrochemical FTIR in situ data permitted to conclude that C-C bond is not broken and the acetate is formed. (author)

  8. Different shades of oxide: from nanoscale wetting mechanisms to contact printing of gallium-based liquid metals.

    Science.gov (United States)

    Doudrick, Kyle; Liu, Shanliangzi; Mutunga, Eva M; Klein, Kate L; Damle, Viraj; Varanasi, Kripa K; Rykaczewski, Konrad

    2014-06-17

    Gallium-based liquid metals are of interest for a variety of applications including flexible electronics, soft robotics, and biomedical devices. Still, nano- to microscale device fabrication with these materials is challenging because, despite having surface tension 10 times higher than water, they strongly adhere to a majority of substrates. This unusually high adhesion is attributed to the formation of a thin oxide shell; however, its role in the adhesion process has not yet been established. In this work, we demonstrate that, dependent on dynamics of formation and resulting morphology of the liquid metal-substrate interface, GaInSn adhesion can occur in two modes. The first mode occurs when the oxide shell is not ruptured as it makes contact with the substrate. Because of the nanoscale topology of the oxide surface, this mode results in minimal adhesion between the liquid metal and most solids, regardless of substrate's surface energy or texture. In the second mode, the formation of the GaInSn-substrate interface involves rupturing of the original oxide skin and formation of a composite interface that includes contact between the substrate and pieces of old oxide, bare liquid metal, and new oxide. We demonstrate that in this latter mode GaInSn adhesion is dominated by the intimate contact between new oxide and substrate. We also show that by varying the pinned contact line length using varied degrees of surface texturing, the adhesion of GaInSn in this mode can be either decreased or increased. Lastly, we demonstrate how these two adhesion modes limit microcontact printing of GaInSn patterns but can be exploited to repeatedly print individual sub-200 nm liquid metal drops.

  9. Wet air oxidation of pretreatment of pharmaceutical wastewater by Cu2+ and [PxWmOy]q- co-catalyst system.

    Science.gov (United States)

    Wang, Guowen; Wang, Dong; Xu, Xiaochen; Liu, Lifen; Yang, Fenglin

    2012-05-30

    This study concentrates on the pretreatment of real wastewater using catalytic wet air oxidation (CWAO). WO(3-) and PO(4)(3-) contained in fosfomycin pharmaceutical wastewater (FPW) and Cu(2+) contained in berberine pharmaceutical wastewater (BPW) were studied as CWAO influent. Mixture of this two streams were reused to form Cu(2+) and [P(x)W(m)O(y)](q-), namely polyoxometalates (POMs) as co-catalyst system to treat themselves. Experiments were conducted to investigate the effects of the initial oxygen pressure and temperature on the COD (chemical oxygen demand), TOC (total organic carbon) removal and biodegradable enhancement, it was discovered that over 40% of COD and TOC removal can be easily realized in an hour of WAO oxidation at 523 K, 1.4 MPa. The BOD(5)/COD (BOD(5), biochemical oxygen demand in 5 days) of this two pharmaceutical mixture ascended from nonexistent to maximum 0.41 depends on the optimal FPW:BPW volume ratio 4:1, to compose POM co-catalyst system. Organic pollutants were incompletely oxidized to propionic acid and other intermediates. Some properties (e.g., TGA, IR, XRF) of POM catalyst separated from effluent, were obtained to provide additional information.

  10. Sewage-sludge-derived carbonaceous materials for catalytic wet hydrogen peroxide oxidation of m-cresol in batch and continuous reactors.

    Science.gov (United States)

    Yu, Yang; Wei, Huangzhao; Yu, Li; Wang, Wei; Zhao, Ying; Gu, Bin; Sun, Chenglin

    2016-01-01

    In this study, four sewage-sludge-derived carbonaceous materials (SWs) were evaluated for their catalytic wet hydrogen peroxide oxidation (CWPO) performance of m-cresol in batch reactor and continuous reactor, respectively. The SWs were produced by carbonization (SW); carbonization with the addition of CaO (CaO-SW); HNO3 pretreatment (HNO3-SW) and steam activation (Activated-SW). The properties of SW catalysts were assessed by thermogravimetric analysis, Brunauer-Emmett-Teller, Fourier Transform Infrared Spectroscopy, X-ray Fluorescence, Scanning electron microscopy, energy dispersive X-ray analysis and zeta potential. The results showed that SW treated by HNO3 (HNO3-SW) had a high conversion of m-cresol in batch reactor and continuous reactor, respectively. Under the conditions of batch reaction (Cm-cresol = 100 mg L(-1), CH2O2 = 15.7 mmol L(-1), initial pH=7.0, 0.5 g L(-1) catalyst, 80°C, 180 min adsorption and 210 min oxidation), the conversion of m-cresol reached 100% and total organic carbon removal was 67.1%. It had a high catalytic activity and stability on the treatment of m-cresol in CWPO for more than 1100 h. Furthermore, a possible reaction mechanism for the oxidation of m-cresol to 2-methyl-p-benzoquinone by CWPO was proposed.

  11. Catalytic wet oxidation of aqueous methylamine: comparative study on the catalytic performance of platinum-ruthenium, platinum, and ruthenium catalysts supported on titania.

    Science.gov (United States)

    Song, Aiying; Lu, Gongxuan

    2015-01-01

    Promotion of the dispersion of Ru species supported on TiO2 was achieved by introduction of Pt component and the role of Pt in enhancing the catalytic performances of Pt-Ru was investigated with catalytic wet air oxidation of methylamine used as a probing reaction. It was found that Pt-Ru/TiO2 displayed a much better catalytic performance compared with Pt/TiO2 and Ru/TiO2 catalysts due to having the highest dispersion of active species. Both high total organic carbon conversion and nitrogen selectivity (∼100%) over Pt-Ru/TiO2 catalyst were achieved at low temperature (200 °C). X-ray photoelectron spectroscopy characterization indicated that there were strong interactions between metal particles and the support, which may increase the catalytic performance of catalysts.

  12. [Catalytic stability in wet air oxidation of carboxylic acids over ZnFe0.25Al1.75 O4 catalyst].

    Science.gov (United States)

    Xu, Ai-hua; Yang, Min; Du, Hong-zhang; Peng, Fu-yong; Sun, Cheng-lin

    2007-07-01

    Oxalic, formic and acetic acid are main intermediate products in catalytic wet air oxidation process (CWAO). The catalytic activity and stability in CWAO of the three short-chain organic acids over ZnFe0.25Al1.75O4 catalyst were studied. Oxalic acid is the only oxidizable intermediate and the largest amount of Fe leaching is 9.5 mg L(-1) at 160 degrees C during CWAO process. Formic and acetic acid have little influence on Fe leaching. Due to the strong reducible ability of oxalic acid, the amount of Fe leaching is larger in nitrogen atmosphere than that in oxygen atmosphere. Salicylic acid can be also degraded by ZnFe0.25Al1.75O4 catalyst with a high catalytic activity and stability.

  13. Treatment of aniline by catalytic wet air oxidation: comparative study over CuO/CeO2 and NiO/Al2O3.

    Science.gov (United States)

    Ersöz, Gülin; Atalay, Süheyda

    2012-12-30

    The treatment of aniline by catalytic wet air oxidation (CWAO) was studied in a bubble reactor. The experiments were performed to investigate the effects of catalyst loading, temperature, reaction time, air flow rate, and pressure on aniline removal. The catalytic effects of the prepared nanostructured catalysts, CuO/CeO(2) (10% wt) and NiO/Al(2)O(3) (10% wt), on the CWAO treatment efficiency were also examined and compared. The prepared catalysts seem to be active having an aniline removal of 45.7% with CuO/CeO(2) and 41.9% with NiO/Al(2)O(3). The amount of N(2) formed was approximately the same for both of the catalysts.

  14. Degradation of H-acid in aqueous solution by microwave assisted wet air oxidation using Ni-loaded GAC as catalyst

    Institute of Scientific and Technical Information of China (English)

    ZHANG Yao-bin; QUAN Xie; ZHAO Hui-min; CHEN Shuo; YANG Feng-lin

    2005-01-01

    A novel process, microwave assisted catalytic wet air oxidation(MW-CWO), was applied for the degradation of H-acid( 1-amino8-naphthol-3, 6-disulfonic acid) in aqueous solution. Ni-loaded granular activated carbon (GAG), prepared by immersion-calcination method, was used as catalyst. The results showed that the MW-CWO process was very effective for the degradation of H-acid in aqueous solution under atmospheric pressure with 87.4% TOC (total organic carbon) reduction in 20 min. Ni on GAC existed in the form of NiO as specified by XRD. Loss of Ni was significant in the initial stage, and then remained almost constant after 20 min reaction. BET surface area results showed that the surface property of GAC after MW-CWO process was superior to that of blank GAC.

  15. Performance of the wet oxidation unit of the HPLC isotope ratio mass spectrometry system for halogenated compounds.

    Science.gov (United States)

    Gilevska, Tetyana; Gehre, Matthias; Richnow, Hans Hermann

    2014-08-05

    The performance of liquid chromatography-isotope ratio mass spectrometry (LC-IRMS) for polar halogenated compounds was evaluated. Oxidation capacity of the system was tested with halogenated acetic acids and halogenated aromatic compounds. Acetic acid (AA) was selected as a reference compound for complete oxidation and compared on the molar basis to the oxidation of other analytes. The isotope values were proofed with calibrated δ(13)C values obtained with an elemental analyzer (EA). Correct isotope values were obtained for mono- and dichlorinated, fluorinated, and tribrominated acetic acids and also for aniline, phenol, benzene, bromobenzene, chlorobenzene, 1,2-dichlorobenzene, 2,4,6-trichlorophenol, pentafluorophenol, and nitrobenzene. Incomplete oxidation of trichloroacetic acid (TCA) and trifluoroacetic acid (TFA) resulted in lower recovery compared to AA (37% and 24%, respectively) and in isotopic shift compared to values obtained with EA (TCA Δδ(13)C(EA/LC-IRMS) = 8.8‰, TFA Δδ(13)C(EA/LC-IRMS) = 6.0‰). Improvement of oxidation by longer reaction time in the reactor and increase in the concentration of sulfate radicals did not lead to complete combustion of TCA and TFA needed for δ(13)C analysis. To the best of our knowledge, this is the first time such highly chlorinated compounds were studied with the LC-IRMS system. This work provides information for method development of LC-IRMS methods for halogenated contaminants that are known as potential threats to public health and the environment.

  16. CuZnAl Mixed Oxide Catalyst Prepared from Hydrotalcite-like Precursor for Catalytic Wet Oxidation of Phenol%由类水滑石前驱体制备的CuZnAl复合氧化物催化剂催化湿氧化处理苯酚

    Institute of Scientific and Technical Information of China (English)

    孙颖; 杨民; 窦和瑞; 何雨; 王炜; 孙承林

    2003-01-01

    @@ The efficiency of several noble metals for catalytic wet oxidation (CWO) of various pollutants has been demonstrated[1,2]. However, the noble metals are expensive, affecting greatly the economics of the corresponding process.

  17. Catalytic wet air oxidation of phenol over RuO2/γ-Al2O3 catalyst

    Institute of Scientific and Technical Information of China (English)

    YANG Shaoxia; FENG Yujie; CAI Weimin; ZHU Wanpeng; JIANG Zhanpeng; WAN Jiafeng

    2004-01-01

    A kind of CWAO catalyst, RuO2/γ-Al2O3, was prepared by dipping Al2O3 into the aqueous solution of RuCl3.3H2O. XRD, SEM and TEM were used to determine the catalytic structure. Influences of the calcination temperature,the initial pH of the feed solution and degradation temperature on the activity of the RuO2/γ-Al2O3 catalyst were investigated and the reaction mechanism was preliminarily studied. Results showed that uniform dispersion of RuO2 crystallites was observed on the surface of the catalyst. The activity of the catalyst was higher at calcination temperature of 300℃ for 3 h and the particle reunion occurred and some large RuO2 crystallites were abundant at high calcination temperature of 500℃. The activity of the catalyst was better in the acid solution than in the alkaline solution. Increasing degradation temperature and using the catalyst could shorten the induction periods so that the phenol and COD removal were increased. For RuO2/γ-Al2O3 catalyst, the phenol and COD removal were respectively 98% and 80% in a temperature of 150℃, pH of 5.6 and pressure of 3 MPa after a 2 h reaction. This indicated that Ru/γ-Al2O3 catalyst had good activity.

  18. Subcritical and supercritical water oxidation of organic, wet wastes for carbon cycling in regenerative life support systems

    Science.gov (United States)

    Ronsse, Frederik; Lasseur, Christophe; Rebeyre, Pierre; Clauwaert, Peter; Luther, Amanda; Rabaey, Korneel; Zhang, Dong Dong; López Barreiro, Diego; Prins, Wolter; Brilman, Wim

    2016-07-01

    For long-term human spaceflight missions, one of the major requirements is the regenerative life support system which has to be capable of recycling carbon, nutrients and water from both solid and liquid wastes generated by the crew and by the local production of food through living organisms (higher plants, fungi, algae, bacteria, …). The European Space Agency's Life Support System, envisioned by the MELiSSA project, consists of a 5 compartment artificial ecosystem, in which the waste receiving compartment (so-called compartment I or briefly 'CI') is based on thermophilic fermentation. However, as the waste generated by the crew compartment and food production compartment contain typical plant fibres (lignin, cellulose and hemicellulose), these recalcitrant fibres end up largely unaffected in the digestate (sludge) generated in the C-I compartment. Therefore, the C-I compartment has to be supplemented with a so-called fibre degradation unit (in short, FDU) for further oxidation or degradation of said plant fibres. A potential solution to degrading these plant fibres and other recalcitrant organics is their oxidation, by means of subcritical or supercritical water, into reusable CO2 while retaining the nutrients in an organic-free liquid effluent. By taking advantage of the altered physicochemical properties of water above or near its critical point (647 K, 22.1 MPa) - including increased solubility of non-polar compounds and oxygen, ion product and diffusivity - process conditions can be created for rapid oxidation of C into CO2. In this research, the oxidizer is provided as a hydrogen peroxide solution which, at elevated temperature, will dissociated into O2. The purpose of this study is to identify ideal process conditions which (a) ensure complete oxidation of carbon, (b) retaining the nutrients other than C in the liquid effluent and (c) require as little oxidizer as possible. Experiments were conducted on a continuous, tubular heated reactor and on batch

  19. Improved method for the determination of nonpurgeable suspended organic carbon in natural water by silver filter filtration, wet chemical oxidation, and infrared spectrometry

    Science.gov (United States)

    Burkhardt, M.R.; Brenton, R.W.; Kammer, J.A.; Jha, V.K.; O'Mara-Lopez, P. G.; Woodworth, M.T.

    1999-01-01

    Precision and accuracy are reported for the first time for the analysis of nonpurgeable suspended organic carbon by silver membrane filtration followed by wet chemical oxidation. A water sample is pressure filtered through a 0.45-??m-pore-size, 47-mm-diameter silver membrane filter. The silver membrane filter then is cut into ribbons and placed in a flame-sealable glass ampule. The organic material trapped on the membrane filter strips is acidified, purged with oxygen to remove inorganic carbonates and volatile organic compounds, and oxidized to carbon dioxide (CO2) using phosphoric acid and potassium persulfate in the sealed glass ampule. The resulting CO2 is measured by a nondispersive infrared CO2 detector. The amount of CO2 is proportional to the concentration of chemically oxidizable nonpurgeable organic carbon in the environmental water sample. The quantitation and method detection limit for routine analysis is 0.2 mg/L. The average percent recovery in five representative matrices was 97 ?? 11%. The errors associated with sampling and sample preparation of nonpurgeable suspended organic carbon are also described.Precision and accuracy are reported for the first time for the analysis of nonpurgeable suspended organic carbon by silver membrane filtration followed by wet chemical oxidation. A water sample is pressure filtered through a 0.45-??m-pore-size, 47-mm-diameter silver membrane filter. The silver membrane filter then is cut into ribbons and placed in a flame-sealable glass ampule. The organic material trapped on the membrane filter strips is acidified, purged with oxygen to remove inorganic carbonates and volatile organic compounds, and oxidized to carbon dioxide (CO2) using phosphoric acid and potassium persulfate in the sealed glass ampule. The resulting CO2 is measured by a nondispersive infrared CO2 detector. The amount of CO2 is proportional to the concentration of chemically oxidizable nonpurgeable organic carbon in the environmental water sample

  20. Micro-arc oxidization of a novel Mg–1Ca alloy in three alkaline KF electrolytes: Corrosion resistance and cytotoxicity

    Energy Technology Data Exchange (ETDEWEB)

    Jia, Z.J.; Li, M.; Liu, Q.; Xu, X.C. [Center for Biomedical Materials and Tissue Engineering, Academy for Advanced Interdisciplinary Studies, Peking University, Beijing 100871 (China); Cheng, Y., E-mail: chengyan@pku.edu.cn [Center for Biomedical Materials and Tissue Engineering, Academy for Advanced Interdisciplinary Studies, Peking University, Beijing 100871 (China); Zheng, Y.F. [Center for Biomedical Materials and Tissue Engineering, Academy for Advanced Interdisciplinary Studies, Peking University, Beijing 100871 (China); Department of Advanced Materials and Nanotechnology, College of Engineering, Peking University, Beijing 100871 (China); Xi, T.F. [Center for Biomedical Materials and Tissue Engineering, Academy for Advanced Interdisciplinary Studies, Peking University, Beijing 100871 (China); Wei, S.C. [Center for Biomedical Materials and Tissue Engineering, Academy for Advanced Interdisciplinary Studies, Peking University, Beijing 100871 (China); Department of Oral and Maxillofacial Surgery, School and Hospital of Stomatology, Peking University, Beijing 100871 (China)

    2014-02-15

    A newly-developed Mg–1Ca (wt%) alloy was treated by micro-arc oxidization (MAO) in KF-silicate- (Si coating), KF-phosphate- (P coating) and KF-silicate-phosphate (SiP coating) electrolytes. The microstructure, composition and corrosion resistance of the resultant MAO coatings were investigated using scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and X-ray diffractometry (XRD). Electrochemical analysis and immersion test in Hanks’ solution and MTT assay for in-vitro toxicity against MG63 cells were subsequently carried out. Results showed that all the three MAO coatings contributed to the improvement of corrosion resistance and cytocompatibility of substrate; however, P coating outperformed the two others due to its specific microstructure and composition.

  1. Efficient visible-light photocatalytic oxidation of gaseous NO with graphitic carbon nitride (g-C3N4) activated by the alkaline hydrothermal treatment and mechanism analysis.

    Science.gov (United States)

    Nie, Haoyu; Ou, Man; Zhong, Qin; Zhang, Shule; Yu, Lemeng

    2015-12-30

    In this paper, an enhanced visible-light photocatalytic oxidation (PCO) of NO (∼ 400 ppm) in the presence of the graphitic carbon nitride (g-C3N4) treated by the alkaline hydrothermal treatment is evaluated. Various g-C3N4 samples were treated in different concentrations of NaOH solutions and the sample treated in 0.12 mol L(-1) of NaOH solution possesses the largest BET specific surface area as well as the optimal ability of the PCO of NO. UV-vis diffuse reflection spectra (DRS) and photoluminescence (PL) spectra were also conducted, and the highly improved photocatalytic performance is ascribed to the large specific surface area and high pore volume, which provides more adsorption and active sites, the wide visible-light adsorption edge and the narrow band gap, which is favorable for visible-light activation, as well as the decreased recombination rate of photo-generated electrons and holes, which could contribute to the production of active species. Fluorescence spectra and a trapping experiment were conducted to further the mechanism analysis of the PCO of NO, illustrating that superoxide radicals (O2(-)) play the dominant role among active species in the PCO of NO.

  2. Effect of magnesium on the aluminothermic reduction rate of zinc oxide obtained from spent alkaline battery anodes for the preparation of Al-Zn-Mg alloys

    Institute of Scientific and Technical Information of China (English)

    Rocio Ochoa; Alfredo Flores; Jesus Torres

    2016-01-01

    The aluminothermic reduction of zinc oxide (ZnO) from alkaline battery anodes using molten Al may be a good option for the elaboration of secondary 7000-series alloys. This process is affected by the initial content of Mg within molten Al, which decreases the sur-face tension of the molten metal and conversely increases the wettability of ZnO particles. The effect of initial Mg concentration on the alu-minothermic reduction rate of ZnO was analyzed at the following values:0.90wt%, 1.20wt%, 4.00t%, 4.25wt%, and 4.40wt%. The ZnO par-ticles were incorporated by mechanical agitation using a graphite paddle inside a bath of molten Al maintained at a constant temperature of 1123 K and at a constant agitation speed of 250 r/min, the treatment time was 240 min and the ZnO particle size was 450-500 mesh. The re-sults show an increase in Zn concentration in the prepared alloys up to 5.43wt%for the highest initial concentration of Mg. The reaction products obtained were characterized by scanning electron microscopy and X-ray diffraction, and the efficiency of the reaction was measured on the basis of the different concentrations of Mg studied.

  3. Effect of magnesium on the aluminothermic reduction rate of zinc oxide obtained from spent alkaline battery anodes for the preparation of Al-Zn-Mg alloys

    Science.gov (United States)

    Ochoa, Rocio; Flores, Alfredo; Torres, Jesus

    2016-04-01

    The aluminothermic reduction of zinc oxide (ZnO) from alkaline battery anodes using molten Al may be a good option for the elaboration of secondary 7000-series alloys. This process is affected by the initial content of Mg within molten Al, which decreases the surface tension of the molten metal and conversely increases the wettability of ZnO particles. The effect of initial Mg concentration on the aluminothermic reduction rate of ZnO was analyzed at the following values: 0.90wt%, 1.20wt%, 4.00t%, 4.25wt%, and 4.40wt%. The ZnO particles were incorporated by mechanical agitation using a graphite paddle inside a bath of molten Al maintained at a constant temperature of 1123 K and at a constant agitation speed of 250 r/min, the treatment time was 240 min and the ZnO particle size was 450-500 mesh. The results show an increase in Zn concentration in the prepared alloys up to 5.43wt% for the highest initial concentration of Mg. The reaction products obtained were characterized by scanning electron microscopy and X-ray diffraction, and the efficiency of the reaction was measured on the basis of the different concentrations of Mg studied.

  4. N-doped carbon@Ni-Al2O3 nanosheet array@graphene oxide composite as an electrocatalyst for hydrogen evolution reaction in alkaline medium

    Science.gov (United States)

    Wang, Juan; Qiu, Tian; Chen, Xu; Lu, Yanluo; Yang, Wensheng

    2015-10-01

    An NiAl-layered double-hydroxide (NiAl-LDH) nanosheet array is grown on a graphene oxide (GO) substrate (NiAl-LDH@GO) by the hydrothermal method. The NiAl-LDH@GO is used as the precursor to synthetize an N-doped carbon@Ni-Al2O3 nanosheet array@GO composite (N-C@Ni-Al2O3@GO) by coating with dopamine followed by calcination. The N-C@Ni-Al2O3@GO is used as a non-noble metal electrocatalyst for hydrogen evolution reaction in alkaline medium, and exhibits high electrocatalytic activity with low onset overpotential (-75 mV). The improved electrocatalytic performance of N-C@Ni-Al2O3@GO arises from its intrinsic features. First, it has a high specific surface area with the Ni nanoparticles in the composite dispersed well and the sizes of Ni nanoparticles are small, which lead to the exposure of more active sites for electrocatalysis. Second, there is a synergistic effect between the Ni nanoparticles and the N-C coating layer, which is beneficial to reduce the activation energy of the Volmer step and improve the electrocatalytic activity. Third, the N-C coating layer and the XC-72 additive can form an electrically conductive network, which serves as a bridge for the transfer of electrons from the electrode to the Ni nanoparticles.

  5. 中(碱)性造纸及其湿部化学助剂的发展趋势%an review of neutral/alkaline papermaking and the development trend of wet end Chemicals

    Institute of Scientific and Technical Information of China (English)

    朱勇强

    2009-01-01

    造纸湿部化学起源于七十年代,国外的造纸生产实践表明,造纸湿部化学的控制水平在很大的程度上取决了造纸生产线的质量和产量,而中性造纸在生产成本,产品质量,能耗,排污以及设备腐蚀等方面具有明显的经济优势,因此,世界性的纸张生产都在从酸性转向中性.本文综述了中性造纸环境中造纸助剂的选用与发展趋势.%Wet-end chemistry originated in the seventies, the practice of foreign countries shows that the quality and yield of paper-making production line rely on the paper wet end chemistry control in a large extent. Neutral papermaking in the production costs, product quality, energy consumption, sewage, as well as corrosion of equipment has obvious economic advantages, therefore, the world's paper production shifted from the neutral acid. The selection and development trends of paper chemicals for neutral paper-making was reviewed In this paper.

  6. Electro-oxidation of methanol in alkaline conditions using Pd–Ni nanoparticles prepared from organometallic precursors and supported on carbon vulcan

    Energy Technology Data Exchange (ETDEWEB)

    Manzo-Robledo, A., E-mail: amanzor@ipn.mx [UPALM, Laboratorio de Electroquímica y Corrosión, Escuela Superior de Ingeniería Química e Industrias Extractivas-IPN (Mexico); Costa, Natália J. S. [Universidade de São Paulo, Instituto de Química (Brazil); Philippot, K. [CNRS, LCC, Laboratoire de Chimie de Coordination (France); Rossi, Liane M. [Universidade de São Paulo, Instituto de Química (Brazil); Ramírez-Meneses, E. [Universidad Iberoamericana, Departamento de Ingeniería y Ciencias Químicas (Mexico); Guerrero-Ortega, L. P. A. [UPALM, Laboratorio de Electroquímica y Corrosión, Escuela Superior de Ingeniería Química e Industrias Extractivas-IPN (Mexico); Ezquerra-Quiroga, S. [Universidad Iberoamericana, Departamento de Ingeniería y Ciencias Químicas (Mexico)

    2015-12-15

    Oxidation of low-molecular weight alcohols as energy sources using metal nanoparticles has attracted considerable interest for use as a power source in portable electronic devices. In this work, a series of mono- and bimetallic nanoparticles based on palladium and nickel (Pd, Pd{sub 90}Ni{sub 10}, Pd{sub 50}Ni{sub 50}, Pd{sub 10}Ni{sub 90}, and Ni) have been synthesized from organometallic precursors, namely tris(dibenzylideneacetone) dipalladium(0), Pd{sub 2}(dba){sub 3}, and bis(1,5-cyclooctadiene)nickel(0), Ni(cod){sub 2}. Well-defined metal particles in the nanometric scale from 4.2 to 6.3 nm were observed by transmission electron microscopy. The as-prepared nanoparticles were mixed with a carbon Vulcan matrix (10 % wt. of the catalyst in turn) for investigation as electrocatalysts in methanol oxidation reaction (MOR) in alkaline conditions. The i–E profiles from cyclic voltammetry for the monometallic systems indicated a redox process attributed only to palladium or nickel, as expected. With the bimetallic nanomaterials, the redox process and the i–E characteristics are functions of the amount of nickel associated to palladium. From a fundamental point of view, it has been established that the OH ions’ interfacial interaction and the MOR kinetics are affected by the presence of nickel (decreasing the faradic current) as supported by the current versus potential profiles obtained as a function of methanol concentration and with temperature variation.

  7. APPLICATION OF MAGNETIC CATALYSTS TO THE CATALYTIC WET PEROXIDE OXIDATION (CWPO OF INDUSTRIAL WASTEWATER CONTAINING NON BIODEGRADABLE ORGANIC POLLUTANTS

    Directory of Open Access Journals (Sweden)

    Macarena Munoz

    2014-03-01

    Full Text Available A new ferromagnetic -Al2O3-supported iron catalyst has been prepared and its activity and stability have been compared with those of a previous iron-based conventional catalyst and with the traditional homogeneous Fenton process in the oxidation of chlorophenols. The use of solid catalysts improved significantly the efficiency on the use of H2O2, achieving higher mineralization degrees. The magnetic catalyst led to significantly higher oxidation rates than the conventional one due to the presence of both Fe (II and Fe (III. On the other hand, the use of a catalyst with magnetic properties is of interest, since it allows rapid recovery after treatment using a magnetic field. Moreover, it showed a high stability with fairly low iron leaching (<1% upon CWPO runs. An additional clear advantage of this new catalyst is its easy separation and recovery from the reaction medium by applying an external magnetic field.

  8. Reactivity of Nanostructured MnO_2 in Alkaline Medium Studied with a Microcavity Electrode: Effect of Oxidizing Agent

    Institute of Scientific and Technical Information of China (English)

    L.Benhaddad; L.Makhloufi; B.Messaoudi1; K.Rahmouni; H.Takenouti

    2011-01-01

    The synthesis of MnO2 powders by hydrothermal method with different oxidizing agents has been successfully achieved. The characterizations by scanning electron microscopy, energy-dispersive X-ray analyses, transmission electron microscopy, and X-ray diffraction techniques confirm the synthesis of nanostructured γ-MnO2 powders. The electrochemical reactivity of these powders in 1 mol/l KOH is investigated by cyclic voltammetry and electrochemical impedance spectroscopy (EIS) by using microcavity electrode. The results reveal that the MnO2 synthesized with Na2S2O8 shows the highest electrochemical reactivity in the test medium. This is due both to its large expanded surface area and its crystallographic variety γ-MnO2 formed in the matrix of ramsdellite, which is largely used as cathodic material for primary batteries. However, the presence of pyrolusite in the structure of γ-MnO2 synthesized with (NH4)2S2O8 decreases its electrochemical reactivity due to its narrow 1×1 size tunnel, which hinders the protons insertion.

  9. Investigation of Co3O4 nanorods supported Pd anode catalyst for methanol oxidation in alkaline solution

    Institute of Scientific and Technical Information of China (English)

    Yanbiao Ren; Shichao Zhang∗; Hua Fang; Xin Wei; Puheng Yang

    2014-01-01

    A Co3 O4 nanorod supported Pd electro-catalyst for the methanol electro-oxidation (MEO) has been fabricated by the combination of hydrother-mal synthesis and microwave-assisted polyol reduction processes. The crystallographic property and microstructure have been characterized using XRD, SEM and TEM. The results demonstrate that Pd nanoparticles (PdNPs) with a narrow particle size distribution (3−5 nm) are uni-formly deposited onto the surface of Co3O4 nanorods. Electrochemical measurements show that this catalyst having a larger electrochemically active surface area and a more negative onset-potential exhibits enhanced catalytic activity of 504 mA/mg Pd for MEO comparing with the Pd/C catalyst (448 mA/mg Pd). The dependency of logI against logv reveals that MEO on Pd-Co3O4 electrode is under a diffusion control. Electrochemical impedance spectroscopy (EIS) measurement agrees well with the CV results. The minimum charge transfer resistance of MEO on Pd-Co3 O4 is observed at−0.05 V, which coincides with the potential of MEO peak.

  10. Study of the electrochemical oxidation and reduction of C.I. Reactive Orange 4 in sodium sulphate alkaline solutions.

    Science.gov (United States)

    del Río, A I; Molina, J; Bonastre, J; Cases, F

    2009-12-15

    Synthetic solutions of hydrolysed C.I. Reactive Orange 4, a monoazo textile dye commercially named Procion Orange MX-2R (PMX2R) and colour index number C.I. 18260, was exposed to electrochemical treatment under galvanostatic conditions and Na2SO4 as electrolyte. The influence of the electrochemical process as well as the applied current density was evaluated. Ti/SnO2-Sb-Pt and stainless steel electrodes were used as anode and cathode, respectively, and the intermediates generated on the cathode during electrochemical reduction were investigated. Aliquots of the solutions treated were analysed by UV-visible and FTIR-ATR spectroscopy confirming the presence of aromatic structures in solution when an electro-reduction was carried out. Electro-oxidation degraded both the azo group and aromatic structures. HPLC measures revealed that all processes followed pseudo-first order kinetics and decolourisation rates showed a considerable dependency on the applied current density. CV experiments and XPS analyses were carried out to study the behaviour of both PMX2R and intermediates and to analyse the state of the cathode after the electrochemical reduction, respectively. It was observed the presence of a main intermediate in solution after an electrochemical reduction whose chemical structure is similar to 2-amino-1,5-naphthalenedisulphonic acid. Moreover, the analysis of the cathode surface after electrochemical reduction reveals the presence of a coating layer with organic nature.

  11. Wet Aerobic Oxidation of Lignin into Aromatic Aldehydes Catalysed by a Perovskite-type Oxide: LaFe1-xCuxO3 (x=0, 0.1, 0.2

    Directory of Open Access Journals (Sweden)

    Lu Lin

    2009-07-01

    Full Text Available The perovskite-type oxide catalyst LaFe1-xCuxO3 (x=0, 0.1, 0.2 was prepared by the sol–gel method, and tested as a catalyst in the wet aerobic oxidation (WAO of lignin into aromatic aldehydes. The lignin conversion and the yield of each aromatic aldehyde were significantly enhanced in the catalytic process, compared with the non-catalyzed process. Moreover, it was shown that the stability of activity and structure of LaFe1-xCuxO3 (x=0, 0.1, 0.2 remained nearly unchanged after a series of successive recyclings of the catalytic reactions, indicating it was an efficient and recyclable heterogeneous catalyst for the conversion of lignin into aromatic aldehydes in the WAO process.

  12. Reliable wet-chemical cleaning of natively oxidized high-efficiency Cu(In,Ga)Se2 thin-film solar cell absorbers

    Science.gov (United States)

    Lehmann, Jascha; Lehmann, Sebastian; Lauermann, Iver; Rissom, Thorsten; Kaufmann, Christian A.; Lux-Steiner, Martha Ch.; Bär, Marcus; Sadewasser, Sascha

    2014-12-01

    Currently, Cu-containing chalcopyrite-based solar cells provide the highest conversion efficiencies among all thin-film photovoltaic (PV) technologies. They have reached efficiency values above 20%, the same performance level as multi-crystalline silicon-wafer technology that dominates the commercial PV market. Chalcopyrite thin-film heterostructures consist of a layer stack with a variety of interfaces between different materials. It is the chalcopyrite/buffer region (forming the p-n junction), which is of crucial importance and therefore frequently investigated using surface and interface science tools, such as photoelectron spectroscopy and scanning probe microscopy. To ensure comparability and validity of the results, a general preparation guide for "realistic" surfaces of polycrystalline chalcopyrite thin films is highly desirable. We present results on wet-chemical cleaning procedures of polycrystalline Cu(In1-xGax)Se2 thin films with an average x = [Ga]/([In] + [Ga]) = 0.29, which were exposed to ambient conditions for different times. The hence natively oxidized sample surfaces were etched in KCN- or NH3-based aqueous solutions. By x-ray photoelectron spectroscopy, we find that the KCN treatment results in a chemical surface structure which is - apart from a slight change in surface composition - identical to a pristine as-received sample surface. Additionally, we discover a different oxidation behavior of In and Ga, in agreement with thermodynamic reference data, and we find indications for the segregation and removal of copper selenide surface phases from the polycrystalline material.

  13. Catalytic wet air oxidation of phenol over CeO2-TiO2 catalyst in the batch reactor and the packed-bed reactor.

    Science.gov (United States)

    Yang, Shaoxia; Zhu, Wanpeng; Wang, Jianbing; Chen, Zhengxiong

    2008-05-30

    CeO2-TiO2 catalysts are prepared by coprecipitation method, and the activity and stability in the catalytic wet air oxidation (CWAO) of phenol are investigated in a batch reactor and packed-bed reactor. CeO2-TiO2 mixed oxides show the higher activity than pure CeO2 and TiO2, and CeO2-TiO2 1/1 catalyst displays the highest activity in the CWAO of phenol. In a batch reactor, COD and TOC removals are about 100% and 77% after 120 min in the CWAO of phenol over CeO2-TiO2 1/1 catalyst at reaction temperature of 150 degrees C, the total pressure of 3 MPa, phenol concentration of 1000 mg/L, and catalyst dosage of 4 g/L. In a packed-bed reactor using CeO2-TiO2 1/1 particle catalyst, over 91% COD and 80% TOC removals are obtained at the reaction temperature of 140 degrees C, the air total pressure of 3.5 MPa, the phenol concentration of 1000 mg/L for 100 h continue reaction. Leaching of metal ions of CeO2-TiO2 1/1 particle catalyst is very low during the continuous reaction. CeO2-TiO2 1/1 catalyst exhibits the excellent activity and stability in the CWAO of phenol.

  14. Ni/MgAlO regeneration for catalytic wet air oxidation of an azo-dye in trickle-bed reaction.

    Science.gov (United States)

    Vallet, Ana; Ovejero, Gabriel; Rodríguez, Araceli; Peres, José A; García, Juan

    2013-01-15

    Active nickel catalysts (7 wt%) supported over Mg-Al mixed oxides have been recently developed and it has also been demonstrated that they are also highly selective in Catalytic Wet air Oxidation (CWAO) of dyes. CWAO of Chromotrope 2R (C2R) has been studied using a trickle bed reactor employing temperatures from 100 to 180 °C, liquid flow rates from 0.1 to 0.7 mL min(-1) and initial dye concentration from 10 to 50 ppm. Total pressure and air flow were 25 bar and 300 mL min(-1), respectively. The catalyst showed a very stable activity up to 24 h on stream with an average TOC conversion of 82% at 150 °C and T(r)=0.098 g(Ni) min mL(-1). After the reaction, a 1.1 wt% C of carbonaceous deposit is formed onto the catalyst and a diminution of 30% of the surface area with respect of the fresh catalyst was observed. An increase in the space time gave higher TOC conversions up to T(r)=0.098 g(Ni) min mL(-1), attaining values of 80% at 180 °C. The performance of TOC and dye removal does not decrease after two regeneration cycles. In total, a 57 h effective reaction has been carried out with no loss of catalytic activity.

  15. Degradation of cationic red GTL by catalytic wet air oxidation over Mo-Zn-Al-O catalyst under room temperature and atmospheric pressure.

    Science.gov (United States)

    Xu, Yin; Li, Xiaoyi; Cheng, Xiang; Sun, Dezhi; Wang, Xueye

    2012-03-06

    To overcome the drawback of catalytic wet air oxidation (CWAO) with high temperature and high pressure, the catalytic activity of Mo-Zn-Al-O catalyst for degradation of cationic red GTL under room temperature and atmospheric pressure was investigated. Mo-Zn-Al-O catalyst was prepared by coprecipitation and impregnation. XRD, TG-DTG, and XPS were used to characterize the resulting sample. Central composition design using response surface methodology was employed to optimize correlation of factors on the decolorization of cationic red GTL. The results show that the optimal conditions of pH value, initial concentration of dye and catalyst dosage were found to be 4.0, 85 mg/L and 2.72 g/L, respectively, for maximum decolorization of 80.1% and TOC removal of 50.9%. Furthermore, the reaction on the Mo-Zn-Al-O catalyst and degradation mechanism of cationic red GTL was studied by Electron spin resonance (ESR) and GC-MS technique. The possible reaction mechanism was that the Mo-Zn-Al-O catalyst can efficiently react with adsorbed oxygen/H(2)O to produce ·OH and (1)O(2) and finally induce the degradation of cationic red GTL. GC-MS analysis of the degradation products indicates that cationic red GTL was initiated by the cleavage of -N ═ N- and the intermediates were further oxidized by ·OH or (1)O(2).

  16. Microwave assisted catalytic wet air oxidation of H-acid in aqueous solution under the atmospheric pressure using activated carbon as catalyst.

    Science.gov (United States)

    Zhang, Yaobin; Quan, Xie; Chen, Shuo; Zhao, Yazhi; Yang, Fenglin

    2006-09-01

    Catalytic wet air oxidation (CWAO) is a promising method for the treatment of heavily contaminated wastewater. However, its application is restricted due to severe operation conditions (high pressure and high temperature). A microwave (MW) assisted oxidation method was investigated aiming to treat heavily contaminated wastewater under milder conditions. H-acid (1-amino-8-naphthol-3, 6-disulfonic acid) was selected as target compound to evaluate the performance of this novel process. The removal of H-acid and TOC (total organic carbon) for H-acid solution of 3000 mg/L reached as high as 92.6% in 20 min and 84.2% in 60 min, respectively under optimal conditions. The existence of activated carbon and oxygen proved to be critical for effective treatment. The activated carbon acted not only as a catalyst for H-acid decomposition, but also as a special material for the absorption of MW energy. Air was supplied to the reactor as an oxygen source at constant flows. The amino group in H-acid was converted ultimately into nitrate, and sulfonic group into sulfate. This observation gave an evidence of H-acid mineralization although other organic intermediates were unable to be determined. The value of BOD(5)/COD (ratio of 5d biochemical oxygen demand to chemical oxygen demand) increased from 0.008 to 0.467 indicating a significant improvement of biodegradability for the solution, which is beneficial for the further biological treatment of the wastewater.

  17. Wet oxidation of phenol on Ce{sub 1{minus}x}Cu{sub x}O{sub 2{minus}{delta}} catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Hocevar, S.; Batista, J. [National Inst. of Chemistry, Ljubljana (Slovenia). Lab. of Catalysis and Chemical Reaction Engineering; Levec, J. [National Inst. of Chemistry, Ljubljana (Slovenia). Lab. of Catalysis and Chemical Reaction Engineering]|[Univ. of Ljubljana (Slovenia). Dept. of Chemical Engineering

    1999-05-15

    Ce{sub 1{minus}x}Cu{sub x}O{sub 2{minus}{delta}} catalysts with 0.05 < x < 0.20 for catalytic wet oxidation of phenol in aqueous solutions have been synthesized using the coprecipitation method. The three most important synthesis parameters, the concentration of the mixed metal salt solution, the rate of coprecipitant addition and the stirrer speed during coprecipitation, were optimized with central composite design using the catalytic activity as a response function. The catalytic activity strongly depends on stirrer speed during coprecipitation. A high mutual dispersion of copper oxide and ceria, having the average crystallite size of about 9 nm, enhances solid solution formation. The unit cell parameter of ceria decreases when the overall concentration of copper in the catalyst increases, most probably obeying Vegard`s law. The catalysts proved to be very stable in hydrothermal reaction conditions at low pH values. After 5 h of reaction in the semibatch CST reactor less than 100 ppm of Cu was leached out of catalyst samples that were calcined in a flow of air for 2 h above 1033 K, and only a very low quantity of carbonaceous deposits were formed on the surface of the catalysts (0.6 wt%). The kinetics of phenol degradation could be interpreted by an equation valid for homogeneous autocatalytic reactions, in which the rate constant depends linearly on the heterogeneous catalyst (Cu) concentrations. This demonstrates that the reaction proceeds through a heterogeneous-homogeneous radical-branched chain mechanism.

  18. Influence of Ce, Nd, Sm and Gd oxides on the properties of alkaline-earth borosilicate glass sealant

    Directory of Open Access Journals (Sweden)

    Nibedita Sasmal

    2016-03-01

    Full Text Available In this study, the influence of CeO2, Nd2O3, Sm2O3 and Gd2O3 on various properties of the melt-quench route derived SrO–CaO–ZnO–B2O3–SiO2 glass have been investigated. Both the precursor glasses and heat treated glasses are characterized by dilatometry, differential scanning calorimetry (DSC, X-ray diffraction (XRD, field emission scanning electron microscopy (FESEM, Fourier transformed infrared spectroscopy (FTIR and X-ray photoelectron spectroscopy (XPS. The density and coefficient of thermal expansion of the glasses varies in the range 3.557–3.804 g cm−3 and 10.5–11.2 × 10−6 K−1 (50–800 °C respectively. Decrease in crystallization tendency with increase in cationic field strength of the ions is well supported by the increasing crystallization activation energy of the glasses calculated by Kissinger, Augis–Bennett and Ozawa models. XPS study revealed the presence of both Ce3+ and Ce4+ ions and an increase in characteristic binding energy of the respective rare earth elements from their core level studies. The Knoop hardness of the glasses varies in the range 6.03–6.28 GPa. The glass transition, glass softening and crystallization temperature; density and hardness of the glasses increased with increase in cationic field strength of the incorporated ions. The thermomechanical properties of the Gd2O3 containing glass advocate its applicability as the most promising sealant in solid oxide fuel cell.

  19. Catalytic wet peroxide oxidation of azo dye (Direct Blue 15) using solvothermally synthesized copper hydroxide nitrate as catalyst.

    Science.gov (United States)

    Zhan, Yuzhong; Zhou, Xiang; Fu, Bei; Chen, Yiliang

    2011-03-15

    Copper hydroxide nitrate (Cu(2)(OH)(3)NO(3)) was synthesized solvothermally in anhydrous ethanol and characterized by XRD, FTIR, TG-DTA and SEM. The peroxide degradation of an azo dye (Direct Blue 15) on this material was evaluated by examining catalyst loading, initial pH, hydrogen peroxide dosage, initial dye concentration and temperature. The leaching of Cu from the copper hydroxide nitrate during the reaction was also measured. The copper hydroxide nitrate synthesized solvothermally, which was of a novel spherical morphology with complex secondary structures and contained high-dispersed Cu(2)O impurity, showed good performance for oxidation degradation of the azo dye, especially high catalytic activity, high utilization of hydrogen peroxide and a wide pH range, whereas the copper hydroxide nitrate synthesized by the direct reaction of copper nitrate and sodium hydroxide showed low catalytic activity.

  20. Selective trans-membrane transport of alkali and alkaline earth cations through graphene oxide membranes based on cation-π interactions.

    Science.gov (United States)

    Sun, Pengzhan; Zheng, Feng; Zhu, Miao; Song, Zhigong; Wang, Kunlin; Zhong, Minlin; Wu, Dehai; Little, Reginald B; Xu, Zhiping; Zhu, Hongwei

    2014-01-28

    Graphene and graphene oxide (G-O) have been demonstrated to be excellent filters for various gases and liquids, showing potential applications in areas such as molecular sieving and water desalination. In this paper, the selective trans-membrane transport properties of alkali and alkaline earth cations through a membrane composed of stacked and overlapped G-O sheets ("G-O membrane") are investigated. The thermodynamics of the ion transport process reveal that the competition between the generated thermal motions and the interactions of cations with the G-O sheets results in the different penetration behaviors to temperature variations for the considered cations (K(+), Mg(2+), Ca(2+), and Ba(2+)). The interactions between the studied metal atoms and graphene are quantified by first-principles calculations based on the plane-wave-basis-set density functional theory (DFT) approach. The mechanism of the selective ion trans-membrane transportation is discussed further and found to be consistent with the concept of cation-π interactions involved in biological systems. The balance between cation-π interactions of the cations considered with the sp(2) clusters of G-O membranes and the desolvation effect of the ions is responsible for the selectivity of G-O membranes toward the penetration of different ions. These results help us better understand the ion transport process through G-O membranes, from which the possibility of modeling the ion transport behavior of cellular membrane using G-O can be discussed further. The selectivity toward different ions also makes G-O membrane a promising candidate in areas of membrane separations.

  1. Photo-Fenton oxidation of phenol and organochlorides (2,4-DCP and 2,4-D) in aqueous alkaline medium with high chloride concentration.

    Science.gov (United States)

    Luna, Airton J; Chiavone-Filho, Osvaldo; Machulek, Amilcar; de Moraes, José Ermírio F; Nascimento, Cláudio A O

    2012-11-30

    A highly concentrated aqueous saline-containing solution of phenol, 2,4-dichlorophenoxyacetic acid (2,4-D) and 2,4-dichlorophenol (2,4-DCP) was treated by the photo-Fenton process in a system composed of an annular reactor with a quartz immersion well and a medium-pressure mercury lamp (450 W). The study was conducted under special conditions to minimize the costs of acidification and neutralization, which are usual steps in this type of process. Photochemical reactions were carried out to investigate the influence of some process variables such as the initial concentration of Fe(2+) ([Fe(2+)](0)) from 1.0 up to 2.5 mM, the rate in mmol of H(2)O(2) fed into the system (FH(2)O(2);in) from 3.67 up to 7.33 mmol of H(2)O(2)/min during 120 min of reaction time, and the initial pH (pH(0)) from 3.0 up to 9.0 in the presence and absence of NaCl (60.0 g/L). Although the optimum pH for the photo-Fenton process is about 3.0, this particular system performed well in experimental conditions starting at alkaline and neutral pH. The results obtained here are promising for industrial applications, particularly in view of the high concentration of chloride, a known hydroxyl radical scavenger and the main oxidant present in photo-Fenton processes.

  2. Determination of a novel ACE inhibitor in the presence of alkaline and oxidative degradation products using smart spectrophotometric and chemometric methods

    Institute of Scientific and Technical Information of China (English)

    Maha Abdel-Monem Hegazy; Maya Shaaban Eissa; Osama Ibrahim Abd El-Sattar; Mohamed Mohamed Abd El-Kawy

    2014-01-01

    Simple, accurate, sensitive and validated UV spectrophotometric and chemometric methods were developed for the determination of imidapril hydrochloride (IMD) in the presence of both its alkaline (AKN) and oxidative (OXI) degradation products and in its pharmaceutical formulation. Method A is the fourth derivative spectra (D4) which allows the determination of IMD in the presence of both AKN and OXD, in pure form and in tablets by measuring the peak amplitude at 243.0 nm. Methods B, C and D, manipulating ratio spectra, were also developed. Method B is the double divisor-ratio difference spectrophotometric one (DD-RD) by computing the difference between the amplitudes of IMD ratio spectra at 232 and 256.3 nm. Method C is the double divisor-first derivative of ratio spectra method (DD-DR1) at 243.2 nm, while method D is the mean centering of ratio spectra (MCR) at 288.0 nm. Methods A, B, C and D could successfully determine IMD in a concentration range of 4.0-32.0 mg/mL. Methods E and F are principal component regression (PCR) and partial least-squares (PLS), respectively, for the simultaneous determination of IMD in the presence of both AKN and OXI, in pure form and in its tablets. The developed methods have the advantage of simultaneous determination of the cited components without any pre-treatment. The accuracy, precision and linearity ranges of the developed methods were determined. The results obtained were statistically compared with those of a reported HPLC method, and there was no significant difference between the proposed methods and the reported method regarding both accuracy and precision.

  3. 湿法烟气脱硫环境下亚硫酸钙的非催化氧化%NON-CATALYTIC OXIDATION KINETICS OF CALCIUM SULFITE IN WET LIMESTONE-GYPSUM FGD PROCESS

    Institute of Scientific and Technical Information of China (English)

    杜谦; 吴少华; 朱群益; 秦裕琨

    2003-01-01

    A study on non-catalytic oxidation kinetics of calcium sulfite is presented under typical conditions of wet flue gas desulfurization (FGD)in this paper. A laboratory-scale mechanically stirred tank reactor is used with continuous feed of both gas and liquid phase. The results show that increasing CaSO3 load from a lower value, the reaction rate increases and is limited by solid sulfite dissolution. The oxidation rate limitation is observed at loads exceeding certain concentration. The rate limitation is possibly caused by solid sulfite solubility or oxygen gas-liquid diffusion. The experimental conclusions are useful for design and operation of the holding tank in forced-oxidation wet FGD.

  4. Investigation of the catalytic wet peroxide oxidation of phenol over different types of Cu/ZSM-5 catalyst.

    Science.gov (United States)

    Valkaj, K Maduna; Katovic, A; Zrncević, S

    2007-06-18

    In this work oxidation of phenol with hydrogen peroxide on Cu/ZSM-5 catalysts was studied. The catalysts samples were prepared by two different methods: by ionic exchange from the protonic form of commercial ZSM-5 zeolite, and by direct hydrothermal synthesis. Characterization of the catalysts extends to X-ray diffraction (XRD), while the adsorption techniques were used for the measurement of the specific surface area. The catalytic tests were carried out in a stainless steel Parr reactor in batch operation mode at the atmospheric pressure and the temperature range from 50 to 80 degrees C. The mass ratio of the active metal component on the zeolite was in the range of 1.62-3.24 wt.%. for catalyst prepared by direct hydrothermal synthesis and 2.23-3.52 wt.% for catalyst prepared by ion exchange method. The initial concentration of phenol and hydrogen peroxide was 0.01 and 0.1 mol dm(-3), respectively. The influence of different methods of Cu/ZSM-5 preparation on their catalytic performance was monitored in terms of phenol conversion and degree of metal leached into aqueous solution.

  5. Reliable wet-chemical cleaning of natively oxidized high-efficiency Cu(In,Ga)Se{sub 2} thin-film solar cell absorbers

    Energy Technology Data Exchange (ETDEWEB)

    Lehmann, Jascha [Renewable Energies, Helmholtz-Zentrum Berlin für Materialien und Energie, Hahn-Meitner-Platz 1, 14109 Berlin (Germany); Potsdam Institute for Climate Impact Research (PIK), 14473 Potsdam (Germany); Lehmann, Sebastian, E-mail: sebastian.lehmann@ftf.lth.se [Renewable Energies, Helmholtz-Zentrum Berlin für Materialien und Energie, Hahn-Meitner-Platz 1, 14109 Berlin (Germany); Solid State Physics, Lund University, Box 118, S-22100 Lund (Sweden); Lauermann, Iver; Rissom, Thorsten; Kaufmann, Christian A.; Lux-Steiner, Martha Ch. [Renewable Energies, Helmholtz-Zentrum Berlin für Materialien und Energie, Hahn-Meitner-Platz 1, 14109 Berlin (Germany); Bär, Marcus, E-mail: marcus.baer@helmholtz-berlin.de [Renewable Energies, Helmholtz-Zentrum Berlin für Materialien und Energie, Hahn-Meitner-Platz 1, 14109 Berlin (Germany); Institut für Physik und Chemie, Brandenburgische Technische Universität Cottbus-Senftenberg, Platz der Deutschen Einheit 1, 03046 Cottbus (Germany); Sadewasser, Sascha, E-mail: sascha.sadewasser@inl.int [Renewable Energies, Helmholtz-Zentrum Berlin für Materialien und Energie, Hahn-Meitner-Platz 1, 14109 Berlin (Germany); International Iberian Nanotechnology Laboratory, Av. Mestre José Veiga s/n, 4715-330 Braga (Portugal)

    2014-12-21

    Currently, Cu-containing chalcopyrite-based solar cells provide the highest conversion efficiencies among all thin-film photovoltaic (PV) technologies. They have reached efficiency values above 20%, the same performance level as multi-crystalline silicon-wafer technology that dominates the commercial PV market. Chalcopyrite thin-film heterostructures consist of a layer stack with a variety of interfaces between different materials. It is the chalcopyrite/buffer region (forming the p-n junction), which is of crucial importance and therefore frequently investigated using surface and interface science tools, such as photoelectron spectroscopy and scanning probe microscopy. To ensure comparability and validity of the results, a general preparation guide for “realistic” surfaces of polycrystalline chalcopyrite thin films is highly desirable. We present results on wet-chemical cleaning procedures of polycrystalline Cu(In{sub 1-x}Ga{sub x})Se{sub 2} thin films with an average x = [Ga]/([In] + [Ga]) = 0.29, which were exposed to ambient conditions for different times. The hence natively oxidized sample surfaces were etched in KCN- or NH{sub 3}-based aqueous solutions. By x-ray photoelectron spectroscopy, we find that the KCN treatment results in a chemical surface structure which is – apart from a slight change in surface composition – identical to a pristine as-received sample surface. Additionally, we discover a different oxidation behavior of In and Ga, in agreement with thermodynamic reference data, and we find indications for the segregation and removal of copper selenide surface phases from the polycrystalline material.

  6. Characteristics of CuO-MoO3-P2O5 catalyst and its catalytic wet oxidation (CWO) of dye wastewater under extremely mild conditions.

    Science.gov (United States)

    Ma, Hongzhu; Zhuo, Qiongfang; Wang, Bo

    2007-11-01

    In order to develop a catalyst with high activity for catalytic wet oxidation (CWO) processing at lower temperatures (35 degrees C) and atmospheric pressure, a new CuO-MoO3-P2O5 catalystwas synthesized by a solid-state reaction method and was characterized by X-ray diffraction (XRD), Fourier transformation infrared spectrometer (FTIR), X-ray photoelectron spectroscopy (XPS), selected area electronic diffraction (SAED), scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDXS) for elemental mapping. Methylene blue (MB) was adopted to investigate the catalytic activity of CuO-MoO3-P2O5 in CWO processing. The results show that this new catalyst has a high catalytic activity to decolorize MB under mild condition. The color removal of MB (the initial concentration was 0.3 g L(-1) and initial pH was 5) can reach to 99.26% within 10 min at 35 degrees C and atmospheric pressure. Catalyst lifespan and selectivity were also tested, and the results show that after the catalyst was used three times, catalyst activity still remains. Selectivity testing shows that CuO-MoO3-P2O5 has high catalytic activity on degradation of MB, whereas this catalyst has less impact on methyl orange (the color removal was 99.65% for MB and 55% for methyl orange under the same conditions). According to the experimental results, a possible mechanism of catalytic degradation of MB was proposed.

  7. Damage-free back channel wet-etch process in amorphous indium-zinc-oxide thin-film transistors using a carbon-nanofilm barrier layer.

    Science.gov (United States)

    Luo, Dongxiang; Zhao, Mingjie; Xu, Miao; Li, Min; Chen, Zikai; Wang, Lang; Zou, Jianhua; Tao, Hong; Wang, Lei; Peng, Junbiao

    2014-07-23

    Amorphous indium-zinc-oxide thin film transistors (IZO-TFTs) with damage-free back channel wet-etch (BCE) process were investigated. A carbon (C) nanofilm was inserted into the interface between IZO layer and source/drain (S/D) electrodes as a barrier layer. Transmittance electron microscope images revealed that the 3 nm-thick C nanofilm exhibited a good corrosion resistance to a commonly used H3PO4-based etchant and could be easily eliminated. The TFT device with a 3 nm-thick C barrier layer showed a saturated field effect mobility of 14.4 cm(2) V(-1) s(-1), a subthreshold swing of 0.21 V/decade, an on-to-off current ratio of 8.3 × 10(10), and a threshold voltage of 2.0 V. The favorable electrical performance of this kind of IZO-TFTs was due to the protection of the inserted C to IZO layer in the back-channel-etch process. Moreover, the low contact resistance of the devices was proved to be due to the graphitization of the C nanofilms after annealing. In addition, the hysteresis and thermal stress testing confirmed that the usage of C barrier nanofilms is an effective method to fabricate the damage-free BCE-type devices with high reliability.

  8. Carbon and nitrogen removal from glucose-glycine melanoidins solution as a model of distillery wastewater by catalytic wet air oxidation.

    Science.gov (United States)

    Phuong Thu, Le; Michèle, Besson

    2016-06-05

    Sugarcane molasses distillery wastewater contains melanoidins, which are dark brown recalcitrant nitrogenous polymer compounds. Studies were carried out in batch mode to evaluate Pt and Ru supported catalysts in the Catalytic Wet Air Oxidation (CWAO) process of a synthetic melanoidins solution, prepared by stoichiometric reaction of glucose with glycine. The addition of a catalyst slightly improved TOC removal compared with the non-catalytic reaction, and especially promoted the conversion of ammonium produced from organically-bound nitrogen in melanoidins to molecular nitrogen and nitrate. The selectivity to N2 attained 89% in the presence of the Pt catalysts in the reaction conditions used (TOC=2200mgL(-1), TN=280mgL(-1), 0.5g catalyst loaded with 3% metal, 210°C, 70bar total air pressure). To avoid leaching of the active metal by organically-bound nitrogen, the reaction was very efficiently performed in a two-step reaction consisting in WAO to convert nitrogen into ammonium, before the introduction of a catalyst.

  9. Photocatalytic oxidation removal of Hg0 using ternary Ag/AgI-Ag2CO3 hybrids in wet scrubbing process under fluorescent light

    Science.gov (United States)

    Zhang, Anchao; Zhang, Lixiang; Chen, Xiaozhuan; Zhu, Qifeng; Liu, Zhichao; Xiang, Jun

    2017-01-01

    A series of ternary Ag/AgI-Ag2CO3 photocatalysts synthesized using a facile coprecipitation method were employed to investigate their performances of Hg0 removal in a wet scrubbing reactor. The hybrids were characterized by N2 adsorption-desorption, XRD, SEM-EDS, HRTEM, XPS, DRS and ESR. The photocatalytic activities of Hg0 removal were evaluated under fluorescent light. The results showed that AgI content, fluorescent light irradiation, reaction temperature all showed significant influences on Hg0 removal. NO exhibited significant effect on Hg0 removal in comparison to SO2. Among these ternary Ag/AgI-Ag2CO3 hybrids, Ag/AgI(0.1)-Ag2CO3 showed the highest Hg0 removal efficiency, which could be ascribed to the effective separation of photogenerated electron-hole pairs between AgI and Ag2CO3 and the surface plasmon resonance (SPR) effect in the visible region by metallic silver nanoparticles (Ag0 NPs). The trapping studies of reactive radicals showed that the superoxide radicals (rad O2-) may play a key role in Hg0 removal under fluorescent light. According to the experimental and characterization results, a possible photocatalytic oxidation mechanism for enhanced Hg0 removal over Ag/AgI(0.1)-Ag2CO3 hybrid under fluorescent light was proposed.

  10. Thermal and sonochemical synthesis of porous (Ce,Zr)O2 mixed oxides from metal β-diketonate precursors and their catalytic activity in wet air oxidation process of formic acid.

    Science.gov (United States)

    Cau, Camille; Guari, Yannick; Chave, Tony; Larionova, Joulia; Nikitenko, Sergey I

    2014-07-01

    Porous (Ce0.5Zr0.5)O2 solid solutions were prepared by thermolysis (T=285 °C) or sonolysis (20 kHz, I=32 W cm(-2), Pac=0.46 W mL(-1), T=200 °C) of Ce(III) and Zr(IV) acetylacetonates in oleylamine or hexadecylamine under argon followed by heat treatment of the precipitates obtained in air at 450 °C. Transmission Electron Microscopy images of the samples show nanoparticles of ca. 4-6 nm for the two synthetic approaches. The powder X-ray diffraction, scanning electron microscopy, energy dispersive X-ray and μ-Raman spectroscopy of solids obtained after heat treatment indicate the formation of (Ce0.5Zr0.5)O2 solid solutions with a metastable tetragonal crystal structure for the two synthetic routes. The specific surface area of the samples varies between 78 and 149 m(2) g(-1) depending on synthesis conditions. The use of Barrett-Joyner-Halenda and t-plot methods reveal the formation of mixed oxides with a hybrid morphology that combines mesoporosity and microporosity regardless of the method of preparation. Platinum nanoparticles were deposited on the surface of the mixed oxides by sonochemical reduction of Pt(IV). It was found that the materials prepared by sonochemistry exhibit better resistance to dissolution during the deposition process of platinum. X-ray photoelectron spectroscopy analysis shows the presence of Pt(0) and Pt(II) on the surface of mixed oxides. Porous (Ce0.5Zr0.5)O2 mixed oxides loaded with 1.5%wt. platinum exhibit high activity in catalytic wet air oxidation of formic acid at 40 °C.

  11. Photocatalytic oxidation of nitric oxide from simulated flue gas by wet scrubbing using ultraviolet/TiO2/H2O2 process

    Institute of Scientific and Technical Information of China (English)

    张波; 仲兆平; 付宗明

    2015-01-01

    Nitric oxide (NO) from flue gas is hard to remove because of low solubility and reactivity. A new technology for photocatalytic oxidation of NO using ultraviolet (UV)/TiO2/H2O2 process is studied in an efficient laboratory-scale reactor. Effects of several key operational parameters on NO removal efficiency are studied, including TiO2 content, H2O2 initial concentration, UV lamp power, NO initial content, oxygen volume fraction and TiO2/H2O2 solution volume. The results illustrate that the NO removal efficiency increases with the increasing of H2O2 initial concentration or UV lamp power. Meanwhile, a lower NO initial content or a higher TiO2/H2O2 solution volume will result in higher NO removal efficiency. In addition, oxygen volume fraction has a little effect. The highest NO removal efficiency is achieved at the TiO2 content of 0.75 g/L, H2O2 initial concentration of 2.5 mol/L, UV lamp power of 36 W, NO initial content of 206×10−6 and TiO2/H2O2 solution volume of 600 mL. It is beneficial for the development and application of NO removal from coal-fired flue gas with UV/TiO2/H2O2 process.

  12. Comparative study of supported CuOx and MnOx catalysts for the catalytic wet air oxidation of β-naphthol

    Science.gov (United States)

    Liu, Jie; Yu, Chaoying; Zhao, Peiqing; Chen, Gexin

    2012-09-01

    MnOx/nano-TiO2, MnOx/Al2O3-TiO2 (Al-Ti), CuOx/nano-TiO2 and CuOx/Al-Ti were prepared and their application in catalytic wet air oxidation (CWAO) of β-naphthol were investigated. The catalysts had been characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and temperature-programmed reduction (TPR) measurements. Phases of CuO, Cu2O, CuAl2O4, MnO2 and Mn2O3 could be found on the surface of the aforementioned catalysts. Significant differences in activities were observed among the prepared catalysts. Compared to CuOx/nano-TiO2, the combined action of highly dispersed CuO as well as CuAl2O4 of CuOx/Al-Ti helped to achieve higher activity for the CWAO of β-naphthol, while the Cu2O component lead to lower efficiency of CuOx/nano-TiO2. On the surface of MnOx/nano-TiO2, both the larger amount of highly dispersed MnO2 and the stronger electron transfer between MnO2 and Mn2O3 were helpful to promote the activity for the degradation of β-naphthol. However, the higher amount of bulk MnO2 and the weaker electron transfer for MnOx/Al-Ti were unfavorable to increase its efficiency. Among the four catalysts as-prepared, MnOx/nano-TiO2 was identified the highest activity with 93.7% COD removal.

  13. The optimization, kinetics and mechanism of m-cresol degradation via catalytic wet peroxide oxidation with sludge-derived carbon catalyst.

    Science.gov (United States)

    Wang, Yamin; Wei, Huangzhao; Zhao, Ying; Sun, Wenjing; Sun, Chenglin

    2017-03-15

    The sludge-derived carbon catalyst modified with 0°C HNO3 solution was tested in catalytic wet peroxide oxidation of m-cresol (100mgL(-1)) with systematical mathematical models and theoretical calculation for the first time. The reaction conditions were optimized by response surface methodology (RSM) as T=60°C, initial pH=3.0, C0,H2O2(30%)=1.20gL(-1) (lower than the stoichiometric amount of 1.80gL(-1)) and Ccat=0.80gL(-1), with 96% of m-cresol and 47% of TOC converted after 16min and 120min of reaction, respectively, and ξ (mg TOC/g H2O2 fed)=83.6mg/g. The end time of the first kinetic period in m-cresol model was disclosed to be correlated with the fixed residue m-cresol concentration of about 33%. Furthermore, the kinetic constants in models of TOC and H2O2 exactly provide convincing proof of three-dimensional response surfaces analysis by RSM, which showed the influence of the interaction between organics and H2O2 on effective H2O2 utilization. The reaction intermediates over time were identified by gas chromatography-mass spectrometer based on kinetics analysis. Four degradation pathways for m-cresol were proposed, of which the possibility and feasibility were well proven by frontier molecule orbital theory and atomic charge distribution via density functional theory method.

  14. 陶瓷-活性炭球为载体的CWAO催化剂%Ceramic-activated carbon sphere supported catalyst for catalytic wet air oxidation(CWAO)

    Institute of Scientific and Technical Information of China (English)

    刘卫民

    2012-01-01

    Ceramic-activated carbon sphere as support of ruthenium catalysts were evaluated through the catalytic wet air oxidation(CWAO) of resin effluent.The effects of the preparation conditions,such as ceramic-activated carbon sphere support,Ru loading,macro-pore diameter of ceramic sphere,etc.on the catalytic activity and stability were investigated.The results show that the catalytic activity varies according to the following order: Ru/KC-120 Ru/KC-80 Ru/KC-60 KC-120 without catalysts.It is found that the 3% Ru/KC-120 catalyst displayed highest stability in the CWAO of resin effluent during 120 min.Chemical oxygen demand(COD) and phenol removal were about 91% and 96%,respectively,at the reaction temperature of 200℃,oxygen pressure of 1.5 MPa.%以陶瓷-活性炭球为载体制备载Ru催化剂,用于催化湿式氧化(CWAO)法处理酚醛树脂废水,考察了陶瓷-活性炭球载体、Ru负载量和陶瓷球宏孔孔径等对催化剂的催化活性和稳定性的影响。实验结果表明,催化剂催化活性的顺序为:Ru/KC-120〉Ru/KC-80〉Ru/KC-60〉KC-120〉无催化剂。在200℃,氧气分压为1.5 MPa等条件下,催化湿式氧化酚醛树脂废水,3%Ru/KC-120催化剂表现良好的催化活性与稳定性,在120 min内,COD和苯酚去除率分别达到91%和96%。

  15. Abatement of phenolic mixtures by catalytic wet oxidation enhanced by Fenton's pretreatment: effect of H2O2 dosage and temperature.

    Science.gov (United States)

    Santos, A; Yustos, P; Rodriguez, S; Simon, E; Garcia-Ochoa, F

    2007-07-31

    Catalytic wet oxidation (CWO) of a phenolic mixture containing phenol, o-cresol and p-cresol (500mg/L on each pollutant) has been carried out using a commercial activated carbon (AC) as catalyst, placed in a continuous three-phase reactor. Total pressure was 16 bar and temperature was 127 degrees C. Pollutant conversion, mineralization, intermediate distribution, and toxicity were measured at the reactor outlet. Under these conditions no detoxification of the inlet effluent was found even at the highest catalyst weight (W) to liquid flow rate (Q(L)) ratio used. On the other hand, some Fenton Runs (FR) have been carried out in a batch way using the same phenolic aqueous mixture previously cited. The concentration of Fe(2+) was set to 10mg/L. The influence of the H(2)O(2) amount (between 10 and 100% of the stoichiometric dose) and temperature (30, 50, and 70 degrees C) on phenols conversion, mineralization, and detoxification have been analyzed. Phenols conversion was near unity at low hydrogen peroxide dosage but mineralization and detoxification achieved an asymptotic value at each temperature conditions. The integration of Fenton reagent as pretreatment of the CWO process remarkably improves the efficiency of the CWO reactor and allows to obtain detoxified effluents at mild temperature conditions and relatively low W/Q(L) values. For a given phenolic mixture a temperature range of 30-50 degrees C in the Fenton pretreatment with a H(2)O(2) dosage between 20 and 40% of the stoichiometric amount required can be proposed.

  16. Integrated catalytic wet air oxidation and aerobic biological treatment in a municipal WWTP of a high-strength o-cresol wastewater.

    Science.gov (United States)

    Suarez-Ojeda, María Eugenia; Guisasola, Albert; Baeza, Juan A; Fabregat, Azael; Stüber, Frank; Fortuny, Agustí; Font, Josep; Carrera, Julián

    2007-02-01

    This study examines the feasibility of coupling a Catalytic Wet Air Oxidation (CWAO), with activated carbon (AC) as catalyst, and an aerobic biological treatment to treat a high-strength o-cresol wastewater. Two goals are pursued: (a) To determine the effect of the main AC/CWAO intermediates on the activated sludge of a municipal WasteWater Treatment Plant (WWTP) and (b) To demonstrate the feasibility of coupling the AC/CWAO effluent as a part of the influent of a municipal WWTP. In a previous study, a high-strength o-cresol wastewater was treated by AC/CWAO aiming to establish the distribution of intermediates and the biodegradability enhancement. In this work, the biodegradability, toxicity and inhibition of the most relevant intermediates detected in the AC/CWAO effluent were determined by respirometry. Also, the results of a pilot scale municipal WWTP study for an integrated AC/CWAO-aerobic biological treatment of this effluent are presented. The biodegradation parameters (i.e. maximum oxygen uptake rate and oxygen consumption) of main AC/CWAO intermediates allowed the classification of the intermediates into readily biodegradable, inert or toxic/inhibitory compounds. This detailed study, allowed to understand the biodegradability enhancement exhibited by an AC/CWAO effluent and to achieve a successful strategy for coupling the AC/CWAO step with an aerobic biological treatment for a high-strength o-cresol wastewater. Using 30%, as COD, of AC/CWAO effluent in the inlet to the pilot scale WWTP, the integrated AC/CWAO-biological treatment achieved a 98% of total COD removal and, particularly, a 91% of AC/CWAO effluent COD removal without any undesirable effect on the biomass.

  17. Cu/TiO2催化湿式氧化甲醛废水%CATALYTIC WET AIR OXIDATION OF FORMALDEHYDE BY Cu/TiO2

    Institute of Scientific and Technical Information of China (English)

    李艳; 张科军; 杜青; 章飞芳; 顾江萍; 梁鑫淼

    2012-01-01

    Formaldehyde wastewater would destroy ecological system and influence human health when discharging the wastewater into the water body. This study mainly focused on the degradation of formaldehyde wastewater by catalytic wet air oxidation (CWAO) with the self-prepared Cu/TiO2 as catalyst. After optimizing the reaction conditions, Total Organic Carbon (TOC) removal reached 85% and the toss of Cu2+ and Ti4+ was very low under 180X?, pH=5, 0.5MPa with 6 g/L catalyst after 2 h reaction. Finally, mcthanol in formaldehyde solution and the degradation products formic acid were detected Results demonstrated that CWAO with Cu/TiO] as catalyst could remove formaldehyde in wastewater efficiently.%甲醛废水排放入水体后,破坏生态系统,影响人们的身体健康.考察了以自制的Cu/TiO2为催化剂,用催化湿式氧化的方法降解甲醛废水的情况.通过优化反应条件,在180℃、pH=5、0.5 MPa、催化剂量为6g/L时反应2h,TOC的去除率高达85%且Cu2+和TP4+基本没有流失.此外还检测了甲醛溶液中甲醇变化情况和经处理后甲醛废水的降解产物甲酸.结果表明,以Cu/TiO2为催化剂的催化湿式氧化能有效地降解甲醛废水.

  18. Investigation on preparation of CuO-SnO2-CeO2/γ-Al2O3 catalysts for catalytic wet air oxidation process and their catalytic activity for degradation of phenol

    Institute of Scientific and Technical Information of China (English)

    SUN Xiao-jun; ZHANG Mi-lin; WAN Jia-feng; XIA Zhi; LIU Xiao-hui; LIU hui

    2008-01-01

    Catalytic Wet Air Oxidation process is an efficient measure for treatment of wastewater with great strength which is not biodegradable. Heterocatalysts now become the key investigation subject of catalytic wet air oxidation process due to their good stability and easy separation. In the paper, CuO-SnOE-CeO2/γ-Al2O3 catalysts are prepared by impregnation method, with SnO2 as a doping component, CuO as an active component, CeO2 as a structure stabilizer, γ-Al2O3 as a substrate. XPS test is carried out to investigate the effect of Sn on the chemical surrounding of Cu and O element on the catalyst surface and their catalytic activity. It is shown that the right do-ping of Sn can increase Cu+ content on the catalyst surface, as a result the quantity of adsorption oxygen is also increased. It is found that Cu + content on the catalyst surface is one of the primary factors that determin catalytic activity of catalyst through analyzing the catalytic wet air oxidation process of phenol.

  19. Assessment and development of an industrial wet oxidation system for burning waste and low upgrade fuels. Final report, Phase 2B: Pilot demonstration of the MODAR supercritical water oxidation process

    Energy Technology Data Exchange (ETDEWEB)

    1994-01-01

    Stone & Webster Engineering Corporation is Project Manager for the Development and Demonstration of an Industrial Wet Oxidation System for Burning Wastes and Low Grade Fuel. This program has been ongoing through a Cooperative Agreement sponsored by the Department of Energy, initiated in June 1988. This report presents a comprehensive discussion of the results of the demonstration project conducted under this cooperative agreement with the overall goal of advancing the state-of-the-art in the practice of Supercritical Water Oxidation (SCWO). In recognition of the Government`s support of this project, we have endeavored to include all material and results that are not proprietary in as much detail as possible while still protecting MODAR`s proprietary technology. A specific example is in the discussion of materials of construction where results are presented while, in some cases, the specific materials are not identified. The report presents the results chronologically. Background material on the earlier phases (Section 2) provide an understanding of the evolution of the program, and bring all reviewers to a common starting point. Section 3 provides a discussion of activities from October 1991 through July 1992, during which the pilot plant was designed; and various studies including computational fluid dynamic modeling of the reactor vessel, and a process HAZOP analyses were conducted. Significant events during fabrication are presented in Section 4. The experimental results of the test program (December 1992--August 1993) are discussed in Section 5.

  20. Using δ15 N- and δ18 O-NO to Evaluate Mechanisms of Nitric Oxide Production Following the Wetting of Dry Soil

    Science.gov (United States)

    Homyak, P. M.; Schimel, J.; Sickman, J. O.

    2014-12-01

    In xeric environments, where soils can remain dry for more than 6 months, abrupt transitions from dry-to-wet conditions produce NO pulses within seconds after soils wet up. During these periods of intense gaseous N production, biological processes (nitrification and denitrification) are known to control NO fluxes, but it is not clear how soil microbes can recover from drought-induced stress within seconds after soils wet up. Are NO pulses immediately following rewetting more so controlled by abiotic NO-producing reactions? Because biotic and abiotic mechanisms can occur simultaneously, distinguishing between these processes can be problematic. To understand the contribution of biotic and abiotic processes to NO pulses, and to better inform biogeochemical models, we measured the δ15N- and δ18O-NO following a field soil rewetting experiment in a California annual grassland. In October, during the end of the dry season, we artificially watered soils and captured NO emissions for up to 15 minutes, 1 hour, 1 day, and 3 days after wet-up. Pulses of NO following the wetting of dry soil were explained by a two-component mixing model, where two distinct sources or processes produced NO. Within 15 minutes after soil wet-up, the isotopic composition of soil NO (δ15N =-8.95 ‰, δ18O=14.28 ‰) was similar to that of atmospheric samples (δ15N =-4.45 ‰, δ18O=15.20 ‰), but became increasingly depleted after 1 hour (δ15N =-21.08 ‰, δ18O=0.53 ‰), and more so after 1 day (δ15N =-37.44 ‰, δ18O=-9.45 ‰). After 3 days, the isotopic composition of NO (δ15N =-28.31 ‰, δ18O=-2.07 ‰) began to return to pre-wet-up conditions closely following the two-component mixing line. We conclude that NO-producing reactions immediately after the wetting of dry soil (up to 15 min) are different than those occurring after 1 hour post-wetting. We hypothesize that abiotic processes control the initial response to wetting, but that biological processes, which discriminate

  1. 采用碱性加压氧化浸出从高铋铅阳极泥中脱除砷锑%Arsenic and antimony removal from bismuth-rich lead anode slime by alkaline pressure oxidation leaching

    Institute of Scientific and Technical Information of China (English)

    李阔; 徐瑞东; 何世伟; 陈汉森; 朱云; 华宏全; 舒波

    2015-01-01

    在碱性溶液中釆用加压氧化浸出对高铋铅阳极泥进行脱除砷锑的研究。考察氧化剂用量、氢氧化钠浓度、液固比、碱浸温度及反应时间对铅阳极泥脱砷、锑效果的影响,优选得到较佳的工艺条件,砷、锑的浸出率分别达到95%和80%以上。碱浸液冷却过滤结晶砷酸钠和锑酸铅后,采用过氧化氢进行沉锑处理,沉锑后的溶液再补加定量的氢氧化钠后能够返回浸出工艺,实现碱浸液的循环利用,并保证砷、锑的有效脱除。%The arsenic and antimony were removed from bismuth-rich lead anode slime by alkaline pressure oxidation leaching. The effects of factors including oxidant dosage, NaOH concentration, ratio of liquid to solid, leaching temperature and leaching time on the arsenic and antimony removal were investigated, and the optimal process conditions were determined by experiments. The results show that the leaching rate of arsenic and antimony can reach over 95% and 80%, respectively. The removal of antimony can be realized by adding hydrogen peroxide after the removal of crystal sodium arsenate and lead antimonate by cooling and filtration. The alkaline leaching solution is returned to the leaching process after adding quantitative sodium hydroxide, which achieves the recycling of alkaline solution and the effective separation of arsenic and antimony from other metals.

  2. DESTRUCTION OF TETRAPHENYLBORATE IN TANK 48H USING WET AIR OXIDATION BATCH BENCH SCALE AUTOCLAVE TESTING WITH ACTUAL RADIOACTIVE TANK 48H WASTE

    Energy Technology Data Exchange (ETDEWEB)

    Adu-Wusu, K; Paul Burket, P

    2009-03-31

    Wet Air Oxidation (WAO) is one of the two technologies being considered for the destruction of Tetraphenylborate (TPB) in Tank 48H. Batch bench-scale autoclave testing with radioactive (actual) Tank 48H waste is among the tests required in the WAO Technology Maturation Plan. The goal of the autoclave testing is to validate that the simulant being used for extensive WAO vendor testing adequately represents the Tank 48H waste. The test objective was to demonstrate comparable test results when running simulated waste and real waste under similar test conditions. Specifically: (1) Confirm the TPB destruction efficiency and rate (same reaction times) obtained from comparable simulant tests, (2) Determine the destruction efficiency of other organics including biphenyl, (3) Identify and quantify the reaction byproducts, and (4) Determine off-gas composition. Batch bench-scale stirred autoclave tests were conducted with simulated and actual Tank 48H wastes at SRNL. Experimental conditions were chosen based on continuous-flow pilot-scale simulant testing performed at Siemens Water Technologies Corporation (SWT) in Rothschild, Wisconsin. The following items were demonstrated as a result of this testing. (1) Tetraphenylborate was destroyed to below detection limits during the 1-hour reaction time at 280 C. Destruction efficiency of TPB was > 99.997%. (2) Other organics (TPB associated compounds), except biphenyl, were destroyed to below their respective detection limits. Biphenyl was partially destroyed in the process, mainly due to its propensity to reside in the vapor phase during the WAO reaction. Biphenyl is expected to be removed in the gas phase during the actual process, which is a continuous-flow system. (3) Reaction byproducts, remnants of MST, and the PUREX sludge, were characterized in this work. Radioactive species, such as Pu, Sr-90 and Cs-137 were quantified in the filtrate and slurry samples. Notably, Cs-137, boron and potassium were shown as soluble as a

  3. The Adsorption and Oxidation of Isopropanol at Platinum Electrode in Alkaline Media%碱性介质中异丙醇在铂电极表面的吸附和电化学氧化

    Institute of Scientific and Technical Information of China (English)

    林珩; 陈国良; 郑子山; 周建章; 陈声培; 林仲华

    2005-01-01

    运用电化学循环伏安、原位FTIR反射光谱和石英晶体微天平(EQCM)等方法研究了碱性介质中异丙醇在Pt电极表面吸附和氧化行为.结果表明:碱性介质中异丙醇电氧化过程不存在自毒化现象.虽然电化学原位FTIR反射光谱未能检测到CO等毒性物种,但EQCM结果证明异丙醇或其解离产物吸附于铂电极上.在实验条件下,碱性介质中异丙醇在铂电极上氧化的最终产物只有丙酮,预示着碱性介质中异丙醇通过脱氢步骤氧化成丙酮.EQCM研究还从电极表面质量定量变化的角度提供了异丙醇吸附和电氧化反应机理的新数据.%The adsorption and oxidation of isopropanol in alkaline media at platinum electrode have been investigated by using electrochemical quartz crystal microbalance (EQCM) and in situ FTIR spectroscopy. The results show thatthere is no self-poisoning in the electrooxidation of isopropanol in alkaline media. Though no poison species, such as CO, are evidenced by in situ FTIR spectroscopy, the adsorption of isopropanol or its dissociative products on Pt surface is suggested by EQCM data. The final product of isopropanol oxidation is only acetone under experimental condition, which suggests that the oxidation of isopropanol into acetone takes place via dehydrogenation step. The EQCM studies provide quantitative results of surface mass variation and have thrown new light in the elucidating isopropanol oxidation.

  4. Wetting in Color

    Science.gov (United States)

    Burgess, Ian Bruce

    Colorimetric litmus tests such as pH paper have enjoyed wide commercial success due to their inexpensive production and exceptional ease of use. However, expansion of colorimetry to new sensing paradigms is challenging because macroscopic color changes are seldom coupled to arbitrary differences in the physical/chemical properties of a system. In this thesis I present in detail the development of Wetting in Color Technology, focusing primarily on its application as an inexpensive and highly selective colorimetric indicator for organic liquids. The technology exploits chemically-encoded inverse-opal photonic crystals to control the infiltration of fluids to liquid-specific spatial patterns, projecting minute differences in liquids' wettability to macroscopically distinct, easy-to-visualize structural color patterns. It is shown experimentally and corroborated with theoretical modeling using percolation theory that the high selectivity of wetting, upon-which the sensitivity of the indicator relies, is caused by the highly symmetric structure of our large-area, defect-free SiO2 inverse-opals. The regular structure also produces a bright iridescent color, which disappears when infiltrated with liquid - naturally coupling the optical and fluidic responses. Surface modification protocols are developed, requiring only silanization and selective oxidation, to facilitate the deterministic design of an indicator that differentiates a broad range of liquids. The resulting tunable, built-in horizontal and vertical chemistry gradients allow the wettability threshold to be tailored to specific liquids across a continuous range, and make the readout rely only on countable color differences. As wetting is a generic fluidic phenomenon, Wetting in Color technology could be suitable for applications in authentication or identification of unknown liquids across a broad range of industries. However, the generic nature of the response also ensures chemical non-specificity. It is shown

  5. Survival of prokaryotes in a polluted waste dump during remediation by alkaline hydrolysis.

    Science.gov (United States)

    Nielsen, Marie Bank; Kjeldsen, Kasper Urup; Lever, Mark Alexander; Ingvorsen, Kjeld

    2014-04-01

    A combination of culture-dependent and culture-independent techniques was used to characterize bacterial and archaeal communities in a highly polluted waste dump and to assess the effect of remediation by alkaline hydrolysis on these communities. This waste dump (Breakwater 42), located in Denmark, contains approximately 100 different toxic compounds including large amounts of organophosphorous pesticides such as parathions. The alkaline hydrolysis (12 months at pH >12) decimated bacterial and archaeal abundances, as estimated by 16S rRNA gene-based qPCR, from 2.1 × 10(4) and 2.9 × 10(3) gene copies per gram wet soil respectively to below the detection limit of the qPCR assay. Clone libraries constructed from PCR-amplified 16S rRNA gene fragments showed a significant reduction in bacterial diversity as a result of the alkaline hydrolysis, with preferential survival of Betaproteobacteria, which increased in relative abundance from 0 to 48 %. Many of the bacterial clone sequences and the 27 isolates were related to known xenobiotic degraders. An archaeal clone library from a non-hydrolyzed sample showed the presence of three main clusters, two representing methanogens and one representing marine aerobic ammonia oxidizers. Isolation of alkalitolerant bacterial pure cultures from the hydrolyzed soil confirmed that although alkaline hydrolysis severely reduces microbial community diversity and size certain bacteria survive a prolonged alkaline hydrolysis process. Some of the isolates from the hydrolyzed soil were capable of growing at high pH (pH 10.0) in synthetic media indicating that they could become active in in situ biodegradation upon hydrolysis.

  6. Investigation of ruthenium promoted palladium catalysts for methanol electrooxidation in alkaline media

    Science.gov (United States)

    Jurzinsky, Tilman; Kammerer, Patricia; Cremers, Carsten; Pinkwart, Karsten; Tübke, Jens

    2016-01-01

    In this study, the investigation of binary palladium based electrocatalysts for methanol oxidation in alkaline media is reported. For this purpose, electrocatalysts with a loading of 20wt% metal on VulcanXC72-R were synthesized via wet chemical reduction with various compositions of palladium and ruthenium. Physical characterization via transmission electron microscopy (TEM), thermogravimetric analysis (TGA) and inductively coupled plasma optical emission spectroscopy (ICP-OES) was done and verified the synthesis of nanoparticles on carbon support. Electrochemical evaluation of the catalytic behavior of Pd/C, Ru/C and PdXRu/C (X = 1, 3, 5) via cyclic voltammetry and chronoamperometry was conducted in a 3-electrode setup. These measurements suggested that Pd3Ru/C is a promising material for methanol oxidation reaction in alkaline media with an onset potential of 0.465 VRHE and a peak current density of over 1 A mg-1Pd. To further investigate the oxidation of methanol on Pd/C and Ru promoted catalysts, differential electrochemical mass spectrometry (DEMS) measurements were done. From these results a higher CO2 current efficiency (CCE) of 86% for Pd3Ru/C compared to 65% for Pd/C was found. Moreover, fuel cell tests verified the results and showed that Pd3Ru/C has the better performance.

  7. Anodes for alkaline electrolysis

    Science.gov (United States)

    Soloveichik, Grigorii Lev

    2011-02-01

    A method of making an anode for alkaline electrolysis cells includes adsorption of precursor material on a carbonaceous material, conversion of the precursor material to hydroxide form and conversion of precursor material from hydroxide form to oxy-hydroxide form within the alkaline electrolysis cell.

  8. Chemical characterization of insoluble macromolecules (kerogen) from marine and lacustrine sediments. Molecular distribution of aliphatic dicarboxylic acids in alkaline KMnO4 oxidation products; Kaiyo oyobi konuma taisekibutsuchu no fuyosei yukibutsu (kerogen) no characterization

    Energy Technology Data Exchange (ETDEWEB)

    Morinaga, S.; Ishiwatari, R.; Machihara, T. [The University of Tokyo, Tokyo (Japan). Faculty of Science

    1996-04-15

    The insoluble macromolecules (kerogen) in marine and lacustrine sediments was oxidated by alkaline KMnO4, and the kerogen was characterized by molecular distribution of produced aliphatic dicarboxylic acids. Seven seas and ten lakes in the world are used as a sample. The oxidation products consist of n-C4-C15 {alpha}, {omega}-dicarboxylic acids, n-C7-C28 mono-carboxylic acids, and benzene carboxylic acids. The dicarboxylic acid decreases from C4 to C15 for the marine kerogen and has a maximum at C8 to C9 for the lacustrine kerogen. The method for representing the molecular distribution by two mathematical expressions was proposed. The marine and lacustrine kerogens are classified into different groups, and the sample of an eruption bay is located between the two kerogens. The polymerized structure of polyhydoroxy acids in these kerogens is assumed to have been transformed into aliphatic dicarboxylic acids by oxidation. This is also backed up by the result of cutin oxidation. 38 refs., 4 figs., 4 tags.

  9. Modeled Wet Nitrate Deposition

    Data.gov (United States)

    U.S. Environmental Protection Agency — Modeled data on nitrate wet deposition was obtained from Dr. Jeff Grimm at Penn State Univ. Nitrate wet depostion causes acidification and eutrophication of surface...

  10. Titratable Acidity and Alkalinity of Red Soil Surfaces

    Institute of Scientific and Technical Information of China (English)

    SHAOZONG-CHEN; HEQUN; 等

    1993-01-01

    The surfaces of red soils have an apparent amphoteric character,carrying titratable acidity and titratable alkalinity simultaneously.The titratable acidity arises from deprotonation of hydroxyl groups of hydrous oxide-type surfaces and dissociation of weak-acid functional groups of soil organic matter,while the titratable alkalinity is derived from release of hydroxyl groups of hydrous oxide-type surfaces.The titratable acidity and titratable alkalinity mainly depended on the composition and content of iron and aluminum oxides in the soils.The results showed that the titratable acidity and titratable alkalinity were in significantly positive correlation not only with the content of amorphous aluminum oxide(Alo) and iron oxide(Feo) extracted with acid ammonium oxalate solution,free iron oxide(Fed) extracted with sodium dithionite-citrate-bicarbonate(DCB) and clays,but also with the zero point of charge (ZPC) of the samples.Organic matter made an important contribution to the titratable acidity.the titratable alkalinity was closely correlated with the amount of fluoride ions adsorbed.The titratable acidity and titratable alkalinity of red soils were influenced by parent materials,being in the order of red soil derived from basalt> that from tuff> that from granite.The titratable acidity and titratable alkalinity ware closely related with origination of the variable charges of red soils,and to a certain extent were responsible for variable negative and positive charges of the soils.

  11. EFFECTIVE ALKALINE PEROXIDE OXIDATION PRETREATMENT OF SHEA TREE SAWDUST FOR THE PRODUCTION OF BIOFUELS: KINETICS OF DELIGNIFICATION AND ENZYMATIC CONVERSION TO SUGAR AND SUBSEQUENT PRODUCTION OF ETHANOL BY FERMENTATION USING Saccharomyces cerevisiae

    Directory of Open Access Journals (Sweden)

    A. O. Ayeni

    Full Text Available Abstract Shea tree sawdust delignification kinetic data during alkaline peroxide pretreatment were investigated at temperatures of 120 °C, 135 °C, and 150 °C. The activation energy during delignification was 76.4 kJ/mol and the Arrhenius constant was calculated as 8.4 x 106 per min. The reducing sugar yield for the treated to the untreated biomass was about 22-fold. Enzymatic hydrolysis conditions studied were; time (72 h and 96 h, substrate concentration (20, 30, 40, and 50 g/L, and enzyme loadings (10, 25, 40, 50 FPU/g dry biomass, which showed the optimum conditions of 96 h, 40 g/L, and 25 FPU/g dry biomass at 45 °C hydrolysis temperature. At the optimized enzymatic hydrolysis conditions, the reducing sugar yield was 416.32 mg equivalent glucose/g treated dry biomass. After 96 h fermentation of treated biomass, the ethanol obtained at 2% effective cellulose loading was 12.73 g/L. Alkaline peroxide oxidation pretreatment and subsequent enzymatic hydrolysis improved the ethanol yield of the biomass.

  12. Haptic perception of wetness

    NARCIS (Netherlands)

    Bergmann Tiest, W.M.; Kosters, N.D.; Daanen, H.A.M.; Kappers, A.M.L.

    2011-01-01

    The sensation of wetness is well-known but barely investigated. There are no specific wetness receptors in the skin, but the sensation is mediated by temperature and pressure perception. In our study, we have measured discrimination thresholds for the haptic perception of wetness of three di erent t

  13. Alkaline battery operational methodology

    Science.gov (United States)

    Sholklapper, Tal; Gallaway, Joshua; Steingart, Daniel; Ingale, Nilesh; Nyce, Michael

    2016-08-16

    Methods of using specific operational charge and discharge parameters to extend the life of alkaline batteries are disclosed. The methods can be used with any commercial primary or secondary alkaline battery, as well as with newer alkaline battery designs, including batteries with flowing electrolyte. The methods include cycling batteries within a narrow operating voltage window, with minimum and maximum cut-off voltages that are set based on battery characteristics and environmental conditions. The narrow voltage window decreases available capacity but allows the batteries to be cycled for hundreds or thousands of times.

  14. Effect of alkaline earth oxides on the physical and spectroscopic properties of Dy3+- doped Li2O-B2O3 glasses for white emitting material application

    Science.gov (United States)

    Shamshad, L.; Rooh, G.; Kirdsiri, K.; Srisittipokakun, N.; Damdee, B.; Kim, H. J.; Kaewkhao, J.

    2017-02-01

    Li2O-MO-B2O3:0.5Dy2O3 glasses mixed with four different alkaline earth modifier oxides MgO, CaO, SrO and BaO were synthesized by melt quench technique. Their physical properties like density, molar volume and refractive index were measured at room temperature and the effect of alkaline earth modifier oxides were studied. Also, optical absorption and photoluminescence spectra of these glasses have been acquired at room temperature. The Judd-Ofelt theory was effectively used to characterize these spectra and spectral intensities (ƒcal), Judd-Ofelt intensity parameters (Ω2, Ω4 and Ω6) and certain radiative properties have been determined. Radiative life-times (τR), branching ratios (βcal), and emission cross-sections (σp) and optical gain parameters (σp × τR) were calculated from the Judd-Ofelt intensity parameters and the variation in these parameters with the variation of glass matrix are discussed. Yellow/Blue (Y/B) ratio and chromacity color coordinates (x,y) are calculated from the emission spectra which indicates the white light generation from all the investigated samples. The correlated color temperature (CCT) for the studied glasses is found to be 4418 K. The fluorescence decay time (τexp) of the 4F9/2 level of Dy3+ has been measured from the decay profiles and compared with calculated lifetimes (τcal). Among all the studied glass matrices, the glass containing BaO exhibits high value of branching ratio, large emission cross-section and high optical gain parameter for 6F9/2 → 6H13 at 575 nm. The results indicates the suitability of all the studied glasses for laser action and white light generation.

  15. The oxidation of chromium(III) by hydroxyl radical in alkaline solution. A stopped-flow and pre-mix pulse radiolysis study

    DEFF Research Database (Denmark)

    Zhao, Zhongwei; Rush, J.D.; Holcman, J.

    1995-01-01

    The pK(a) for the equilibrium Cr(III)(H2O)3(OH)3(OH)3 reversible Cr(III)(H2O)2(OH)4- + H+ was determined to be 12.8 at 25-degrees-C. The dimerization of the two monomeric forms was studied in alkaline solutions using the stopped-flow method: k2[Cr(III)(H2O)3(OH)3 + Cr(III)(H2O)3(OH)3] = (2.5 +/- ......(VI)-(O-Cr(III))n]. Furthermore, a second-order reaction between two Cr(IV) monomers to yield a species which may be either a (Cr)2IV,IV or a (Cr)2III,V mixed-valence dimer was observed. The corresponding spectra in both the UV and visible range were determined....

  16. 湿式催化氧化催化剂及其活性组分流失控制的研究%Research on Catalyst and Control of Active Catalyst Components Lossing in Catalytic Wet Air Oxidation

    Institute of Scientific and Technical Information of China (English)

    王锐; 尹华强; 李建军; 郭家秀; 任吉萍

    2011-01-01

    Catalytic Wet Air Oxidation is an efficient and feasible technology for high concentration and refractory organic wastewater treatment. But the lossing of the active components of catalyst induced decreased catalytic activity, shorter life, higher investment costs, etc. in industrial operation In the paper, the catalytic wet oxidation technology and catalyst applications were described. What's more, the loss mechanism of the catalyst, affecting factors and methods to improve catalyst stability were emphatically illustrated, at the same time, related experiments and the results obtained are introduced.%湿式催化氧化技术是一种处理高浓度、难降解有机废水的高效、可行的技术,但是在使用过程中,活性组分易流失,在工业化应用中带来催化活性降低、使用寿命变短、投资成本增高等问题。文中介绍了湿式催化氧化技术及催化剂研究,着重讲述催化剂流失机理、影响因素以及提高催化剂稳定的方法,同时对相关实验和成果也做了介绍。

  17. Secondary alkaline batteries

    Science.gov (United States)

    McBreen, J.

    1984-03-01

    The overall reactions (charge/discharge characteristics); electrode structures and materials; and cell construction are studied for nickel oxide-cadmium, nickel oxide-iron, nickel oxide-hydrogen, nickel oxide-zinc, silver oxide-zinc, and silver oxide-cadmium, silver oxide-iron, and manganese dioxide-zinc batteries.

  18. Uranium in alkaline rocks

    Energy Technology Data Exchange (ETDEWEB)

    Murphy, M.; Wollenberg, H.; Strisower, B.; Bowman, H.; Flexser, S.; Carmichael, I.

    1978-04-01

    Geologic and geochemical criteria were developed for the occurrence of economic uranium deposits in alkaline igneous rocks. A literature search, a limited chemical analytical program, and visits to three prominent alkaline-rock localities (Ilimaussaq, Greenland; Pocos de Caldas, Brazil; and Powderhorn, Colorado) were made to establish criteria to determine if a site had some uranium resource potential. From the literature, four alkaline-intrusive occurrences of differing character were identified as type-localities for uranium mineralization, and the important aspects of these localities were described. These characteristics were used to categorize and evaluate U.S. occurrences. The literature search disclosed 69 U.S. sites, encompassing nepheline syenite, alkaline granite, and carbonatite. It was possible to compare two-thirds of these sites to the type localities. A ranking system identified ten of the sites as most likely to have uranium resource potential.

  19. H 2 O2湿式氧化法脱除铝酸钠溶液中的有机物%Removal of Organics From Industrial Sodium Aluminate Solution by Hydrogen Peroxide Wet Oxidation

    Institute of Scientific and Technical Information of China (English)

    杜振华; 李军旗; 金会心; 米秋秋

    2014-01-01

    By wet hydrogen peroxide oxidation ,the effects of alkali concentration ,oxidation time ,the amount of hydrogen peroxide and oxidation temperature on the removal of organics in Bayer liquor were investigated .The experiment results show that wet hydrogen peroxide oxidation method can effectively eliminate most of the organics in the sodium aluminate solution .T he better oxidation conditions is alkali concentration of 280 g/L ,oxidation temperature of 80 ℃ ,the amount of hydrogen peroxide of 80 mL ,oxidation time of 120 min for sodium aluminate solution of 80 mL .The removal rate of sodium oxalate is 65 .31% and the removal rate of total organic carbon is 60 .86% at the best conditions .T he process is simple ,no impurity is introduced in the system .%研究了采用 H2 O2湿式氧化法脱除某铝厂分解母液中的有机物,考察了母液苛性碱浓度、氧化时间、双氧水用量、温度对脱除有机物的影响。结果表明:H2 O2湿式氧化法可有效脱除铝酸钠溶液中的大部分有机物;试验获得的适宜工艺条件为苛性碱质量浓度280 g/L ,氧化时间120 min ,氧化温度80℃,双氧水用量80 mL。适宜条件下,草酸钠脱除率为65.31%,总有机物脱除率为60.86%。H2 O2湿式氧化法脱除铝酸钠溶液中有机物工艺简单,系统中不引入杂质。

  20. Use Alkalinity Monitoring to Optimize Bioreactor Performance.

    Science.gov (United States)

    Jones, Christopher S; Kult, Keegan J

    2016-05-01

    In recent years, the agricultural community has reduced flow of nitrogen from farmed landscapes to stream networks through the use of woodchip denitrification bioreactors. Although deployment of this practice is becoming more common to treat high-nitrate water from agricultural drainage pipes, information about bioreactor management strategies is sparse. This study focuses on the use of water monitoring, and especially the use of alkalinity monitoring, in five Iowa woodchip bioreactors to provide insights into and to help manage bioreactor chemistry in ways that will produce desirable outcomes. Results reported here for the five bioreactors show average annual nitrate load reductions between 50 and 80%, which is acceptable according to established practice standards. Alkalinity data, however, imply that nitrous oxide formation may have regularly occurred in at least three of the bioreactors that are considered to be closed systems. Nitrous oxide measurements of influent and effluent water provide evidence that alkalinity may be an important indicator of bioreactor performance. Bioreactor chemistry can be managed by manipulation of water throughput in ways that produce adequate nitrate removal while preventing undesirable side effects. We conclude that (i) water should be retained for longer periods of time in bioreactors where nitrous oxide formation is indicated, (ii) measuring only nitrate and sulfate concentrations is insufficient for proper bioreactor operation, and (iii) alkalinity monitoring should be implemented into protocols for bioreactor management.

  1. Kinetics and mechanism of uncatalyzed and ruthenium(III)-catalyzed oxidation of formamidine derivative by hexacyanoferrate(III) in aqueous alkaline medium

    Indian Academy of Sciences (India)

    AHMED FAWZY

    2016-05-01

    The catalytic effect of ruthenium(III) on the oxidation of N,N-dimethyl-N-(4H-1,2,4-triazol-3-yl) formamidine (ATF) by hexacyanoferrate(III) (HCF) was studied spectrophotometrically in aqueous alkalinemedium. Both uncatalyzed and catalyzed reactions showed first order kinetics with respect to [HCF],whereas the reaction orders with respect to [ATF] and $[OH^{-}]$ were apparently less than unity over the concentrationrange studied. A first order dependence with respect to $[Ru^{III}]$ was obtained. Increasing ionic strengthincreased the rate of uncatalyzed reaction and decreased the rate of the catalyzed one Plausible mechanisticschemes of oxidation reactions have been proposed. In both cases, the final oxidation products are identifiedas aminotriazole, dimethyl amine and carbon dioxide. The rate laws associated with the reaction mechanismsare derived. The reaction constants involved in the different steps of the mechanisms were calculated. Theactivation and thermodynamic parameters have been computed and discussed.

  2. The electro-oxidation of the mixture of formaldehyde and 2-propanol on gold (100 and (111 single crystal planes in alkaline medium

    Directory of Open Access Journals (Sweden)

    BRANISLAV Z. NIKOLIC

    2000-12-01

    Full Text Available The effect of formaldehyde on the oxidation of 2-propanol and vice versa on gold single crystal planes (100 and 111 was studied. An activating effect in the reaction of the simultaneous oxidation of 2-propanol and formaldehyde was obtained on a gold (100 plane. In the case of a gold (111 electrode, the activation effect was not obtained. It was concluded that the adsorption of formaldehyde on the electrode surface prevents the adsorption of poisoning species formed during the electro-oxidation of 2-propanol on the Au(100 plane, while this is not the case on the Au(111 plane. The different behaviour is caused by the difference in the symmetry of the surface atoms of these two Au single-crystal planes.

  3. CO Oxidation and Subsequent CO2 Chemisorption on Alkaline Zirconates: Li2 ZrO3 and Na2 ZrO3

    Energy Technology Data Exchange (ETDEWEB)

    Alcántar-Vázquez, Brenda; Duan, Yuhua; Pfeiffer, Heriberto

    2016-09-21

    Here, two different alkaline zirconates (Li2ZrO3 and Na2ZrO3) were studied as possible bifunctional catalytic-captor materials for CO oxidation and the subsequent CO2 chemisorption process. Initially, CO oxidation reactions were analyzed in a catalytic reactor coupled to a gas chromatograph, using Li2ZrO3 and Na2ZrO3, under different O2 partial flows. We found results clearly showed that Na2ZrO3 possesses much better catalytic properties than Li2ZrO3. After the CO-O2 oxidation catalytic analysis, CO2 chemisorption process was analyzed by thermogravimetric analysis, only for the Na2ZrO3 ceramic. The results confirmed that Na2ZrO3 is able to work as a bifunctional material (CO oxidation and subsequent CO2 chemisorption), although the kinetic CO2 capture process was not the best one under the physicochemical condition used in this case. For Na2ZrO3, the best CO conversions were found between 445 and 580 °C (100%), while Li2ZrO3 only showed a 35% of efficiency between 460 and 503 °C. However, in the Na2ZrO3 case, at temperatures higher than 580 °C its catalytic activity gradually decreases as a result of CO2 capture process. Finally, all these experiments were compared and supported with theoretical thermodynamic data.

  4. Effect of CeO2 doping on catalytic activity of Fe2O3/gamma-Al2O(3) catalyst for catalytic wet peroxide oxidation of azo dyes.

    Science.gov (United States)

    Liu, Yan; Sun, Dezhi

    2007-05-08

    In order to find a catalyst with high activity and stability for catalytic wet peroxide oxidation (CWPO) process under normal condition, with Fe(2)O(3)/gamma-Al(2)O(3) and Fe(2)O(3)-CeO(2)/gamma-Al(2)O(3) catalysts prepared by impregnation method, the effect of CeO(2) doping on the structure and catalytic activity of Fe(2)O(3)/gamma-Al(2)O(3) for catalytic wet peroxide oxidation of azo dyes at 25 degrees C and atmospheric pressure is evaluated using BET, SEM, XRF, XRD, XPS and chemical analysis techniques, and test results show that, better dispersion and smaller size of Fe(2)O(3) crystal can be achieved by adding CeO(2), and the content of chemisorbed oxygen can also be increased on the surface of catalyst. CWPO experimental results indicate that azo dyes in simulated wastewater can be efficiently mineralized and the catalytic activity of Fe(2)O(3)-CeO(2)/gamma-Al(2)O(3) can be increased by about 10% compared with that of Fe(2)O(3)/gamma-Al(2)O(3) because of the promotion of the structural and redox properties of the ferric oxide by ceria doped. Leaching tests indicate that Fe(2)O(3)/gamma-Al(2)O(3) and Fe(2)O(3)-CeO(2)/gamma-Al(2)O(3) are stable with a negligible amount of irons found in the aqueous solution after reaction for 2h. It can therefore be concluded from results and discussion that in comparison with Fe(2)O(3)/gamma-Al(2)O(3), Fe(2)O(3)-CeO(2)/gamma-Al(2)O(3) is a suitable catalyst, which can effectively degrade contaminants at normal temperature and atmospheric pressure.

  5. 湿式过氧化氢氧化处理高浓度染料废水的工艺研究%Technological Study on Treatment of High Concentration Dye Wastewater by the Wet Peroxide Oxidation

    Institute of Scientific and Technical Information of China (English)

    周书天; 杨润昌; 黄明; 谢磊

    2001-01-01

    Advanced treatment were used to degrade azodyes at highconcentration.Wet pe roxide oxidation(WPO)-iron filings scree ning -coagulation process was found to b e the best method in terms of color and COD removal.Methyl orange,the least biod egradable was chosen as a model dye for determining the most suitable reaction c onditions.The results showed that the re moval efficiency of COD,and color could reach 85%and 99% respectively.Temperatur e,FeSO4 amount,sulfuric acid amount and added hydrogen peroxide amount affected the wet peroxide oxidation(WPO).The remo val of COD and color were found to be ve ry sensitive to the reactio temperature .The COD removal rate was found to be pr oportional to the dosage of hydrogen per oxide,the color removal was also found t o be closely.Related to the removal of C OD until an equilibrium COD was reached.%采用湿式过氧化氢氧化—铁屑过滤—混凝技术处理高浓度偶氮染料废水,用难生化降解的甲基橙进行模拟试验。实验结果表明,该工艺COD和色度的去除率分别高达85%和99%。湿式过氧化氢氧化处理过程受温度、硫酸投量、Fe2+投量、H2O2投量的影响,反应温度对COD和色度的去除率影响较大,COD去除率的增加与H2O2投量成正比,色度的去除率随COD的增高而增大。

  6. Method for removal of nitrogen oxides from stationary combustion sources

    Science.gov (United States)

    Cooper, Charles D. (Inventor); Clausen, III, Christian A. (Inventor); Collins, Michelle M. (Inventor)

    2004-01-01

    A method for removing NO.sub.X from gas streams emanating from stationary combustion sources and manufacturing plants utilizes the injection of hydrogen peroxide into the gas stream for rapid gas-phase oxidation of NO to NO.sub.2 and water-soluble nitrogen acids HNO.sub.2 and HNO.sub.3. The nitrogen acids may be removed from the oxidized gas stream by wet scrubbing or by contact with a particulate alkaline material to form a nitrite/nitrate salt.

  7. Morphology and performances of the anodic oxide films on Ti6Al4V alloy formed in alkaline-silicate electrolyte with aminopropyl silane addition under low potential

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Jiali; Wang, Jinwei, E-mail: wangjw@ustb.edu.cn; Yuan, Hongye

    2013-11-01

    Oxide films on Ti6Al4V alloy are prepared using sodium hydroxide–sodium silicate as the base electrolyte with addition of aminopropyl trimethoxysilane (APS) as additive by potentiostatic anodizing under 10 V. APS is incorporated into the films during anodizing and the surface morphology of the oxide films is changed from particle stacked to honeycomb-like porous surfaces as shown by scanning electron microscopy (SEM) with Energy Disperse Spectroscopy (EDX). The surface roughness and aminopropyl existence on the oxide films result in their differences in wettability as tested by the surface profile topography and contact angle measurements. The anti-abrasive ability of the anodic films is improved with the addition of APS due to its toughening effects and serving as lubricants in the ceramic oxide films as measured by ball-on-disk friction test. Also, potentiodynamic corrosion test proves that their anticorrosive ability in 3.5 wt.% NaCl is greatly improved as reflected by their much lower corrosion current (I{sub corr}) and higher corrosion potential (E{sub corr}) than those of the substrate.

  8. Double layer effects in electrocatalysis: the oxygen reduction reaction and ethanol oxidation reaction on Au(111), Pt(111) and Ir(111) in alkaline media containing Na and Li cations.

    Energy Technology Data Exchange (ETDEWEB)

    Lopes, Pietro P.; Strmcnik, Dusan; Jirkovsky, Jakub S.; Connell, Justin G.; Stamenkovic, Vojislav; Markovic, Nenad

    2016-03-15

    Oxygen reduction and ethanol oxidation reactions were studied on Au(111), Pt(111) and Ir(111) in alkaline solutions containing sodium and/or lithium cations. By keeping the same (111) surface orientation and exploring oxophilicity trends and non-covalent interactions between OHad and alkali metal cations (AMCn+), we were able to gain deep insights into the multiple roles that OHad plays in these important electrocatalytic reactions. Cyclic voltammetry experiments revealed that OHad formation initiates at distinct electrode potentials, governed by the oxophilicity of the specific metal surface, with further OHad adlayer stabilization by non-covalent alkali-cation interactions and affecting the formation of a “true oxide” layer at higher electrode potentials. Although OHad is a simple spectator for the ORR, it promotes the ethanol oxidation reaction (EOR) at lower potentials and act as spectator at high OHad coverages. By changing the alkali metal cation at the interface (Li+) on more oxophilic surfaces, it was possible to promote the EOR even more, relative to Na+, without changing the product distribution for the reaction. This cation effect suggests that OHad---Li+(H2O)x clusters can stabilize the ethoxide adlayer, thus improving the EOR activity. Our results indicate the importance of the entire electrochemical interface in determining the electrocatalytic activity during reaction.

  9. Catalytic activity of ruthenium(III) on the oxidation of an anticholinergic drug-atropine sulfate monohydrate by copper(III) periodate complex in aqueous alkaline medium - decarboxylation and free radical mechanism.

    Science.gov (United States)

    Byadagi, Kirthi S; Nandibewoor, Sharanappa T; Chimatadar, Shivamurti A

    2013-01-01

    Atropine sulfate monohydrate (ASM) is an anticholinergic drug, having a wide spectrum of activity. Hence, the kinetics of oxidation of ASM by diperiodatocuperate (DPC) in the presence of micro (10-6) amounts of Ru(III) catalyst has been investigated spectrophotometrically in aqueous alkaline medium at I = 0.50 mol dm-3. The reaction between DPC and ASM exhibits 1:2 stoichiometry (ASM:DPC) i. e., one mole of ASM require two moles of DPC to give products. The main oxidation products were confirmed by spectral studies. The reaction is first order with respect to [DPC] and [Ru(III)], while the order with respect to [ASM] and [OH-] was less than unity. The rates decreased with increase in periodate concentration. The reaction rates revealed that Ru(III) catalyzed reaction was about seven-fold faster than the uncatalyzed reaction. The catalytic constant (KC) was also determined at different temperatures. A plausible mechanism is proposed. The activation parameters with respect to slow step of the mechanism were calculated and the thermodynamic quantities were also determined. Kinetic experiments suggest that [Cu(H2IO6)(H2O)2] is the reactive Cu(III) species and [Ru(H2O)5OH]2+ is the reactive Ru(III) species.

  10. Comprehensive study of pore evolution, mesostructural stability, and simultaneous surface functionalization of ordered mesoporous carbon (FDU-15) by wet oxidation as a promising adsorbent.

    Science.gov (United States)

    Wu, Zhangxiong; Webley, Paul A; Zhao, Dongyuan

    2010-06-15

    Fuctionalization of porous carbon materials through chemical methods orientates the development of new hybrid materials with specific functions. In this paper, a comprehensive study of pore evolution, mesostructural oxidation resistance, and simultaneous surface functionalization of ordered mesoporous carbon FDU-15 under various oxidation conditions is presented for the first time. The mesostructure and pore evolution with increasing oxidative strength are retrieved from XRD, TEM, and N(2) sorption techniques. The textural properties can be conveniently manipulated by changing the oxidation parameters, including different oxidative solution, temperature, and duration. It is revealed that the mesoporous carbon FDU-15 shows excellent structural stability under severe oxidation treatments by acidic (NH(4))(2)S(2)O(8), HNO(3), and H(2)O(2) solutions, much more stable than the mesostructural analogue CMK-3 carbon prepared by the nanocasting method. The surface area and porosity deteriorate to a large extent compared to the pristine carbon, with the micropores/small mesopores as the major contribution to the deterioration. The micropore/small mesopore can be blocked by the attached surface oxides under mild oxidation, while reopened with more carbon layer dissolution under more severe conditions. Simultaneously, high densities of surface oxygen complexes, especially carboxylic groups, can be generated. The contents and properties of the surface oxygen-containing groups are extensively studied by FTIR, TG, elemental analyses, and water and ammonia adsorption techniques. Such surface-functionalized mesoporous carbons can be used as a highly efficient adsorbent for immobilization of heavy metal ions as well as functional organic and biomolecules, with high capacities and excellent binding capabilities. Thus, we believe that the functionalized mesoporous carbon materials can be utilized as a promising solid and stable support for water treatment and organic

  11. Interfacial Reactions and Cubic Neodymium Oxide Formation in Low Dispersed Nd2O3-SiO2 System by Wet Chemical Method

    Institute of Scientific and Technical Information of China (English)

    S. Duhan; P. Aghamkar

    2009-01-01

    Neodymium (binary oxide) powders are synthesized by a solgel technique. Prepared powders are heat treated under different temperature for different time duration and obtained nanostructure of Nd. Metal particle have diameters in the range 7.8-21.6nm. It is found that the heat treatment plays an important role to produce different structure of Nd-doped silica matrix. The peak position shifts to lower angle as the size of the nano metal oxide particles size increases.

  12. High performance of alkaline anion-exchange membranes based on chitosan/poly (vinyl) alcohol doped with graphene oxide for the electrooxidation of primary alcohols

    OpenAIRE

    García Cruz, Leticia; Casado Coterillo, Clara; Irabien Gulías, José Ángel; Montiel Leguey, Vicente; Iniesta Valcárcel, Jesús

    2016-01-01

    Mixed matrix membranes (MMM) based on chitosan (CS) and poly (vinyl) alcohol (PVA) with a 50:50 w/w ratio doped with graphene oxide (GO) are prepared by solution casting and characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), thermogravimetric analysis (TGA), water uptake, alcohol permeability, ion exchange capacity (IEC) and OH− conductivity measurements. The SEM analysis revealed a dense MMM where the GO nanosheets were well dispersed over the entire polymer matrix...

  13. Wetting and Photocatalytic Properties of TiO2 Nanotube Arrays Prepared via Anodic Oxidation of E-Beam Evaporated Ti Thin Films

    Directory of Open Access Journals (Sweden)

    Soon Wook Kim

    2015-01-01

    Full Text Available TiO2 nanotube arrays (TNAs are fabricated on quartz substrate by anodizing E-beam evaporated Ti films. E-beam evaporated Ti films are directly anodized at various anodizing voltages ranging from 20 to 45 V and their morphological, wetting, and photocatalytic properties are examined. The photocatalytic activity of the prepared TNAs is evaluated by the photodecomposition of methylene blue under UV illumination. The TNAs prepared at an anodizing voltage of 30 V have a high roughness of 30.1 nm and a low water contact angle of 7.5°, resulting in a high photocatalytic performance. The surface roughness of the TNAs is found to correlate inversely with the water contact angle. High roughness (i.e., high surface area, which leads to high hydrophilicity, is desirable for effective photocatalytic activity.

  14. Alkaline earth metal thioindates

    Energy Technology Data Exchange (ETDEWEB)

    Ivanov-Ehmin, B.N.; Ivlieva, V.I.; Filatenko, L.A.; Zajtsev, B.E.; Kaziev, G.Z.; Sarabiya, M.G.

    1984-08-01

    Alkaline earth metal thioindates of MIn/sub 2/S/sub 4/ composition were synthesized by interaction of alkaline earth metal oxoindates with hydrogen sulfide during heating. Investigation into the compounds by X-ray analysis showed that calcium compound crystallizes in cubic crystal system and strontium and barium compounds in rhombic crystal system. Lattice parameters and the number of formula units were determined. Thioindates of M/sub 3/In/sub 2/S/sub 6/ composition were synthesized, their individuality was shown.

  15. Facile electrochemical co-deposition of a graphene-cobalt nanocomposite for highly efficient water oxidation in alkaline media: direct detection of underlying electron transfer reactions under catalytic turnover conditions.

    Science.gov (United States)

    Guo, Si-Xuan; Liu, Yuping; Bond, Alan M; Zhang, Jie; Esakki Karthik, P; Maheshwaran, I; Senthil Kumar, S; Phani, K L N

    2014-09-21

    A facile electrochemical co-deposition method has been developed for the fabrication of graphene-cobalt nanocomposite modified electrodes that achieve exceptionally efficient water oxidation in highly alkaline media. In the method reported, a graphene-cobalt nanocomposite film was deposited electrochemically from a medium containing 1 mg ml(-1) graphene oxide, 0.8 mM cobalt nitrate and 0.05 M phytic acid (pH 7). The formation of the nanocomposite film was confirmed using electrochemical, Raman spectroscopic and scanning electron microscopic techniques. The nanocomposite film exhibits excellent activity and stability towards water oxidation to generate oxygen in 1 M NaOH aqueous electrolyte media. A turn over frequency of 34 s(-1) at an overpotential of 0.59 V and a faradaic efficiency of 97.7% were deduced from analysis of data obtained by rotating ring disk electrode voltammetry. Controlled potential electrolysis data suggests that the graphene supported catalyst exhibits excellent stability under these harsh conditions. Phytate anion acts as stabilizer for the electrochemical formation of cobalt nanoparticles. Fourier transformed ac voltammetry allowed the redox chemistry associated with catalysis to be detected directly under catalytic turnover conditions. Estimates of formal reversible potentials obtained from this method and derived from the overall reactions 3Co(OH)2 + 2OH(-) ⇌ Co3O4 + 4H2O + 2e(-), Co3O4 + OH(-) ⇌ 3CoOOH + e(-) and CoOOH + OH(-) ⇌ CoO2 + H2O + e(-) are 0.10, 0.44 and 0.59 V vs. Ag/AgCl, respectively.

  16. WetVegEurope

    NARCIS (Netherlands)

    Landucci, Flavia; Řezníčková, Marcela; Šumberová, Kateřina; Hennekens, S.M.; Schaminée, J.H.J.

    2015-01-01

    WetVegEurope is a research project (http://www.sci.muni.cz/botany/vegsci/wetveg) whose goal is to provide a synthesized formalized classification of the aquatic and marsh vegetation across Europe at the level of phytosociological associations. In order to achieve the project objective, a WetVegEu

  17. Catalytic behaviour and copper leaching of Cu0.10Zn0.90Al1.90Fe0.10O4 spinel for catalytic wet air oxidation of phenol.

    Science.gov (United States)

    Xu, Aihua; Sun, Chenglin

    2012-06-01

    A Cu0.10Zn0.90Al1.90Fe0.10O4 spinel catalyst prepared by the sol-gel method was tested for catalytic wet air oxidation (CWAO) of phenol. The catalyst showed high activity for phenol degradation. During successive test at 170 degrees C, 100% phenol conversion and 95% chemical oxygen demand (COD) removal were observed. Results from scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR) and X-ray diffraction (XRD) indicated that the catalyst structure remained unchanged during reaction. From the analysis of temperature programmed reduction (TPR), diffuse reflectance UV-Vis spectra (DR UV-Vis) and activity assay at basic solution pH, it can be suggested that the highly dispersed copper ions on the catalyst surface were almost completely dissolved into the reaction solution, whereas the tetra-coordinated copper ions were not only stable against leaching but also active towards phenol degradation.

  18. 湿式催化氧化法中催化剂的选择和实验条件的优化%Selection of Catalysts and Optimization of Experimental Condition in Catalytic Wet Oxidation

    Institute of Scientific and Technical Information of China (English)

    董岳刚; 严莲荷; 周进; 周申范

    2001-01-01

    本文研究了湿式催化氧化法(Catalytic Wet Oxidation,CWO)处理高浓度有机水中催化剂的选择和实验条件的优化.在优选催化剂中共计制备十四种催化剂并进行实验,得出Ce、Cu复合催化剂活性最高.在实验条件优化中根据对正交实验数据结果进行的极差分析发现CWO法处理废水时的各影响因素的主次关系是:H2O2用量>Ce、Cu复合催化剂用量>反应时间.

  19. Research Progress on Catalytic Wet Air Oxidation for Treating Highly Concentrated Wastewater%催化湿式氧化处理高浓度有机废水的研究进展

    Institute of Scientific and Technical Information of China (English)

    李云; 袁志文

    2013-01-01

    The reaction principle,technical flow and catalyst research progress of catalytic wet air oxidation technology were introduced.Its application in wastewater treatment was analyzed and summarized.The problems existing in current application were reviewed,and some pieces of advice about the research were proposed.%介绍了催化湿式氧化技术的反应原理、工艺流程以及近些年来不同种催化剂的研究进展,分析和归纳了催化湿式氧化技术在污水处理中的应用现状,对实际应用中出现的问题进行了总结,并提出了一些建议.

  20. In Situ Surface-Enhanced Raman Spectroscopy Study of the Electrocatalytic Effect of PtFe/C Nanocatalyst on Ethanol Electro-Oxidation in Alkaline Medium

    Directory of Open Access Journals (Sweden)

    A. C. Gómez-Monsiváis

    2017-03-01

    Full Text Available Currently, the ethanol electro-oxidation reaction has attracted considerable attention in fuel cells because of new green ethanol synthetic methods based on biomass processes that have emerged. In this study, PtFe/C and Pt/C nanoparticles were synthesized by a chemical reduction method and tested in the ethanol electro-oxidation reaction. Furthermore, the electrocatalytic effect of the PtFe bimetallic catalyst was analyzed by in situ surface-enhanced Raman spectroscopy (SERS coupled to an electrochemical cell. X-ray diffractograms showed typical face-centered cubic structures with crystallite sizes of 3.31 and 3.94 for Pt/C and PtFe/C, respectively. TEM micrographs revealed nanoparticle sizes of 2 ± 0.4 nm and 3 ± 0.6 nm for Pt/C and PtFe/C respectively. PtFe/C exhibited a Pt90Fe10 composition by both X-ray fluorescence and energy-dispersive X-ray spectroscopy. A better electrocatalytic activity as function of concentration was obtained through the incorporation of a small amount of Fe into the Pt lattice and the presence of Fe2+/Fe3+ (observed by X-ray photoelectron spectroscopy. According to SERS experiments, the presence of these iron species promotes the chemisorption of ethanol, the formation of formic acid as main product and renewal of the catalytic sites, resulting in current densities that were at least three fold higher than the values obtained for the Pt/C nanocatalyst.