Assessment for development of an industrial wet oxidation system for burning waste and low-grade fuels. Final report, October 18, 1989--February 28, 1995

International Nuclear Information System (INIS)

Sundback, C.

1995-05-01

The ultimate goal of this program was to demonstrate safe, reliable, and effective operation of the supercritical water oxidation process (SCWO) at a pilot plant-level throughput. This program was a three phase program. Phase 1 of the program preceded MODEC's participation in the program. MODEC did participate in Phases 2 and 3 of the program. In Phase 2, the target waste and industry were pulp mill sludges from the pulp and paper industry. In Phase 3, the target was modified to be DOE-generated mixed low level waste; wastes containing RCRA hazardous constituents and radionuclide surrogates were used as model wastes. The paper describes the research unit planning and design; bench-scale development of SCWO; research and development of wet oxidation of fuels; and the design of a super-critical water pilot plant

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

2016-01-01

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. PMID:27452148

Oxidation behavior of steels and Alloy 800 in supercritical water

International Nuclear Information System (INIS)

Olmedo, A.M.; Bordoni, R.; Dominguez, G.; Alvarez, M.G.

2011-01-01

The oxidation behavior of a ferritic-martensitic steel T91 and a martensitic steel AISI 403 up to 750 h, and of AISI 316L and Alloy 800 up to 336 h in deaerated supercritical water, 450ºC-25 MPa, was investigated in this paper. After exposure up to 750 h, the weight gain data, for steels T91 and AISI 403, was fitted by ∆W=k t n , were n are similar for both steels and k is a little higher for T91. The oxide films grown in the steels were characterized using gravimetry, scanning electron microscopy/energy dispersive X-ray spectroscopy (SEM/EDS) and X-ray diffraction. The films were adherent and exhibited a low porosity. For this low oxygen content supercritical water exposure, the oxide scale exhibited a typical duplex structure, in which the scale is composed of an outer iron oxide layer of magnetite (Fe 3 O 4 ) and an inner iron/chromium oxide layer of a non-stoichiometric iron chromite (Fe,Cr) 3 O 4 . Preliminary results, with AISI 316L and Alloy 800, for two exposure periods (168 and 336 h), are also reported. The morphology shown for the oxide films grown on both materials up to 336 h of oxidation in supercritical water, resembles that of a duplex layer film like that shown by stainless steels and Alloy 800 oxide films grown in a in a high temperature and pressure (220-350ºC) of a primary or secondary coolant of a plant. (author) [es

Oxidation of oily sludge in supercritical water

International Nuclear Information System (INIS)

Cui Baochen; Cui Fuyi; Jing Guolin; Xu Shengli; Huo Weijing; Liu Shuzhi

2009-01-01

The oxidation of oily sludge in supercritical water is performed in a batch reactor at reaction temperatures between 663 and 723 K, the reaction times between 1 and 10 min and pressure between 23 and 27 MPa. Effect of reaction parameters such as reaction time, temperature, pressure, O 2 excess and initial COD on oxidation of oily sludge is investigated. The results indicate that chemical oxygen demand (COD) removal rate of 92% can be reached in 10 min. COD removal rate increases as the reaction time, temperature and initial COD increase. Pressure and O 2 excess have no remarkable affect on reaction. By taking into account the dependence of reaction rate on COD concentration, a global power-law rate expression was regressed from experimental data. The resulting pre-exponential factor was 8.99 x 10 14 (mol L -1 ) -0.405 s -1 ; the activation energy was 213.13 ± 1.33 kJ/mol; and the reaction order for oily sludge (based on COD) is 1.405. It was concluded that supercritical water oxidation (SCWO) is a rapidly emerging oily sludge processing technology.

US-UK Phase 3 Task 1 Oxidation in Supercritical Fluids

Energy Technology Data Exchange (ETDEWEB)

Holcomb, Gordon R. [National Energy Technology Lab. (NETL), Albany, OR (United States)

2017-03-20

A presentation of the US-UK Phase 3 Task 1 Oxidation in Supercritical Fluids. Includes slides on Supercritical Steam, sCO₂ Power Cycles – Indirect, sCO₂ Power Cycles – Direct, Experimental Exposures, Alloys, Why Si, Results—Ni-xCr Alloys (5-24Cr), Fatigue Crack Growth$-$Experiment, and Alloys and Samples, Fatigue Crack Growth—Results (H282).

Effects of Gravity on Supercritical Water Oxidation (SCWO) Processes

Science.gov (United States)

Hegde, Uday; Hicks, Michael

2013-01-01

The effects of gravity on the fluid mechanics of supercritical water jets are being studied at NASA to develop a better understanding of flow behaviors for purposes of advancing supercritical water oxidation (SCWO) technologies for applications in reduced gravity environments. These studies provide guidance for the development of future SCWO experiments in new experimental platforms that will extend the current operational range of the DECLIC (Device for the Study of Critical Liquids and Crystallization) Facility on board the International Space Station (ISS). The hydrodynamics of supercritical fluid jets is one of the basic unit processes of a SCWO reactor. These hydrodynamics are often complicated by significant changes in the thermo-physical properties that govern flow behavior (e.g., viscosity, thermal conductivity, specific heat, compressibility, etc), particularly when fluids transition from sub-critical to supercritical conditions. Experiments were conducted in a 150 ml reactor cell under constant pressure with water injections at various flow rates. Flow configurations included supercritical jets injected into either sub-critical or supercritical water. Profound gravitational influences were observed, particularly in the transition to turbulence, for the flow conditions under study. These results will be presented and the parameters of the flow that control jet behavior will be examined and discussed.

Supercritical Water Oxidation Program (SCWOP)

International Nuclear Information System (INIS)

1994-02-01

Purpose of SCWOP is to develop and demonstrate supercritical water oxidation as a viable technology for treating DOE hazardous and mixed wastes and to coordinate SCWO research, development, demonstration, testing, and evaluation activities. The process involves bringing together organic waste, water, and an oxidant (air, O 2 , etc.) to temperatures and pressures above water's critical point (374 C, 22.1 MPa); organic destruction is >99.99% efficient, and the resulting effluents (mostly water, CO 2 ) are relatively benign. Pilot-scale (300--500 gallons/day) SCWO units are to be constructed and demonstrated. Two phases will be conducted: hazardous waste pilot plant demonstration and mixed waste pilot demonstration. Contacts for further information and for getting involved are given

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.

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. © 2016 The Authors, Journal of Separation Science Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Supercritical water oxidation treatment of textile sludge.

Science.gov (United States)

Zhang, Jie; Wang, Shuzhong; Li, Yanhui; Lu, Jinling; Chen, Senlin; Luo, XingQi

2017-08-01

In this work, we studied the supercritical water oxidation (SCWO) of the textile sludge, the hydrothermal conversion of typical textile compounds and the corrosion properties of stainless steel 316. Moreover, the influence mechanisms of NaOH during these related processes were explored. The results show that decomposition efficiency for organic matter in liquid phase of the textile sludge was improved with the increment of reaction temperature or oxidation coefficient. However, the organic substance in solid phase can be oxidized completely in supercritical water. Serious coking occurred during the high pressure water at 250-450°C for the Reactive Orange 7, while at 300 and 350°C for the polyvinyl alcohol. The addition of NaOH not only accelerated the destruction of organic contaminants in the SCWO reactor, but effectively inhibited the dehydration conversion of textile compounds during the preheating process, which was favorable for the treatment system of textile sludge. The corrosion experiment results indicate that the stainless steel 316 could be competent for the body materials of the reactor and the heat exchangers. Furthermore, there was prominent enhancement of sodium hydroxide for the corrosion resistance of 316 in subcritical water. On the contrary the effect was almost none during SCWO.

Flow analysis in a supercritical water oxidation reactor

International Nuclear Information System (INIS)

Oh, C.H.; Kochan, R.J.; Beller, J.M.

1996-01-01

Supercritical water oxidation (SCWO), also known as hydrothermal oxidation (HTO), involves the oxidation of hazardous waste at conditions of elevated temperature and pressure (e.g., 500 C--600 C and 234.4 bar) in the presence of approximately 90% of water and a 10% to 20% excess amount of oxidant over the stoichiometric requirement. Under these conditions, organic compounds are completely miscible with supercritical water, oxygen and nitrogen, and are rapidly oxidized to carbon dioxide and water. The essential part of the process is the reactor. Many reactor designs such as tubular, vertical vessel, and transpiring wall type have been proposed, patented, and tested at both bench and pilot scales. These designs and performances need to be scaled up to a waste throughput 10--100 times that currently being tested. Scaling of this magnitude will be done by creating a numerical thermal-hydraulic model of the smaller reactor for which test data is available, validating the model against the available data, and then using the validated model to investigate the larger reactor performance. This paper presents a flow analysis of the MODAR bench scale reactor (vertical vessel type). These results will help in the design of the reactor in an efficient manner because the flow mixing coupled with chemical kinetics eventually affects the process destruction efficiency

COAL CONVERSION WASTEWATER TREATMENT BY CATALYTIC OXIDATION IN SUPERCRITICAL WATER; FINAL

International Nuclear Information System (INIS)

Phillip E. Savage

1999-01-01

Wastewaters from coal-conversion processes contain phenolic compounds in appreciable concentrations. These compounds need to be removed so that the water can be discharged or re-used. Catalytic oxidation in supercritical water is one potential means of treating coal-conversion wastewaters, and this project examined the reactions of phenol over different heterogeneous oxidation catalysts in supercritical water. More specifically, we examined the oxidation of phenol over a commercial catalyst and over bulk MnO(sub 2), bulk TiO(sub 2), and CuO supported on Al(sub 2) O(sub 3). We used phenol as the model pollutant because it is ubiquitous in coal-conversion wastewaters and there is a large database for non-catalytic supercritical water oxidation (SCWO) with which we can contrast results from catalytic SCWO. The overall objective of this research project is to obtain the reaction engineering information required to evaluate the utility of catalytic supercritical water oxidation for treating wastes arising from coal conversion processes. All four materials were active for catalytic supercritical water oxidation. Indeed, all four materials produced phenol conversions and CO(sub 2) yields in excess of those obtained from purely homogeneous, uncatalyzed oxidation reactions. The commercial catalyst was so active that we could not reliably measure reaction rates that were not limited by pore diffusion. Therefore, we performed experiments with bulk transition metal oxides. The bulk MnO(sub 2) and TiO(sub 2) catalysts enhance both the phenol disappearance and CO(sub 2) formation rates during SCWO. MnO(sub 2) does not affect the selectivity to CO(sub 2), or to the phenol dimers at a given phenol conversion. However, the selectivities to CO(sub 2) are increased and the selectivities to phenol dimers are decreased in the presence of TiO(sub 2) , which are desirable trends for a catalytic SCWO process. The role of the catalyst appears to be accelerating the rate of formation of

Reactivity of micas and cap-rock in wet supercritical CO_2 with SO_2 and O_2 at CO_2 storage conditions

International Nuclear Information System (INIS)

Pearce, Julie K.; Dawson, Grant K.W.; Law, Alison C.K.; Biddle, Dean; Golding, Suzanne D.

2016-01-01

buffered by carbonate dissolution. Ca-sulfate, and Fe-bearing precipitates were observed post SO_2-CO_2 reaction, mainly centered on surface cracks and an illite rich illite-smectite precipitate quantified. Water saturated impure supercritical CO_2 was observed to have reactivity to rock-forming biotite, muscovite and phlogopite mineral separates. In the cap-rock core however carbonates and chlorite were the main reacting minerals showing the importance of assessing actual whole core. - Highlights: • Reactivity of micas and cap-rock in wet supercritical CO_2 with SO_2 and O_2 impurities or gas saturated water. • Precipitation of sulphates observed at mica cracks and sheet edges, jarosite, smectite and hematite saturated in models. • Low pH formed in presence of O_2 and SO_2, with mobilized cations including Fe from micas. • Corrosion of carbonates and Fe-chlorite from cap-rock with the presence of SO_2. • Precipitation of sulphates (in surface cracks), oxides, and silicates on cap-rock surface.

Supercritical water oxidation data acquisition testing. Final report, Volume I

International Nuclear Information System (INIS)

1996-11-01

This report discusses the phase one testing of a data acquisition system for a supercritical water waste oxidation system. The system is designed to destroy a wide range of organic materials in mixed wastes. The design and testing of the MODAR Oxidizer is discussed. An analysis of the optimized runs is included

Enhanced metal recovery through oxidation in liquid and/or supercritical carbon dioxide

KAUST Repository

Blanco, Mario; Buttner, Ulrich

2017-01-01

Process for enhanced metal recovery from, for example, metal-containing feedstock using liquid and/or supercritical fluid carbon dioxide and a source of oxidation. The oxidation agent can be free of complexing agent. The metal-containing feedstock

Ion exchange resins destruction in a stirred supercritical water oxidation reactor

International Nuclear Information System (INIS)

Leybros, A.; Roubaud, A.; Guichardon, P.; Boutin, O.

2010-01-01

Spent ion exchange resins (IERs) are radioactive process wastes for which there is no satisfactory industrial treatment. Supercritical water oxidation offers a viable treatment alternative to destroy the organic structure of resins, used to remove radioactivity. Up to now, studies carried out in supercritical water for IER destruction showed that degradation rates higher than 99% are difficult to obtain even using a catalyst or a large oxidant excess. In this study, a co-fuel, isopropanol, has been used in order to improve degradation rates by initiating the oxidation reaction and increasing temperature of the reaction medium. Concentrations up to 20 wt% were tested for anionic and cationic resins. Total organic carbon reduction rates higher than 99% were obtained from this process, without the use of a catalyst. The influence of operating parameters such as IERs feed concentration, nature and counterions of exchanged IERs were also studied. (authors)

Supercritical water oxidation data acquisition testing. Final report, Volume II

International Nuclear Information System (INIS)

1996-11-01

Supercritical Water Oxidation (SCWO) technology holds great promise for treating mixed wastes, in an environmentally safe and efficient manner. In the spring of 1994 the US Department of Energy (DOE), Idaho Operations Office awarded Stone ampersand Webster Engineering Corporation, of Boston Massachusetts and its sub-contractor MODAR, Inc. of Natick Massachusetts a Supercritical Water Oxidation Data Acquisition Testing (SCWODAT) program. The SCWODAT program was contracted through a Cooperative Agreement that was co-funded by the US Department of Energy and the Strategic Environmental Research and Development Program. The SCWODAT testing scope outlined by the DOE in the original Cooperative Agreement and amendments thereto was initiated in June 1994 and successfully completed in December 1995. The SCWODAT program provided further information and operational data on the effectiveness of treating both simulated mixed waste and typical Navy hazardous waste using the MODAR SCWO technology

Can supercritical oxidation of sewage sludge be an alternative for supercritical gasification?; Kan superkritische oxidatie van zuiveringsslib een alternatief zijn voor superkritische vergassing?

Energy Technology Data Exchange (ETDEWEB)

Rulkens, W. [Wageningen UR, Wageningen (Netherlands); Wentink, J. [Horizon Solutions, Leiden (Netherlands)

2013-05-15

In the context of the development of The Energy Factory a number of technologies has been identified that may be interesting to develop further. Two of these techniques relate to the conversion of sludge in supercritical water: supercritical gasification of sludge and supercritical oxidation of sludge [Dutch] In het kader van de ontwikkeling van De Energiefabriek is een aantal technologieen geidentificeerd die mogelijk interessant zijn om verder te ontwikkelen. Twee van deze technieken hebben betrekking op de conversie van slib in superkritisch water: superkritische slibvergassing en superkritische sliboxidatie.

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 reactio...

Enhanced metal recovery through oxidation in liquid and/or supercritical carbon dioxide

KAUST Repository

Blanco, Mario

2017-08-24

Process for enhanced metal recovery from, for example, metal-containing feedstock using liquid and/or supercritical fluid carbon dioxide and a source of oxidation. The oxidation agent can be free of complexing agent. The metal-containing feedstock can be a mineral such as a refractory mineral. The mineral can be an ore with high sulfide content or an ore rich in carbonaceous material. Waste can also be used as the metal-containing feedstock. The metal-containing feedstock can be used which is not subjected to ultrafine grinding. Relatively low temperatures and pressures can be used. The metal-containing feedstock can be fed into the reactor at a temperature below the critical temperature of the carbon dioxide, and an exotherm from the oxidation reaction can provide the supercritical temperature. The oxidant can be added to the reactor at a rate to maintain isothermal conditions in the reactor. Minimal amounts of water can be used as an extractive medium.

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.

Method and apparatus for waste destruction using supercritical water oxidation

Science.gov (United States)

Haroldsen, Brent Lowell; Wu, Benjamin Chiau-pin

2000-01-01

The invention relates to an improved apparatus and method for initiating and sustaining an oxidation reaction. A hazardous waste, is introduced into a reaction zone within a pressurized containment vessel. An oxidizer, preferably hydrogen peroxide, is mixed with a carrier fluid, preferably water, and the mixture is heated until the fluid achieves supercritical conditions of temperature and pressure. The heating means comprise cartridge heaters placed in closed-end tubes extending into the center region of the pressure vessel along the reactor longitudinal axis. A cooling jacket surrounds the pressure vessel to remove excess heat at the walls. Heating and cooling the fluid mixture in this manner creates a limited reaction zone near the center of the pressure vessel by establishing a steady state density gradient in the fluid mixture which gradually forces the fluid to circulate internally. This circulation allows the fluid mixture to oscillate between supercritical and subcritical states as it is heated and cooled.

Corrosion behavior of oxide dispersion strengthened ferritic steels in supercritical water

Energy Technology Data Exchange (ETDEWEB)

Gao, Wenhua [School of Nuclear Science and Engineering, Shanghai Jiao Tong University, No. 800 Dongchuan Road, Shanghai 200240 (China); Guo, Xianglong, E-mail: guoxianglong@sjtu.edu.cn [School of Nuclear Science and Engineering, Shanghai Jiao Tong University, No. 800 Dongchuan Road, Shanghai 200240 (China); Shen, Zhao [Department of Materials Science, University of Oxford, Parks Road, Oxford OX1 3PH (United Kingdom); Zhang, Lefu, E-mail: lfzhang@sjtu.edu.cn [School of Nuclear Science and Engineering, Shanghai Jiao Tong University, No. 800 Dongchuan Road, Shanghai 200240 (China)

2017-04-01

The corrosion resistance of three different Cr content oxide dispersion strengthened (ODS) ferritic steels in supercritical water (SCW) and their passive films formed on the surface have been investigated. The results show that the dissolved oxygen (DO) and chemical composition have significant influence on the corrosion behavior of the ODS ferritic steels. In 2000 ppb DO SCW at 650 °C, the 14Cr-4Al ODS steel forms a tri-layer oxide film and the surface morphologies have experienced four structures. For the tri-layer oxide film, the middle layer is mainly Fe-Cr spinel and the Al is gradually enriched in the inner layer. - Highlights: • We evaluated the corrosion resistance of three different Cr content ODS steels at 650 °C in supercritical water. • Corrosion behavior of ODS steels is rarely reported and ODS steel may be promising material for generation IV reactors. • We found total opposite phenomenon compared to Lee's work before. Our result may be more reasonable.

Supercritical carbon dioxide as an innovative reaction medium for selective oxidation

Energy Technology Data Exchange (ETDEWEB)

Loeker, F.; Leitner, W. [Max-Planck-Institut fuer Kohlenforschung, Muelheim an der Ruhr (Germany)

1998-12-31

Although the catalytic efficiency of all catalytic oxidation processes studied in scCO{sub 2} up to now is far from being satisfactory, the principle possibility to carry out such reactions in this medium is clearly evident. Future research in our group will be directed towards the development of homogeneous and heterogeneous catalysts that are adopted to the special requirements of both the oxidation process and the supercritical reaction medium. Preliminary results from these studies regarding the epoxidation of olefins with molecular oxygen as oxidant will be presented on the conference poster. (orig.)

Evaluation of tubular reactor designs for supercritical water oxidation of U.S. Department of Energy mixed waste

International Nuclear Information System (INIS)

Barnes, C.M.

1994-12-01

Supercritical water oxidation (SCWO) is an emerging technology for industrial waste treatment and is being developed for treatment of the US Department of Energy (DOE) mixed hazardous and radioactive wastes. In the SCWO process, wastes containing organic material are oxidized in the presence of water at conditions of temperature and pressure above the critical point of water, 374 C and 22.1 MPa. DOE mixed wastes consist of a broad spectrum of liquids, sludges, and solids containing a wide variety of organic components plus inorganic components including radionuclides. This report is a review and evaluation of tubular reactor designs for supercritical water oxidation of US Department of Energy mixed waste. Tubular reactors are evaluated against requirements for treatment of US Department of Energy mixed waste. Requirements that play major roles in the evaluation include achieving acceptable corrosion, deposition, and heat removal rates. A general evaluation is made of tubular reactors and specific reactors are discussed. Based on the evaluations, recommendations are made regarding continued development of supercritical water oxidation reactors for US Department of Energy mixed waste

Oxidation performance of high temperature steels and coatings for future supercritical power plants

Energy Technology Data Exchange (ETDEWEB)

Auerkari, Pertti; Salonen, Jorma; Toivonen, Aki; Penttilae, Sami [VTT, Espoo (Finland); Haekkilae, Juha [Foster Wheeler Energia, Varkaus (Finland); Aguero, Alina; Gutierrez, Marcos; Muelas, Raul [INTA, Madrid (Spain); Fry, Tony [NPL (United Kingdom)

2010-07-01

The operating efficiency of current and future thermal power plants is largely dependent on the applied temperature and pressure, which are in part limited by the internal oxidation resistance of the structural materials in the steam systems. Alternative and reference materials for such systems have been tested within the COST 536 (ACCEPT) project, including bulk reference materials (ferritic P92 and austenitic 316 LN steels) and several types of coatings under supercritical combined (oxygen) water chemistry (150 ppb DO) at 650 C/300 bar. The testing results from a circulating USC autoclave showed that under such conditions the reference bulk steels performed poorly, with extensive oxidation already after relatively short term exposure to the supercritical medium. Better protection was attained by suitable coatings, although there were clear differences in the protective capabilities between different coating types, and some challenges remain in applying (and repairing) coatings for the internal surfaces of welded structures. The materials performance seems to be worse in supercritical than in subcritical conditions, and this appears not to be only due to the effect of temperature. The implications are considered from the point of view of the operating conditions and materials selection for future power plants. (orig.)

Delocalized organic pollutant destruction through a self-sustaining supercritical water oxidation process

International Nuclear Information System (INIS)

Lavric, E.D.; Weyten, H.; Ruyck, J. de; Plesu, V.; Lavric, V.

2005-01-01

Supercritical water oxidation (SCWO) is a recent development aiming at the destruction of organic pollutants present with low concentrations in waste waters. The present paper focuses on the process simulation of SCWO with emphasis on the proper modelling of supercritical thermodynamic conditions and on the possibility to make the SCWO process self-sufficient from the energetic viewpoint. Self-sufficiency may be of interest to encourage more delocalization of waste water treatment. The process of SCWO for dilute waste water (no more than 5 wt.%) is modelled through the ASPEN Plus copyright process simulator. Studies were made to search for energetic self-sufficiency conditions using various technologies for power production from the heat of reaction, like supercritical water expansion in a turbine, use of a closed Brayton cycle (CBC) and use of an organic Rankine cycle (ORC). The results obtained showed that the process is energetically self-sufficient using either a small supercritical turbine, or an ORC. In less restrictive conditions regarding the component efficiencies, the CBC, in theory, also leads to self-sufficiency, but from the analysis, it appears that this solution is less realistic

Formation of ZnO at zinc oxidation by near- and supercritical water under the constant electric field

Science.gov (United States)

Shishkin, A. V.; Sokol, M. Ya.; Shatrova, A. V.; Fedyaeva, O. N.; Vostrikov, A. A.

2014-12-01

The work has detected an influence of a constant electric field (up to E = 300 kV/m) on the structure of a nanocrystalline layer of zinc oxide, formed on the surface of a planar zinc anode in water under supercritical (673 K and 23 MPa) and near-critical (673 K and 17. 5 MPa) conditions. The effect of an increase of zinc oxidation rate with an increase in E is observed under supercritical conditions and is absent at near-critical ones. Increase in the field strength leads to the formation of a looser structure in the inner part of the zinc oxide layer.

Identification of significant process variables for a flow-through supercritical water oxidation reactor

International Nuclear Information System (INIS)

Rossi, R.E.

1992-05-01

The effects of four process variables on the destruction efficiency of a flow-through supercritical water oxidation reactor were investigated. These process variables included: (1) reactor throughput (GPH), (2) concentration of the surrogate waste (% acetone), (3) maximum reactor tube-wall temperature (OC), and (4) applied stoichiometric oxygen. The analysis was conducted utilizing two-level factorial experiments, steepest ascent methods, and central composite designs. This experimental protocol assures efficient experimentation and allows for an empirical response surface model of the system to be developed. This experimentation identified a significant positive effect for stoichiometric oxygen applied and temperature variations between 400 to 500 degrees C. The increase in destruction efficiency due to stoichiometric 0 2 provides strong evidence that supercritical water oxidations are catalyzed by excess oxygen, and the strong temperature effect is a result of large increases in the kinetic rates for this temperature range. However, increasing temperature between 550 to 650 degrees C does not provide substantial increases in destruction efficiency. In addition, destruction efficiency is significantly unproved by increasing the Reynolds number and residence time. The destruction efficiency of the reactor is also dependent upon the initial concentration of surrogate waste. This concentration dependence may indicate first-order supercritical CO kinetics is inadequate for describing all waste types and reactor configurations. Alternatively, it may indicate reactant mixing, caused by local turbulence at the oxidation fronts of these higher concentration waste streams, results in higher destruction efficiencies

Supercritical water oxidation of ion exchange resins: Degradation mechanisms

Energy Technology Data Exchange (ETDEWEB)

Leybros, A.; Roubaud, A. [CEA Marcoule, DEN DTCD SPDE LFSM, F-30207 Bagnols Sur Ceze (France); Guichardon, P. [Ecole Cent Marseille, F-13451 Marseille 20 (France); Boutin, O. [Aix Marseille Univ, UMR CNRS 6181, F-13545 Aix En Provence 4 (France)

2010-07-01

Spent ion exchange resins are radioactive process wastes for which there is no satisfactory industrial treatment. Supercritical water oxidation could offer a viable treatment alternative to destroy the organic structure of resins and contain radioactivity. IER degradation experiments were carried out in a continuous supercritical water reactor. Total organic carbon degradation rates in the range of 95-98% were obtained depending on operating conditions. GC-MS chromatography analyses were carried out to determine intermediate products formed during the reaction. Around 50 species were identified for cationic and anionic resins. Degradation of poly-styrenic structure leads to the formation of low molecular weight compounds. Benzoic acid, phenol and acetic acid are the main compounds. However, other products are detected in appreciable yields such as phenolic species or heterocycles, for anionic IERs degradation. Intermediates produced by intramolecular rearrangements are also obtained. A radical degradation mechanism is proposed for each resin. In this overall mechanism, several hypotheses are foreseen, according to HOO center dot radical attack sites. (authors)

Hazard classification for the supercritical water oxidation test bed. Revision 1

International Nuclear Information System (INIS)

Ramos, A.G.

1994-10-01

A hazard classification of ''routinely accepted by the public'' has been determined for the operation of the supercritical water oxidation test bed at the Idaho National Engineering Laboratory. This determination is based on the fact that the design and proposed operation meet or exceed appropriate national standards so that the risks are equivalent to those present in similar activities conducted in private industry. Each of the 17 criteria for hazards ''routinely accepted by the public,'' identified in the EG and G Idaho, Inc., Safety Manual, were analyzed. The supercritical water oxidation (SCWO) test bed will treat simulated mixed waste without the radioactive component. It will be designed to operate with eight test wastes. These test wastes have been chosen to represent a broad cross-section of candidate mixed wastes anticipated for storage or generation by DOE. In particular, the test bed will generate data to evaluate the ability of the technology to treat chlorinated waste and other wastes that have in the past caused severe corrosion and deposition in SCWO reactors

Role of Cu-Mg-Al mixed oxide catalysts in lignin depolymerization in supercritical ethanol

NARCIS (Netherlands)

Huang, X.; Ceylanpinar, A.; Koranyi, T.I.; Boot, M.D.; Hensen, E.J.M.

2015-01-01

We investigate the role of Cu-Mg-Al mixed oxides in depolymerization of soda lignin in supercritical ethanol. A series of mixed oxides with varying Cu content and (Cu+Mg)/Al ratio were prepared. The optimum catalyst containing 20 wt% Cu and having a (Cu+Mg)/Al ratio of 4 yielded 36 wt% monomers

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.

Preliminary comparison of three processes of AlN oxidation: dry, wet and mixed ones

Directory of Open Access Journals (Sweden)

Korbutowicz R.

2016-03-01

Full Text Available Three methods of AlN layers oxidation: dry, wet and mixed (wet with oxygen were compared. Some physical parameters of oxidized thin films of aluminum nitride (AlN layers grown on silicon Si(1 1 1 were investigated by means Energy-Dispersive X-ray Spectroscopy (EDS and Spectroscopic Ellipsometry (SE. Three series of the thermal oxidations processes were carried out at 1012 °C in pure nitrogen as carrying gas and various gas ambients: (a dry oxidation with oxygen, (b wet oxidation with water steam and (c mixed atmosphere with various process times. All the research methods have shown that along with the rising of the oxidation time, AlN layer across the aluminum oxide nitride transforms to aluminum oxide. The mixed oxidation was a faster method than the dry or wet ones.

Reactive turbulent flow CFD study in supercritical water oxidation process: application to a stirred double shell reactor

International Nuclear Information System (INIS)

Moussiere, S.

2006-12-01

Supercritical water oxidation is an innovative process to treat organic liquid waste which uses supercritical water properties to mix efficiency the oxidant and the organic compounds. The reactor is a stirred double shell reactor. In the step of adaptation to nuclear constraints, the computational fluid dynamic modeling is a good tool to know required temperature field in the reactor for safety analysis. Firstly, the CFD modeling of tubular reactor confirms the hypothesis of an incompressible fluid and the use of k-w turbulence model to represent the hydrodynamic. Moreover, the EDC model is as efficiency as the kinetic to compute the reaction rate in this reactor. Secondly, the study of turbulent flow in the double shell reactor confirms the use of 2D axisymmetric geometry instead of 3D geometry to compute heat transfer. Moreover, this study reports that water-air mixing is not in single phase. The reactive turbulent flow is well represented by EDC model after adaptation of initial conditions. The reaction rate in supercritical water oxidation reactor is mainly controlled by the mixing. (author)

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. Copyright © 2015 Elsevier Ltd. All rights reserved.

Reacting flow simulations of supercritical water oxidation of PCB-contaminated transformer oil in a pilot plant reactor

Directory of Open Access Journals (Sweden)

V. Marulanda

2011-06-01

Full Text Available The scale-up of a supercritical water oxidation process, based on recent advancements in kinetic aspects, reactor configuration and optimal operational conditions, depends on the research and development of simulation tools, which allow the designer not only to understand the complex multiphysics phenomena that describe the system, but also to optimize the operational parameters to attain the best profit for the process and guarantee its safe operation. Accordingly, this paper reports a multiphysics simulation with the CFD software Comsol Multiphysics 3.3 of a pilot plant reactor for the supercritical water oxidation of a heavily PCB-contaminated mineral transformer oil. The proposed model was based on available information for the kinetic aspects of the complex mixture and the optimal operational conditions obtained in a lab-scale continuous supercritical water oxidation unit. The pilot plant simulation results indicate that it is not feasible to scale-up directly the optimal operational conditions obtained in the isothermal lab-scale experiments, due to the excess heat released by the exothermic oxidation reactions that result in outlet temperatures higher than 600°C, even at reactor inlet temperatures as low as 400°C. Consequently, different alternatives such as decreasing organic flowrates or a new reactor set-up with multiple oxidant injections should be considered to guarantee a safe operation.

Design and operational parameters of transportable supercritical water oxidation waste destruction unit

International Nuclear Information System (INIS)

McFarland, R.D.; Brewer, G.R.; Rofer, C.K.

1991-12-01

Supercritical water oxidation (SCWO) is the destruction of hazardous waste by oxidation in the presence of water at temperatures and pressures above its critical point. A 1 gal/h SCWO waste destruction unit (WDU) has been designed, built, and operated at Los Alamos National Laboratory. This unit is transportable and is intended to demonstrate the SCWO technology on wastes at Department of Energy sites. This report describes the design of the WDU and the preliminary testing phase leading to demonstration

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...

Isolation of oxidative degradation products of atorvastatin with supercritical fluid chromatography.

Science.gov (United States)

Klobčar, Slavko; Prosen, Helena

2015-12-01

The isolation of four oxidative degradation products of atorvastatin using preparative high-performance liquid chromatography applying at least two chromatographic steps is known from the literature. In this paper it is shown that the same four impurities could be isolated from similarly prepared mixtures in only one step using supercritical fluid chromatography. The methods for separation were developed and optimized. The preparation of the mixtures was altered in such a way as to enhance the concentration of desired impurities. Appropriate solvents were applied for collection of separated impurities in order to prevent degradation. The structures of the isolated impurities were confirmed and their purity determined. The preparative supercritical fluid chromatography has proven to be superior to preparative HPLC regarding achieved purity of standards applying fewer chromatographic as well as isolation steps. Copyright © 2015 John Wiley & Sons, Ltd.

Supercritical Water Oxidation: A Solution for the Elimination of Back-End Organic Reprocessing Wastes

Energy Technology Data Exchange (ETDEWEB)

Leybros, A.; Roubaud, A.; Turc, H.A.; Fournel, B. [Supercritical fluids and membranes Laboratory, CEA Valrho, BP 17171, 30207 Bagnols/Ceze Cedex (France)

2008-07-01

Supercritical water oxidation (SCWO) is a very efficient technique for total elimination of organic wastes from reprocessing activities on the way of 'zero wastes' facilities. This technology uses the properties of supercritical water (P > 221 bars and T > 647 K) to obtain a good mixing between oxygen (the oxidant) and the organic waste. Thereby, the oxidation reaction is fast and complete. Using the SCWO process, contamination contained in organic materials like spent solvents can be confined in a closed space, like a reactor in a glovebox. A new application is tested for the treatment of solid organic wastes like ion exchange resins (IER). Experiments are made with suspensions of IER in water and isopropyl-alcohol. A nuclear version of the process with the double shell reactor has been constructed and is being tested. The aim of this work is to obtain a treatment capacity of 1 kg/h for the nuclear version with the same global set-up, concept of process and security as well as contamination management as for a 200 g/h pilot. (authors)

Supercritical Water Oxidation: A Solution for the Elimination of Back-End Organic Reprocessing Wastes

International Nuclear Information System (INIS)

Leybros, A.; Roubaud, A.; Turc, H.A.; Fournel, B.

2008-01-01

Supercritical water oxidation (SCWO) is a very efficient technique for total elimination of organic wastes from reprocessing activities on the way of 'zero wastes' facilities. This technology uses the properties of supercritical water (P > 221 bars and T > 647 K) to obtain a good mixing between oxygen (the oxidant) and the organic waste. Thereby, the oxidation reaction is fast and complete. Using the SCWO process, contamination contained in organic materials like spent solvents can be confined in a closed space, like a reactor in a glovebox. A new application is tested for the treatment of solid organic wastes like ion exchange resins (IER). Experiments are made with suspensions of IER in water and isopropyl-alcohol. A nuclear version of the process with the double shell reactor has been constructed and is being tested. The aim of this work is to obtain a treatment capacity of 1 kg/h for the nuclear version with the same global set-up, concept of process and security as well as contamination management as for a 200 g/h pilot. (authors)

Photocatalytic and chemical oxidation of organic compounds in supercritical carbon dioxide. 1998 annual progress report

International Nuclear Information System (INIS)

Blake, D.M.

1998-01-01

'This report summarizes the results of work done during the first 1.3 years of a three year project. During the first nine months effort focussed on the design, construction and testing of a closed recirculating system that can be used to study photochemistry in supercritical carbon dioxide at pressures up to 5,000 psi and temperatures up to about 50 C. This was followed by a period of work in which the photocatalytic oxidation of benzene and acetone in supercritical, liquid, and gaseous carbon dioxide containing dissolved oxygen was demonstrated. The photocatalyst was titanium dioxide supported on glass spheres. This was the first time it was possible to observe photocatalytic oxidation in a supercritical fluid and to compare reaction in the three fluid phases of a solvent. This also demonstrated that it is possible to purify supercritical and liquid carbon dioxide using photochemical oxidation with no chemical additions other than oxygen. The oxidation of benzene produced no intermediates detectable using on line spectroscopic analysis or by gas chromatographic analysis of samples taken from the flow system. The catalyst surface did darken as the reaction proceeded indicating that oxidation products were accumulating on the surface. This is analogous to the behavior of aromatic compounds in air phase photocatalytic oxidation. The reaction of acetone under similar conditions resulted in the formation of low levels of by-products. Two were identified as products of the reaction of acetone with itself (4-methyl-3-penten-2-one and 4-hydroxy-4-methyl-2-pentanone) using gas chromatography with a mass spectrometer detector. Two other by-products also appear to be from the self-reaction of acetone. By-products of this type had not been observed in prior studies of the gas-phase photocatalytic oxidation of acetone. The by-products that have been observed can also be oxidized under the treatment conditions. The above results establish that photocatalytic oxidation of

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

International Nuclear Information System (INIS)

Hung, C.-M.

2009-01-01

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

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

Energy Technology Data Exchange (ETDEWEB)

Hung, C.-M. [Department of Industry Engineering and Management, Yung-Ta Institute of Technology and Commerce, 316 Chung-shan Road, Linlo, Pingtung 909, Taiwan (China)], E-mail: hungcm1031@gmail.com

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{sub 2}PtCl{sub 6}, Pd(NO{sub 3}){sub 3} and Rh(NO{sub 3}){sub 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{sup -1} in the wet catalytic processes.

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.

Investigation on leaching of actinide oxides into supercritical fluids

International Nuclear Information System (INIS)

Shafikov, D.N.; Kamachev, V.A.; Babain, V.A.; Murzin, A.A.; Shadrin, A.Yu.; Podojnitsin, S.V.

2006-01-01

The extraction of actinide oxides into solutions of the TBP-HNO 3 complex in supercritical (SC) CO 2 was investigated. Experiments on the extraction of the TBP-HNO 3 complex into SC CO 2 were first conducted. It was found that a constant concentration of TBP in SC CO 2 of 13.5-14.8 % vol. can be attained using a constant molar ratio of [HNO 3 ]:[TBP] about 2.5 : 1. Joint leaching of uranium, plutonium and neptunium from mixtures of actinide oxides with solutions of TBP-HNO 3 in SC CO 2 was found feasible. If the leaching of uranium is about 95 %, its purification coefficients from major gamma-emitting radionuclides (Cs and Sr) exceed 100, while the purification coefficients of uranium from rare earth elements are 10-20

Biodiesel from sunflower oil in supercritical methanol with calcium oxide

International Nuclear Information System (INIS)

Demirbas, Ayhan

2007-01-01

In this study, sunflower seed oil was subjected to the transesterification reaction with calcium oxide (CaO) in supercritical methanol for obtaining biodiesel. Methanol is used most frequently as the alcohol in the transesterification process. Calcium oxide (CaO) can considerably improve the transesterification reaction of sunflower seed oil in supercritical methanol. The variables affecting the methyl ester yield during the transesterification reaction, such as the catalyst content, reaction temperature and the molar ratio of soybean oil to alcohol, were investigated and compared with those of non-catalyst runs. The catalytic transesterification ability of CaO is quite weak under ambient temperature. At a temperature of 335 K, the yield of methyl ester is only about 5% in 3 h. When CaO was added from 1.0% to 3.0%, the transesterification speed increased evidently, while when the catalyst content was further enhanced to 5%, the yield of methyl ester slowly reached to a plateau. It was observed that increasing the reaction temperature had a favorable influence on the methyl ester yield. In addition, for molar ratios ranging from 1 to 41, as the higher molar ratios of methanol to oil were charged, the greater transesterification speed was obtained. When the temperature was increased to 525 K, the transesterification reaction was essentially completed within 6 min with 3 wt% CaO and 41:1 methanol/oil molar ratio

Partial oxidation of landfill leachate in supercritical water: Optimization by response surface methodology

International Nuclear Information System (INIS)

Gong, Yanmeng; Wang, Shuzhong; Xu, Haidong; Guo, Yang; Tang, Xingying

2015-01-01

Highlights: • Partial oxidation of landfill leachate in supercritical water was investigated. • The process was optimized by Box–Behnken design and response surface methodology. • GY H2 , TRE and CR could exhibit up to 14.32 mmol·gTOC −1 , 82.54% and 94.56%. • Small amounts of oxidant can decrease the generation of tar and char. - Abstract: To achieve the maximum H 2 yield (GY H2 ), TOC removal rate (TRE) and carbon recovery rate (CR), response surface methodology was applied to optimize the process parameters for supercritical water partial oxidation (SWPO) of landfill leachate in a batch reactor. Quadratic polynomial models for GY H2 , CR and TRE were established with Box–Behnken design. GY H2 , CR and TRE reached up to 14.32 mmol·gTOC −1 , 82.54% and 94.56% under optimum conditions, respectively. TRE was invariably above 91.87%. In contrast, TC removal rate (TR) only changed from 8.76% to 32.98%. Furthermore, carbonate and bicarbonate were the most abundant carbonaceous substances in product, whereas CO 2 and H 2 were the most abundant gaseous products. As a product of nitrogen-containing organics, NH 3 has an important effect on gas composition. The carbon balance cannot be reached duo to the formation of tar and char. CR increased with the increase of temperature and oxidation coefficient

Supercritical waste oxidation pump investigation

International Nuclear Information System (INIS)

Thurston, G.; Garcia, K.

1993-02-01

This report investigates the pumping techniques and pumping equipment that would be appropriate for a 5,000 gallon per day supercritical water oxidation waste disposal facility. The pumps must boost water, waste, and additives from atmospheric pressure to approximately 27.6 MPa (4,000 psia). The required flow ranges from 10 gpm to less than 0.1 gpm. For the higher flows, many commercial piston pumps are available. These pumps have packing and check-valves that will require periodic maintenance; probably at 2 to 6 month intervals. Several commercial diaphragm pumps were also discovered that could pump the higher flow rates. Diaphragm pumps have the advantage of not requiring dynamic seals. For the lower flows associated with the waste and additive materials, commercial diaphragm pumps. are available. Difficult to pump materials that are sticky, radioactive, or contain solids, could be injected with an accumulator using an inert gas as the driving mechanism. The information presented in this report serves as a spring board for trade studies and the development of equipment specifications

Oxidation kinetics of model compounds of metabolic waste in supercritical water

Science.gov (United States)

Webley, Paul A.; Holgate, Henry R.; Stevenson, David M.; Tester, Jefferson W.

1990-01-01

In this NASA-funded study, the oxidation kinetics of methanol and ammonia in supercritical water have been experimentally determined in an isothermal plug flow reactor. Theoretical studies have also been carried out to characterize key reaction pathways. Methanol oxidation rates were found to be proportional to the first power of methanol concentration and independent of oxygen concentration and were highly activated with an activation energy of approximately 98 kcal/mole over the temperature range 480 to 540 C at 246 bar. The oxidation of ammonia was found to be catalytic with an activation energy of 38 kcal/mole over temperatures ranging from 640 to 700 C. An elementary reaction model for methanol oxidation was applied after correction for the effect of high pressure on the rate constants. The conversion of methanol predicted by the model was in good agreement with experimental data.

Degradation of quinoline by wet oxidation - kinetic aspects and reaction mechanisms

DEFF Research Database (Denmark)

Thomsen, A.B.

1998-01-01

The high temperature, high pressure wet oxidation reaction of quinoline has been studied as a function of initial concentration, pH and temperature. At neutral to acidic pH, it is effective in the oxidation of quinoline at 240 degrees C and above, whereas under alkaline conditions the reaction...... is markedly slowed down. The results indicate that the reaction is an auto-catalysed, free radical chain reaction transforming 99% of quinoline to other substances. Of the quinoline. 30-50% was oxidised to CO2 and H2O depending on the initial concentration. Wet oxidation of deuterium-labelled quinoline...

Oxidation-extraction of uranium from wet-process phosphoric acid

International Nuclear Information System (INIS)

Lawes, B.C.

1985-01-01

The invention involves an improvement to the reductive stripping process for recovering uranium values from wet-process phosphoric acid solution, where uranium in the solution is oxidized to uranium (VI) oxidation state and then extracted from the solution by contact with a water immiscible organic solvent, by adding sufficient oxidant, hydrogen peroxide, to obtain greater than 90 percent conversion of the uranium to the uranium (VI) oxidation state to the phosphoric acid solution and simultaneously extracting the uranium (VI)

Enhanced wet air oxidation : synergistic rate acceleration upon effluent recirculation

Science.gov (United States)

Matthew J. Birchmeier; Charles G. Hill; Carl J. Houtman; Rajai H. Atalla; Ira A. Weinstock

2000-01-01

Wet air oxidation (WAO) reactions of cellobiose, phenol, and syringic acid were carried out under mild conditions (155°C; 0.93MPa 02; soluble catalyst, Na5[PV2Mo10O40]). Initial oxidation rates were rapid but decreased to small values as less reactive oxidation products accumulated. Recalcitrant oxidation products were consumed more rapidly, however, if additional...

Partial oxidation of landfill leachate in supercritical water: Optimization by response surface methodology

Energy Technology Data Exchange (ETDEWEB)

Gong, Yanmeng; Wang, Shuzhong; Xu, Haidong; Guo, Yang; Tang, Xingying

2015-09-15

Highlights: • Partial oxidation of landfill leachate in supercritical water was investigated. • The process was optimized by Box–Behnken design and response surface methodology. • GY{sub H2}, TRE and CR could exhibit up to 14.32 mmol·gTOC{sup −1}, 82.54% and 94.56%. • Small amounts of oxidant can decrease the generation of tar and char. - Abstract: To achieve the maximum H{sub 2} yield (GY{sub H2}), TOC removal rate (TRE) and carbon recovery rate (CR), response surface methodology was applied to optimize the process parameters for supercritical water partial oxidation (SWPO) of landfill leachate in a batch reactor. Quadratic polynomial models for GY{sub H2}, CR and TRE were established with Box–Behnken design. GY{sub H2}, CR and TRE reached up to 14.32 mmol·gTOC{sup −1}, 82.54% and 94.56% under optimum conditions, respectively. TRE was invariably above 91.87%. In contrast, TC removal rate (TR) only changed from 8.76% to 32.98%. Furthermore, carbonate and bicarbonate were the most abundant carbonaceous substances in product, whereas CO{sub 2} and H{sub 2} were the most abundant gaseous products. As a product of nitrogen-containing organics, NH{sub 3} has an important effect on gas composition. The carbon balance cannot be reached duo to the formation of tar and char. CR increased with the increase of temperature and oxidation coefficient.

Supercritical water oxidation of dioxins and furans in waste incinerator fly ash, sewage sludge and industrial soil.

Science.gov (United States)

Zainal, Safari; Onwudili, Jude A; Williams, Paul T

2014-08-01

Three environmental samples containing dioxins and furans have been oxidized in the presence of hydrogen peroxide under supercritical water oxidation conditions. The samples consisted of a waste incinerator fly ash, sewage sludge and contaminated industrial soil. The reactor system was a batch, autoclave reactor operated at temperatures between 350 degrees C and 450degrees C, corresponding to pressures of approximately 20-33.5 MPa and with hydrogen peroxide concentrations from 0.0 to 11.25 vol%. Hydrogen peroxide concentration and temperature/pressure had a strong positive effect on the oxidation of dioxins and furans. At the highest temperatures and pressure of supercritical water oxidation of 4500C and 33.5 MPa and with 11.25 vol% of hydrogen peroxide, the destruction efficiencies of the individual polychlorinated dibenzo-p-dioxins/polychlorinated dibenzofurans (PCDD/PCDF) isomers were between 90% and 99%. There did not appear to be any significant differences in the PCDD/PCDF destruction efficiencies in relation to the different sample matrices of the waste incinerator fly ash, sewage sludge and contaminated industrial soil.

A flow reactor for the flow supercritical water oxidation of wastes to mitigate the reactor corrosion problem

International Nuclear Information System (INIS)

Chitanvis, S.M.

1994-01-01

We have designed a flow tube reactor for supercritical water oxidation of wastes that confines the oxidation reaction to the vicinity of the axis of the tube. This prevents high temperatures and reactants as well as reaction products from coming in intimate contact with reactor walls. This implies a lessening of corrosion of the walls of the reactor. We display numerical simulations for a vertical reactor with conservative design parameters that illustrate our concept. We performed our calculations for the destruction of sodium nitrate by ammonium hydroxide In the presence of supercritical water, where the production of sodium hydroxide causes corrosion. We have compared these results with that for a horizontal set-up where the sodium hydroxide created during the reaction ends up on the floor of the tube, implying a higher probability of corrosion

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.

Performance improvement and better scalability of wet-recessed and wet-oxidized AlGaN/GaN high electron mobility transistors

Science.gov (United States)

Takhar, Kuldeep; Meer, Mudassar; Upadhyay, Bhanu B.; Ganguly, Swaroop; Saha, Dipankar

2017-05-01

We have demonstrated that a thin layer of Al2O3 grown by wet-oxidation of wet-recessed AlGaN barrier layer in an AlGaN/GaN heterostructure can significantly improve the performance of GaN based high electron mobility transistors (HEMTs). The wet-etching leads to a damage free recession of the gate region and compensates for the decreased gate capacitance and increased gate leakage. The performance improvement is manifested as an increase in the saturation drain current, transconductance, and unity current gain frequency (fT). This is further augmented with a large decrease in the subthreshold current. The performance improvement is primarily ascribed to an increase in the effective velocity in two-dimensional electron gas without sacrificing gate capacitance, which make the wet-recessed gate oxide-HEMTs much more scalable in comparison to their conventional counterpart. The improved scalability leads to an increase in the product of unity current gain frequency and gate length (fT × Lg).

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).

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

International Nuclear Information System (INIS)

Hung, Chang-Mao

2009-01-01

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 .

Physico-chemical effects of supercritical carbon dioxide post polymerization treatment on HCl-doped polyaniline prepared via oxidative chemical polymerization

Science.gov (United States)

Fernando, J. G.; Vequizo, R. M.; Odarve, M. K. G.; Sambo, B. R. B.; Alguno, A. C.; Malaluan, R. M.; Candidato, R. T., Jr.; Gambe, J. E.; Jabian, M.; Paylaga, G. J.; Bagsican, F. R. G.; Miyata, H.

2015-06-01

Polyanilinefilms doped with varying HClconcentrations (0.2 M, 0.6 M and 1.0 M) were synthesized on glass substrates via oxidative polymerization of aniline. The films were treated with supercritical carbon dioxide (SC-CO2) at 30 MPa and 40°C for 30 minutes. Their structural, optical and morphological properties were studied and compared to conventionally prepared polyanilinefilms using FTIR analysis, UVVisspectroscopy and scanning electron microscopy. It was observed that supercritical carbon dioxide (SC-CO2) could interact with PANI films that consequently altered the bandgapsand changed the film thickness. SC-CO2 treatment also increased the oxidation level of polyanilinefilms and modified the morphology of polyanilinefilm doped with 1M HCl.

Supercritical water oxidation benchscale testing metallurgical analysis report

International Nuclear Information System (INIS)

Norby, B.C.

1993-02-01

This report describes metallurgical evaluation of witness wires from a series of tests using supercritical water oxidation (SCWO) to process cutting oil containing a simulated radionuclide. The goal of the tests was to evaluate the technology's ability to process a highly chlorinated waste representative of many mixed waste streams generated in the DOE complex. The testing was conducted with a bench-scale SCWO system developed by the Modell Development Corporation. Significant test objectives included process optimization for adequate destruction efficiency, tracking the radionuclide simulant and certain metals in the effluent streams, and assessment of reactor material degradation resulting from processing a highly chlorinated waste. The metallurgical evaluation described herein includes results of metallographic analysis and Scanning Electron Microscopy analysis of witness wires exposed to the SCWO environment for one test series

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...

Partial oxidation of n-hexadecane through decomposition of hydrogen peroxide in supercritical water

KAUST Repository

Alshammari, Y.M.

2015-01-01

© 2014 The Institution of Chemical Engineers. This work reports the experimental analysis of partial oxidation of n-hexadecane under supercritical water conditions. A novel reactor flow system was developed which allows for total decomposition of hydrogen peroxide in a separate reactor followed partial oxidation of n-hexadecane in a gasification reactor instead of having both reactions in one reactor. The kinetics of hydrothermal decomposition of hydrogen peroxide was studied in order to confirm its full conversion into water and oxygen under the desired partial oxidation conditions, and the kinetic data were found in a good agreement with previously reported literature. The gas yield and gasification efficiency were investigated under different operating parameters. Furthermore, the profile of C-C/C=C ratio was studied which showed the favourable conditions for maximising yields of n-alkanes via hydrogenation of their corresponding 1-alkenes. Enhanced hydrogenation of 1-alkenes was observed at higher O/C ratios and higher residence times, shown by the increase in the C-C/C=C ratio to more than unity, while increasing the temperature has shown much less effect on the C-C/C=C ratio at the current experimental conditions. In addition, GC-MS analysis of liquid samples revealed the formation of heavy oxygenated compounds which may suggest a new addition reaction to account for their formation under the current experimental conditions. Results show new promising routes for hydrogen production with in situ hydrogenation of heavy hydrocarbons in a supercritical water reactor.

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

Energy Technology Data Exchange (ETDEWEB)

Hung, Chang-Mao, E-mail: hungcm1031@gmail.com [Department of Industry Engineering and Management, Yung-Ta Institute of Technology and Commerce, 316 Chung-shan Road, Linlo, Pingtung 909, Taiwan (China)

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{sup -1}.

Low Temperature Synthesis of Metal Oxides by a Supercritical Seed Enhanced Crystallization (SSEC) Process

DEFF Research Database (Denmark)

Jensen, Henrik; Brummerstedt Iversen, Steen; Joensen, Karsten Dan

2006-01-01

A novel method for producing crystalline nanosized metal oxides by a Supercritical Seed Enhanced Crystallization (SSEC) Process has been developed. The process is a modified sol-gel process taking place at temperatures as low as 95 ºC with supercritical CO2 as solvent and polypropylene as seeding...... material. The nanocrystalline product is obtained without having to resort to costly post-reaction processing and the product is obtained directly after the SSEC process. TiO2 powders produced by the SSEC process were shown to have a crystallinity of 60 % and a crystal size of 7.3 ± 2.6 nm....... The crystallinity can be controlled by changing the heating rate of the initial formation of the nanoparticles and the morphology can be altered by changing the process time....

Operation and Performance of the Supercritical Fluids Reactor (SFR)

National Research Council Canada - National Science Library

Hanush, R

1996-01-01

The Supercritical Fluids Reactor (SFR) at Sandia National Laboratories, CA has been developed to examine and solve engineering, process, and fundamental chemistry issues regarding the development of supercritical water oxidation (SCWO...

Partial oxidation of municipal sludge with activited carbon catalyst in supercritical water

International Nuclear Information System (INIS)

Guo Yang; Wang Shuzhong; Gong Yanmeng; Xu Donghai; Tang Xingying; Ma Honghe

2010-01-01

The partial oxidation (POX) characteristics of municipal sludge in supercritical water (SCW) were investigated by using batch reactor. Effects of reaction parameters such as oxidant equivalent ratio (OER), reaction time and temperature were investigated. Activated carbon (AC) could effectively improve the mole fraction of H 2 in gas product at low OER. However, high OER (greater than 0.3) not only led to the combustion reaction of CO and H 2 , but also caused corrosion of reactor inner wall. Hydrogenation and polymerization of the intermediate products are possible reasons for the relative low COD removal rate in our tests. Metal oxide leached from the reactor inner wall and the main components of the granular sludge were deposited in the AC catalyst. Reaction time had more significant effect on BET surface area of AC than OER had. Long reaction time led to the methanation reaction following hydrolysis and oxidation reaction of AC in SCW in the presence of oxygen. Correspondingly, the possible reaction mechanisms were proposed.

Development studies of a novel wet oxidation process

International Nuclear Information System (INIS)

Rogers, T.W.; Dhooge, P.M.

1995-01-01

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

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.

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

International Nuclear Information System (INIS)

Chen, Zhi-Yuan; Wang, Li-Jun; Li, Fu-Shen; Chou, Kuo-Chih

2013-01-01

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 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

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.

Depolymerization of organosolv lignin using doped porous metal oxides in supercritical methanol

DEFF Research Database (Denmark)

Warner, Genoa; Hansen, Thomas Søndergaard; Riisager, Anders

2014-01-01

conversion to methanol-soluble products, without char formation, were based on copper in combination with other dopants based on relatively earth-abundant metals. Nearly complete conversion of lignin to bio-oil composed of monomers and low-mass oligomers with high aromatic content was obtained in 6. h at 310......An isolated, solvent-extracted lignin from candlenut (Aleurites moluccana) biomass was subjected to catalytic depolymerization in the presence of supercritical methanol, using a range of porous metal oxides derived from hydrotalcite-like precursors. The most effective catalysts in terms of lignin...

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

, 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......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...... 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...

Functionalization of silicon oxide using supercritical fluid deposition of 3,4-epoxybutyltrimethoxysilane for the immobilization of amino-modified oligonucleotide

Energy Technology Data Exchange (ETDEWEB)

Rull, Jordi [Université Grenoble Alpes, Grenoble F38000 (France); CEA, LETI, MINATEC Campus, Grenoble Cedex 9 F38054 (France); CEA, iRTSV, LCBM, Grenoble 38054 (France); CNRS, UMR 5249, Grenoble (France); Nonglaton, Guillaume, E-mail: guillaume.nonglaton@cea.fr [Université Grenoble Alpes, Grenoble F38000 (France); CEA, LETI, MINATEC Campus, Grenoble Cedex 9 F38054 (France); Costa, Guillaume; Fontelaye, Caroline [Université Grenoble Alpes, Grenoble F38000 (France); CEA, LETI, MINATEC Campus, Grenoble Cedex 9 F38054 (France); Marchi-Delapierre, Caroline; Ménage, Stéphane [Université Grenoble Alpes, Grenoble F38000 (France); CEA, iRTSV, LCBM, Grenoble 38054 (France); CNRS, UMR 5249, Grenoble (France); Marchand, Gilles [Université Grenoble Alpes, Grenoble F38000 (France); CEA, LETI, MINATEC Campus, Grenoble Cedex 9 F38054 (France)

2015-11-01

Graphical abstract: - Highlights: • First example of grafting of 3,4-epoxybutyltrimethoxysilane (EBTMOS) onto silicon oxide by supercritical fluid deposition. • Extraordinary efficiency of the supercritical fluid deposition for the grafting of the EBTMOS compared with the conventional solution or vapor phase methodologies. • Demonstration of the efficiency of this functionalization process for the immobilization of amino-modified oligonucleotides. - Abstract: The functionalization of silicon oxide based substrates using silanes is generally performed through liquid phase methodologies. These processes involve a huge quantity of potentially toxic solvents and present some important disadvantages for the functionalization of microdevices or porous materials, for example the low diffusion. To overcome this drawback, solvent-free methodologies like molecular vapor deposition (MVD) or supercritical fluid deposition (SFD) have been developed. In this paper, the deposition process of 3,4-epoxybutyltrimethoxysilane (EBTMOS) on silicon oxide using supercritical carbon dioxide (scCO{sub 2}) as a solvent is studied for the first time. The oxirane ring of epoxy silanes readily reacts with amine group and is of particular interest for the grafting of amino-modified oligonucleotides or antibodies for diagnostic application. Then the ability of this specific EBTMOS layer to react with amine functions has been evaluated using the immobilization of amino-modified oligonucleotide probes. The presence of the probes is revealed by fluorescence using hybridization with a fluorescent target oligonucleotide. The performances of SFD of EBTMOS have been optimized and then compared with the dip coating and molecular vapor deposition methods, evidencing a better grafting efficiency and homogeneity, a lower reaction time in addition to the eco-friendly properties of the supercritical carbon dioxide. The epoxysilane layers have been characterized by surface enhanced ellipsometric

Effect of yttria addition on the stability of porous chromium oxide ceramics in supercritical water

International Nuclear Information System (INIS)

Dong Ziqiang; Chen Weixing; Zheng Wenyue; Guzonas, Dave

2013-01-01

Porous chromium oxide (Cr 2 O 3 ) ceramics were prepared by oxidizing highly porous chromium carbides that were obtained by a reactive sintering method, and were evaluated at temperatures ranging from 375 °C to 625 °C in supercritical water (SCW) environments with a fixed pressure of 25–30 MPa. Reactive element yttrium was introduced to the porous oxide ceramic by adding various amounts of yttria of 5, 10 and 20 wt.%, respectively, prior to reactive sintering. The exposure in SCW shows that the porous chromium oxide is quite stable in SCW at 375 °C. However, the stability decreased with increasing temperature. It is well known that chromium oxide can be oxidized to soluble chromium (VI) species in SCW when oxygen is present. Adding yttria increases the stability of chromium oxide in SCW environments. However, adding yttria higher than 5 wt.% increased the weight loss of porous chromium oxide samples because of the direct dissociation of Y 2 O 3 in SCW.

Effect of supercritical CO2 on the morphology and fluorescent behavior of fluorinated polyylidenefluorenes derivative/graphene oxide nanohybrids

NARCIS (Netherlands)

Li, Jing; Zheng, Shijun; Wang, Xiaobo; Yang, Hongxia; Loos, Katja; Xu, Qun

2015-01-01

Fluorinated polyylidenefluorenes derivative, poly [(9-ylidene-{2-tetradecyloxy-5-tetrafluorophthalimide-phenyl}fluorenyl-2,7-diyl)-alt-(1,4-phenyl)] (PFFB)/graphene oxide (GO) nanohybrids (SC-PFFB/GO) were successfully fabricated via a facile method with the assistance of supercritical CO2 (SC CO2).

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

Energy Technology Data Exchange (ETDEWEB)

Angermann, Heike, E-mail: angermann@helmholtz-berlin.de

2014-09-01

Highlights: • Determination of electronic interface properties by contact-less surface photovoltage (SPV) technique. • Systematic correlations of substrate morphology and surface electronic properties. • Optimization of surface pre-treatment for flat, saw damage etched, and textured Si solar cell substrates. • Ultra-thin passivating Si oxide layers with low densities of rechargeable states by wet-chemical oxidation and subsequent annealing. • Environmentally acceptable processes, utilizing hot water, diluted HCl, or ozone low cost alternative to current approaches with concentrated chemicals. • The effect of optimized wet-chemical pre-treatments can be preserved during subsequent layer deposition. - Abstract: 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 D{sub it}(E), and density D{sub it,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

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

International Nuclear Information System (INIS)

Angermann, Heike

2014-01-01

Highlights: • Determination of electronic interface properties by contact-less surface photovoltage (SPV) technique. • Systematic correlations of substrate morphology and surface electronic properties. • Optimization of surface pre-treatment for flat, saw damage etched, and textured Si solar cell substrates. • Ultra-thin passivating Si oxide layers with low densities of rechargeable states by wet-chemical oxidation and subsequent annealing. • Environmentally acceptable processes, utilizing hot water, diluted HCl, or ozone low cost alternative to current approaches with concentrated chemicals. • The effect of optimized wet-chemical pre-treatments can be preserved during subsequent layer deposition. - Abstract: 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 D it (E), and density D it,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

Measurement of the oxidation-extraction of uranium from wet-process phosphoric acid

International Nuclear Information System (INIS)

Lawes, B.C.

1985-01-01

The present invention relates to processes for the recovery of uranium from wet-process phosphoric acid and more particularly to the oxidation-extraction steps in the DEPA-TOPO process for such recovery. A more efficient use of oxidant is obtained by monitoring the redox potential during the extraction step

Wet oxidation pretreatment of rape straw for ethanol production

International Nuclear Information System (INIS)

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 produced by WO at 205 °C for 3 min with 12 bar of oxygen gas pressure and featured with presoaking in water. At these conditions after pre-treatment, cellulose and hemicellulose was recovered quantitatively (100%) together with 86% of the lignin. WO treatments of 2–3 min at 205–210 °C with 12 bar of oxygen gas produced higher ethanol yields and cellulose, hemicelluloses, and lignin recoveries, than 15 min WO treatment at 195 °C. Also, recycling filtrate and use of higher oxygen gas pressure reduced recovery of materials. The use of filtrate could be inhibitory for the yeast, but also reduced lactic acid formation in SSF. -- Highlights: ► Wet Oxidation pretreatment on rape straw for sugar and ethanol production. ► Variables were reaction time, temperature, and oxygen gas pressure. ► Also, other configurations for increase of water and energy efficiency. ► Short Wet oxidation pretreatment (2–3 min) produced highest ethanol yield. ► After these pretreatment conditions recovery of lignin in solids was 86%.

Kinetics of Chemical Agents Destruction in Supercritical Water

National Research Council Canada - National Science Library

Tester, Jefferson

2003-01-01

.... An experimental study of methylphosphonic acid (MPA) oxidation has been completed that includes macroscopic modeling of the overall global rate law for MPA oxidation in supercritical water (SCW...

Evaporation and wet oxidation of steam generator cleaning solutions

International Nuclear Information System (INIS)

Baldwin, P.N. Jr.

1996-01-01

Ethylene diamine tetra acetic acid (EDTA) is used in metal-cleaning formulations. Usually the form of the EDTA used is the tetra ammonium salt. When these powerful cleaning solutions are used in steam generators, they attract the key metals of interest--iron and copper. A reduction in the volume of these cleaners and EDTA destruction is required to meet waste management and disposal standards. One method of volume reduction is described: concentration by evaporation. Once volume is reduced, the liquid waste can then be further volume reduced and treated for EDTA content through the use of wet oxidation. The effect of this process on the total organic carbon (TOC) in the form of EDTA contained in the copper as well as the iron spent cleaning solutions is reviewed, including regression analysis of selected benchmark and production data. A regressive analysis is made of the relationship between the EDTA and the TOC analyzed in the wet-oxidation batch residuals as well as the summary effects of hydrogen peroxide, sulfuric acid, and reaction time on the percentage of TOC destroyed

Wet oxidative destruction of spent ion-exchange resins using hydrogen peroxide

International Nuclear Information System (INIS)

Srinivas, C.; Ramaswamy, M.; Theyyunni, T.K.

1994-01-01

Spent organic ion exchange resins are generated in large quantities during the operation of nuclear facilities. Wet oxidation as a mode of treatment of these gel-type ion exchange resins was investigated using H 2 O 2 as oxidant in the presence of CuSO 4 as catalyst. Experiments using commercial samples were conducted at 95-100 deg C under reflux conditions at atmospheric pressure. It was found that the reaction of cation resin with H 2 O 2 was instantaneous whereas with anion resin, there was a lag time. For efficient utilization of the oxidant, low rate of addition of H 2 O 2 , 0.01M concentration of CuSO 4 and neutral pH in mixed resin reactions, were found to be useful. Foaming was noted during reactions involving anion resins. This could be controlled by silicone-based agents. The residual solution left after resin oxidation is aqueous in nature and is expected to contain all the radioactivity originally present in the resin. Preliminary experiments showed that it could be efficiently trapped using available inorganic sorbents. Wet oxidation system offers a simple method of converting organic waste into environmentally acceptable inorganic products. (author). 8 refs., 6 figs., 2 tabs

Catalytic upgrading of sugar fractions from pyrolysis oils in supercritical mono-alcohols over Cu doped porous metal oxide

NARCIS (Netherlands)

Yin, Wang; Venderbosch, Hendrikus; Bottari, Giovanni; Krawzcyk, Krzysztof K.; Barta, Katalin; Heeres, Hero Jan

In this work, we report on the catalytic valorization of sugar fractions, obtained by aqueous phase extraction of fast pyrolysis oils, in supercritical methanol (scMeOH) and ethanol (scEtOH) over a copper doped porous metal oxide (Cu-PMO). The product mixtures obtained are, in principle, suitable

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.

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)

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

International Nuclear Information System (INIS)

Hashemi, Mohammed M.; Eftekhari-Sis, Bagher; Khalili, Behzad; Karimi-Jaberi, Zahed

2005-01-01

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)

Synergy in lignin upgrading by a combination of Cu-based mixed oxide and Ni-phosphide catalysts in supercritical ethanol

NARCIS (Netherlands)

Koranyi, T.I.; Huang, X.; Coumans, A.E.; Hensen, E.J.M.

2017-01-01

The depolymerization of lignin to bioaromatics usually requires a hydrodeoxygenation (HDO) step to lower the oxygen content. A mixed Cu–Mg–Al oxide (CuMgAlOx) is an effective catalyst for the depolymerization of lignin in supercritical ethanol. We explored the use of Ni-based cocatalysts, i.e.

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.)

[Kinetics of catalytic wet air oxidation of phenol in trickle bed reactor].

Science.gov (United States)

Li, Guang-ming; Zhao, Jian-fu; Wang, Hua; Zhao, Xiu-hua; Zhou, Yang-yuan

2004-05-01

By using a trickle bed reactor which was designed by the authors, the catalytic wet air oxidation reaction of phenol on CuO/gamma-Al2O3 catalyst was studied. The results showed that in mild operation conditions (at temperature of 180 degrees C, pressure of 3 MPa, liquid feed rate of 1.668 L x h(-1) and oxygen feed rate of 160 L x h(-1)), the removal of phenol can be over 90%. The curve of phenol conversion is similar to "S" like autocatalytic reaction, and is accordance with chain reaction of free radical. The kinetic model of pseudo homogenous reactor fits the catalytic wet air oxidation reaction of phenol. The effects of initial concentration of phenol, liquid feed rate and temperature for reaction also were investigated.

Wet Oxidation of Maleic Acid by a Pumice Supported Copper (II ...

African Journals Online (AJOL)

Pumice supported Cu (II) Schiff base catalysts were prepared by surface chemical modification followed by complexation with Cu (II) acetate. The resulting materials were characterised by Diffuse Reflectance Fourier Transform Spectroscopy (DRIFTS) to confirm the modification. The materials were tested in a wet oxidation ...

Development of a porous wall reactor for Oxidation in Supercritical Water. Hydrodynamic Modelling and application to salty wastes

International Nuclear Information System (INIS)

Fauvel, E.

2002-01-01

This report deals with a transpiring wall reactor for supercritical water oxidation of organic effluents. The singularity of the reactor lies on the inner porous tube made of alumina to minimise both limiting problems, corrosion and salt precipitation. The presence of the inner tube implies a rather complex hydrodynamics. Thus, an hydrodynamic study was performed, in an original way, in a supercritical fluid using the method of the residence time distribution. It enabled to determine the hydrodynamic model of the reactor. Moreover, an inspecting device of the resistance of the inner tube to thermal gradients was developed. Lastly, the performances of the transpiring wall reactor were tested on model compounds such as sodium sulphate and the mixture of dodecane/tributylphosphate. (author) [fr

High Materials Performance in Supercritical CO2 in Comparison with Atmospheric Pressure CO2 and Supercritical Steam

Energy Technology Data Exchange (ETDEWEB)

Holcomb, Gordon [National Energy Technology Lab. (NETL), Pittsburgh, PA, (United States); Tylczak, Joseph [National Energy Technology Lab. (NETL), Pittsburgh, PA, (United States); Carney, Casey [National Energy Technology Lab. (NETL), Pittsburgh, PA, (United States); Dogan, Omer N. [National Energy Technology Lab. (NETL), Pittsburgh, PA, (United States)

2017-02-26

This presentation covers environments (including advanced ultra-supercritical (A-USC) steam boiler/turbine and sCO2 indirect power cycle), effects of pressure, exposure tests, oxidation results, and mechanical behavior after exposure.

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...... treatment gave a more reactive surface than alkaline wet oxidation for wheat straw, whereas the opposite was observed for beech. Fourier transform infrared (FT-IR) spectroscopy showed an almost complete loss of the ester carbonyl stretching signal and the corresponding C-C-O stretching in wet...

Experimental Determination and Modeling of the Phase Behavior for the Selective Oxidation of Benzyl Alcohol in Supercritical CO2

DEFF Research Database (Denmark)

Tsivintzelis, Ioannis; Beier, Matthias Josef; Grunwaldt, Jan-Dierk

2011-01-01

In this study the phase behavior of mixtures relevant to the selective catalytic oxidation of benzyl alcohol to benzaldehyde by molecular oxygen in supercritical CO2 is investigated. Initially, the solubility of N2 in benzaldehyde as well as the dew points of CO2–benzyl alcohol–O2 and CO2...

Molecular Simulation Study of Montmorillonite in Contact with Variably Wet Supercritical Carbon Dioxide

KAUST Repository

Kadoura, Ahmad Salim; Nair, Arun Kumar Narayanan; Sun, Shuyu

2017-01-01

We perform grand canonical Monte Carlo simulations to study the detailed molecular mechanism of intercalation behavior of CO2 in Na-, Ca-, and Mg- montmorillonite exposed to variably hydrated supercritical CO2 at 323.15 K and 90 bar, The simulations

Treatment of toxic and hazardous organic wastes by wet oxidation process with oxygenated water at low temperature

International Nuclear Information System (INIS)

Piccinno, T.; Salluzzo, A.; Nardi, L.; Gili, M.; Luce, A.; Troiani, F.; Cornacchia, G.

1989-11-01

The wet oxidation process using air or molecular oxygen is a well-known process from long time. It is suitable to oxidize several types of waste refractory to the usual biological, thermal and chemical treatments. The drastic operating conditions (high pressures and temperatures) prevented its industrial development. In the last years a new interest was assigned to the process for the treatment of nuclear wastes (organic resins and exhaust organic wastes); the treatment is carried out at widely reduced operating conditions (atmospheric pressure and boiling temperature) by means of metallic catalysts and hydrogen peroxide. With some limits, the wet oxidation with hydrogen peroxide at low temperature can be applied to conventional waste waters containing toxic organic compounds. In the present report are summarized the activities developed at ENEA Fuel Cycle Department by the task force 'Deox' constituted by laboratory and plant specialists in order to verify the application of the wet oxidation process to the treatment of the toxic wastes. (author)

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.

Synergetic effect of copper-plating wastewater as a catalyst for the destruction of acrylonitrile wastewater in supercritical water oxidation

Energy Technology Data Exchange (ETDEWEB)

Shin, Young Ho; Lee, Hong-shik; Lee, Young-Ho [School of Chemical and Biological Engineering and Institute of Chemical Processes, Seoul National University, 599 Gwanangno, Gwanak-gu, Seoul 151-744 (Korea, Republic of); Kim, Jaehoon; Kim, Jae-Duck [Supercritical Fluid Research Laboratory, Energy and Environment Research Division, Korea Institute of Science and Technology (KIST), 39-1 Hawolgok-dong, Seongbuk-gu, Seoul 136-791 (Korea, Republic of); Lee, Youn-Woo, E-mail: ywlee@snu.ac.kr [School of Chemical and Biological Engineering and Institute of Chemical Processes, Seoul National University, 599 Gwanangno, Gwanak-gu, Seoul 151-744 (Korea, Republic of)

2009-08-15

A new supercritical water oxidation process for the simultaneous treatment of mixed wastewater containing wastewater from acrylonitrile manufacturing processes and copper-plating processes was investigated using a continuous tubular reactor system. Experiments were carried out at temperatures ranging from 400 to 600 deg. C and a pressure of 25 MPa. The residence time was fixed at 2 s by changing the flow rates of feeds, depending on reaction temperature. The initial total organic carbon (TOC) concentration of the wastewaters and the O{sub 2} concentration at the reactor inlet were kept constant at 0.49 and 0.74 mol/L. It was confirmed that the copper-plating wastewater accelerated the TOC conversion of acrylonitrile wastewater from 17.6% to 67.3% at a temperature of 450 deg. C. Moreover, copper and copper oxide nanoparticles were generated in the process of supercritical water oxidation (SCWO) of mixed wastewater. 99.8% of copper in mixed wastewater was recovered as solid copper and copper oxides at a temperature of 600 deg. C, with their average sizes ranging from 150 to 160 nm. Our study showed that SCWO provides a synergetic effect for simultaneous treatment of acrylonitrile and copper-plating wastewater. During the reaction, the oxidation rate of acrylonitrile wastewater was enhanced due to the in situ formation of nano-catalysts of copper and/or copper oxides, while the exothermic decomposition of acrylonitrile wastewater supplied enough heat for the recovery of solid copper and copper oxides from copper-plating wastewater. The synergetic effect of wastewater treatment by the newly proposed SCWO process leads to full TOC conversion, color removal, detoxification, and odor elimination, as well as full recovery of copper.

2D and 3D CFD modelling of a reactive turbulent flow in a double shell supercritical water oxidation reactor

International Nuclear Information System (INIS)

Moussiere, S.; Roubaud, A.; Fournel, B.; Joussot-Dubien, C.; Boutin, O.; Guichardon, P.

2012-01-01

In order to design and define appropriate dimensions for a supercritical oxidation reactor, a comparative 2D and 3D simulation of the fluid dynamics and heat transfer during an oxidation process has been performed. The solver used is a commercial code, Fluent 6.2 (R). The turbulent flow field in the reactor, created by the stirrer, is taken into account with a k-omega model and a swirl imposed to the fluid. In the 3D case the rotation of the stirrer can be modelled using the sliding mesh model and the moving reference frame model. This work allows comparing 2D and 3D velocity and heat transfer calculations. The predicted values (mainly species concentrations and temperature profiles) are of the same order in both cases. The reactivity of the system is taken into account with a classical Eddy Dissipation Concept combustion model. Comparisons with experimental temperature measurements validate the ability of the CFD modelling to simulate the supercritical water oxidation reactive medium. Results indicate that the flow can be considered as plug flow-like and that heat transfer is strongly enhanced by the stirring. (authors)

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.

Supercritical Production of Nanoparticles - Part I: The SSEC Process - Part II: Characterization of Nanopartic

DEFF Research Database (Denmark)

Jensen, Henrik

with the crystallite size. Therefore special interest is being devoted to investigating these changes by developing new synthesis and characterizing methods. Wet chemical and gas phase syntheses are among the number of synthesis techniques that have been developed for nanoparticle formation. The sol-gel technique...... is the most broadly applied wet chemical process and it can be used for the production of nanosized materials in the formof particles or coatings for a wide range of materials. However, conventional sol-gel techniques have a number of drawbacks. The process maintains long reaction times and requires post....... The work presented in this thesis addresses the problems related to the conventional sol-gel techniques by using supercritical CO2 as the reaction media. Supercritical fluids exhibit gas like mass transfer properties and liquid like densities which are both particularly attractive to the sol-gel process...

Disposition of nonflammable low-level radioactive wastes using supercritical water with ruthenium(IV) oxide catalyst

International Nuclear Information System (INIS)

Sugiyama, Wataru

2013-01-01

This paper presents the distribution behavior of iron, cobalt, cesium, iodine and strontium attached to nonflammable organic materials, in solid, liquid and gas phases during the decomposition of these materials using supercritical water with ruthenium(IV) oxide (RuO 2 ) catalyst. The distributions of these elements under various conditions (initial amounts, with/without precipitation reagent) were determined by using their radioisotopes as simulated low-level radioactive wastes (LLW) in order to ease the detection of trace amounts of elements even in solid and gas phases. Iron and cobalt were found only in the solid phase when iron hydroxide was added as a precipitation reagent before the supercritical water reaction. Cesium, iodine and strontium were found in the liquid phase after the reaction. Therefore, by adding precipitation reagents such as sodium tetraphenylborate, and sodium carbonate (Na 2 CO 3 ) (or sodium hydrogen carbonate (NaHCO 3 )) and silver nitrate (AgNO 3 ) aqueous solutions to each resultant liquid phase containing cesium, strontium and iodine, respectively, these elements can be successfully recovered only in the solid phase. The gases produced during the decomposition of the organic material contain no radioactivity under all conditions in this study. These results indicate that all of the elements investigated in this study (iron, cobalt, cesium, iodine and strontium) can be recovered successfully by this supercritical water process using RuO 2 Consequently, this process is suggested as a predominant candidate for the treatment of nonflammable organic materials in LLW. (author)

Selective Oxidation and Reactive Wetting During Hot-Dip Galvanizing of a 1.0 pct Al-0.5 pct Si TRIP-Assisted Steel

Science.gov (United States)

Bellhouse, E. M.; McDermid, J. R.

2012-07-01

Selective oxidation and reactive wetting during continuous galvanizing were studied for a low-alloy transformation induced plasticity (TRIP)-assisted steel with 0.2 pct C, 1.5 pct Mn, 1.0 pct Al and 0.5 pct Si. Three process atmospheres were tested during annealing prior to galvanizing: 220 K (-53 °C) dew point (dp) N2-20 pct H2, 243 K (-30 °C) dp N2-5 pct H2 and 278 K (+5 °C) dp N2-5 pct H2. The process atmosphere oxygen partial pressure affected the oxide chemistry, morphology and thickness. For the 220 K (-53 °C) dp and 243 K (-30 °C) dp process atmospheres, film and nodule-type manganese, silicon and aluminum containing oxides were observed at the surface. For the 278 K (+5 °C) dp atmosphere, MnO was observed at the grain boundaries and as thicker localized surface films. Oxide morphology, thickness and chemistry affected reactive wetting, with complete wetting being observed for the 220 K (-53 °C) dp and 243 K (-30 °C) dp process atmospheres and incomplete reactive wetting being observed for the 278 K (+5 °C) dp atmosphere. Complete reactive wetting for the 220 K (-53 °C) dp and 243 K (-30 °C) dp process atmospheres was attributed to a combination of zinc bridging of oxides, aluminothermic reduction of surface oxides and wetting of the oxides. Incomplete wetting for the 278 K (+5 °C) dp atmosphere was attributed to localized thick MnO films.

Degradation of paracetamol by catalytic wet air oxidation and sequential adsorption – Catalytic wet air oxidation on activated carbons

International Nuclear Information System (INIS)

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

2012-01-01

Highlights: ► Three activated carbons (AC) compared as adsorbents and oxidation catalysts. ► Similar evolution for catalytic and adsorptive properties of AC over reuses. ► Acidic and mesoporous AC to be preferred, despite lower initial efficiency. ► Oxidative degradation of paracetamol improves biodegradability. ► 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.

Development studies for a novel wet oxidation process

International Nuclear Information System (INIS)

Dhooge, P.M.; Hakim, L.B.

1994-01-01

A catalytic wet oxidation process (DETOX), which uses an acidic iron solution to oxidize organic compounds to carbon dioxide, water, and other simple products, was investigated as a potential method for the treatment of multicomponent hazardous and mixed wastes. The organic compounds picric acid, poly(vinyl chloride), tetrachlorothiophene, pentachloropyridine, Aroclor 1260 (a polychlorinated biphenyl), and hexachlorobenzene were oxidized in 125 ml reaction vessels. The metals arsenic, barium, beryllium, cadmium, cerium (as a surrogate for plutonium), chromium, lead, mercury, neodymium (as a surrogate for uranium), nickel, and vanadium were tested in the DETOX solution. Barium, beryllium, cerium, chromium, mercury, neodymium, nickel, and vanadium were all found to be very soluble (>100 g/l) in the DETOX chloride-based solution. Arsenic, barium, cadmium, and lead solubilities were lower. Lead could be selectively precipitated from the DETOX solution. Chromium(VI) was reduced to relatively non-toxic chromium(III) by the solution. Six soils were contaminated with arsenic, barium, beryllium, chromium, lead, and neodymium oxides at approximately 0.1% by weight, and benzene, trichloroethene, mineral oil, and Aroclor 1260 at approximately 5% by weight total, and 5.g amounts treated with the DETOX solution in unstirred 125. ml reaction bombs. It is felt that soil treatment in a properly designed system is entirely possible despite incomplete oxidation of the less volatile organic materials in these unstirred tests

Recovery of copper and lead from waste printed circuit boards by supercritical water oxidation combined with electrokinetic process

International Nuclear Information System (INIS)

Xiu Furong; Zhang Fushen

2009-01-01

An effective and benign process for copper and lead recovery from waste printed circuit boards (PCBs) was developed. In the process, the PCBs was pre-treated in supercritical water, then subjected to electrokinetic (EK) process. Experimental results showed that supercritical water oxidation (SCWO) process was strong enough to decompose the organic compounds of PCBs, and XRD spectra indicated that copper and lead were oxidized into CuO, Cu 2 O and β-PbO 2 in the process. The optimum SCWO treatment conditions were 60 min, 713 K, 30 MPa, and EK treatment time, constant current density were 11 h, 20 mA cm -2 , respectively. The recovery percentages of copper and lead under optimum SCWO + EK treatment conditions were around 84.2% and 89.4%, respectively. In the optimized EK treatment, 74% of Cu was recovered as a deposit on the cathode with a purity of 97.6%, while Pb was recovered as concentrated solutions in either anode (23.1%) or cathode (66.3%) compartments but little was deposited on the electrodes. It is believed that the process is effective and practical for Cu and Pb recovery from waste electric and electronic equipments.

Testing of wet scrap recovery equipment for mixed oxide scrap reprocessing

International Nuclear Information System (INIS)

Demiter, J.A.; Klem, M.J.; Owen, T.J.

1984-08-01

The Wet Scrap Recovery (WSR) program was initiated at the Hanford Engineering Development Laboratory (HEDL) by Westinghouse Hanford Company in Richland, Washington to demonstrate fuel fabrication scrap recovery and reconversion to fuel grade oxide powder using the continuous coprecipitation-calcination (COPRECAL) conversion process. Advancements in process control equipment and instrumentation were also developed and demonstrated

PREPARATION OF MESOPOROUS TITANIA-SILICA AEROGELS BY CO2 SUPERCRITICAL EXTRACTION

Directory of Open Access Journals (Sweden)

Silvester Tursiloadi

2010-06-01

Full Text Available Stable anatase is attractive because of its notable functions for photocatalysis and photon-electron transfer.  TiO2-nanoparticles dispersed SiO2 wet gels were prepared by hydrolysis of Ti(OC4H9n4 and Si(OC2H54 in a 2-propanol solution with acid catalyst.  The solvent in the wet gels was supercritically extracted using CO2 at 60 oC and 22 Mpa in one-step.  Thermal evolution of the microstructure of the extracted gels (aerogels was evaluated by XRD measurements, TEM and N2 adsorption measurements. The as-extracted aerogel with a large specific surface area, more than 365 m2g-1, contained anatase nanoparticles, about 5 nm in diameter.  The anatase phase was stable after calcinations at temperatures up to 1000 oC, and BET specific surface area, total pore volume and average pore diameter did not change significantly after calcinations at temperature up to 800 oC.   Keywords: Stable anatase, sol-gel, CO2 supercritical extraction.

Industrial waste water treatment by advanced oxidation processes; Tratamiento de aguas residuales industriales mediante procesos de oxidacion avanzada

Energy Technology Data Exchange (ETDEWEB)

Gasso, S.; Baldasano, J.M.

1996-06-01

Advanced Oxidation Technologies have been defined as processes which involve the generation of highly reactive oxy radicals. These systems show promise for the destruction of non biodegradable and hazardous organic substances in industrial wastewater. Two types of advanced oxidation processes are considered in this paper: (1) systems that use high energy oxidants (O{sub 3}, H{sub 2}O{sub 2}, UV, etc) at ambient temperature to initiate the oxidation reaction, and (2) processes that use molecular oxygen and high temperature and pressure to initiate the reaction (wet oxidation at subcritical and supercritical conditions). The fundamental aspects of these oxidation technologies are discussed, the application framework is defined and the technology development is indicated. (Author) 33 refs.

Destruction of DOE/DP surrogate wastes with supercritical water oxidation technology

International Nuclear Information System (INIS)

Bramlette, T.T.; Mills, B.E.; Hencken, K.R.; Brynildson, M.E.; Johnston, S.C.; Hruby, J.M.; Freemster, H.C.; Odegard, B.C.; Modell, M.

1990-11-01

Surrogate wastes of specific interest to DOE/DP production facilities (Hanford and Rocky Flats), and the electronics industry have been successfully processed in a laboratory-scale, supercritical water oxidation flow reactor. In all cases, the observed destruction/reduction efficiencies for the organic components were in excess of 99.9%, limited by instrumentation detection capability. Separation of the inorganic components of the Hanford process stream was more difficult to accomplish than destruction of the organic component. Large fractions of all metals contained in this stream were found both in the solids separator effluent and in deposits removed from the reactor. Mass closure was not achieved. Of the process stream's non-metallic, inorganic components, the sulfates and phosphates precipitated, while the nitrates tended to stay in solution. The inorganic material that did precipitate from the simulated Hanford mixed waste accumulated in zones that may be associated with changes in the chemical and physical properties of the supercritical fluid. Corrosion is expected to be a significant problem. Witness wires of Inconel 625, Hastalloy C-276, and titanium placed in the preheater, reactor and cooldown exchanger indicated selective dissolution of chromium, nickel, and molybdenum for some conditions, and non-selective dissolution for others. While these results are very promising, further research is required to evaluate the scalability, reliability, and economics of SCWO reactor components and systems, particularly for mixed wastes. Future research must explore a parameter space (temperature, pressure, pH, residence time, etc.) focused on selecting conditions and materials for specific process streams

Generic supercritical water technology; Generic technology to shite no chorinkaisui riyo gijutsu

Energy Technology Data Exchange (ETDEWEB)

Arai, K; Ajiri, M; Inomata, H; Smith, R; Hakuta, Y [Tohoku University, Sendai (Japan). Faculty of Engineering; Yokoyama, C [Tohoku University, Sendai (Japan). The Institute forChemical Reaction Science; Chin, L [New Energy and Industrial Technology Development Organization, Tokyo, (Japan)

1997-02-01

This paper describes the measurement and analysis for clarifying solution structure of supercritical water and exhibition mechanism of solvent functions. It also describes the development of new processes using supercritical water as reaction solvent. The PVT measurements were conducted in the supercritical region using pure water and NaCl aqueous solution, to confirm the reduction of molar volume of the electrolyte solution. The hydration structure was examined in the supercritical aqueous solution by the molecular dynamic simulation. As a result, presence of hydrogen bond structure, where the contribution of two branching hydrogen bond can not be ignored, was suggested under the supercritical condition. Characteristics of supercritical aqueous solutions are analyzed through in-situ Raman and scattered X-ray spectral measurements. Moreover, this paper introduces developments of some processes in the supercritical water, such as decomposition of wasted polymers, recovery of chemical materials, reforming of heavy hydrocarbons by contact hydrogenation, and synthesis of fine powders of metal oxide by reaction crystallization.

Destruction of polyphasic systems in supercritical water reaction media

International Nuclear Information System (INIS)

Leybros, A.

2009-12-01

Spent ion exchange resins (IER) are, hence, radioactive process wastes for which there is no satisfactory industrial treatment. Supercritical water oxidation offers a viable alternative treatment to destroy the organic structure of resins by using supercritical water properties. The reactor used in Supercritical Fluids and Membranes Laboratory is a double shell stirred reactor. Total Organic Carbon reduction rates higher than 99% were obtained thanks to POSCEA2 experimental set-up when using a co-fuel, isopropyl alcohol. Influence of operating parameters was studied. A detailed reactional mechanism for cationic and anionic resins is created. For the solubilization of the particles in supercritical water, a mechanism has been created with the identified rate determining species and implemented into Fluent software through the EDC approach. Experimental temperature profiles are well represented by EDC model. Reaction rates are hence controlled by the chemical species mixing. (author)

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.

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

International Nuclear Information System (INIS)

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

Mechanism study of c.f.c Fe-Ni-Cr alloy corrosion in supercritical water

International Nuclear Information System (INIS)

Payet, M.

2011-01-01

Supercritical water can be use as a high pressure coolant in order to improve the thermodynamic efficiency of power plants. For nuclear concept, lifetime is an important safety parameter for materials. Thus materials selection criteria concern high temperature yield stress, creep resistance, resistance to irradiation embrittlement and also to both uniform corrosion and stress corrosion cracking.This study aims for supplying a new insight on uniform corrosion mechanism of Fe-Ni-Cr f.c.c. alloys in deaerated supercritical water at 600 C and 25 MPa. Corrosion tests were performed on 316L and 690 alloys as sample autoclaves taking into account the effect of surface finishes. Morphologies, compositions and crystallographic structure of the oxides were determined using FEG scanning electron microscopy, glow discharge spectroscopy and X-ray diffraction. If supercritical water is expected to have a gas-like behaviour in the test conditions, the results show a significant dissolution of the alloy species. Thus the corrosion in supercritical water can be considered similar to corrosion in under-critical water assuming the higher temperature and its effect on the solid state diffusion. For alloy 690, the protective oxide layer formed on polished surface consists of a chromia film topped with an iron and nickel mixed chromite or spinel. The double oxide layer formed on 316L steel seems less protective with an outer porous layer of magnetite and an inhomogeneous Cr-rich inner layer. For each alloy, the study of the inner protective scale growth mechanisms by marker or tracer experiments reveals that diffusion in the oxide scale is governed by an anionic process. However, surface finishes impact deeply the growth mechanisms. Comparisons between the results for the steel suggest that there is a competition between the oxidation of iron and chromium in supercritical water. Sufficient available chromium is required in order to form a thin oxide layer. Highly deformed or ultra fine

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.

Reactions of nitrate salts with ammonia in supercritical water

International Nuclear Information System (INIS)

Dell'Orco, P.C.; Gloyna, E.F.; Buelow, S.J.

1997-01-01

Reactions involving nitrate salts and ammonia were investigated in supercritical water at temperatures from 450 to 530 C and pressures near 300 bar. Reaction products included nitrite, nitrogen gas, and nitrous oxide. Observed reaction rates and product distributions provided evidence for a free-radical reaction mechanism with NO 2 , NO, and NH 2 · as the primary reactive species at supercritical conditions. In the proposed elementary mechanism, the rate-limiting reaction step was determined to be the hydrolysis of MNO 3 species, which resulted in the formation of nitric acid and subsequently NO 2 . A simple second-order reaction model was used to represent the data. In developing an empirical kinetic model, nitrate and nitrate were lumped as an NO x - reactant. Empirical kinetic parameters were developed for four MNO x /NH 3 reacting systems, assuming first orders in both NH 3 and NO x - . Observed MNO x /NH 3 reaction rates and mechanisms suggest immediately a practical significance of these reactions for nitrogen control strategies in supercritical water oxidation processes

An Energy Analysis on Gasification of Sewage Sludge by a Direct Injection in Supercritical Water

NARCIS (Netherlands)

Yukananto, Riza; Louwes, Alexander Charnchai; Bramer, Eduard A.; Brem, Gerrit

2017-01-01

Supercritical Water Gasification is an efficient technology in converting wet biomass into H2 and CH4 in comparison to other conventional thermochemical processes. Coke deposition, however, remains as a major challenge in this technology. Coke formation is the result of polymerization reactions that

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. Copyright © 2012 Elsevier B.V. All rights reserved.

Preparation of minute particle using supercritical fluid; Chorinkai ryutai wo mochiita biryushi no chosei

Energy Technology Data Exchange (ETDEWEB)

Ajiri, T [Tohoku University, Sendai (Japan). Faculty of Engineering

1995-03-05

The metal oxide minute particle synthesis method according to the water-heat reaction in supercritical water was described. Metal salt liquid solution was subjected to hydrolysis when heated to become metal hydroxide but dehydration reaction was generated at a high temperature to generate metal oxide minute particle. Metal salt aqueous solution was supplied to a circulation system unit to contact heated water and was rapidly heated to supercritical state and then was subjected to hydrolysis/dehydration reaction, thus continuously collecting metal oxide minute particles. The hydrolysis speed was in first order for the metal ion concentration and the reaction speed was accelerated by several tens of times when entering supercritical region from subcritical region. When the temperature was rapidly increased to the supercritical state, a radical hydrolysis was generated and a high saturation was instantly reached and minute particles tended to be generated easily since the dissolution force of supercritical water for a product was small. A minute particle with a crystallizability of 5 nm was obtained by synthesizing ceria super-minute particle which was the abrasive of an optical glass material. A single phase of a high magnetization characteristic was synthesized continuously and quickly (faster than a conventional method by two orders or more) in the continuous synthesis of Ba ferrite as a magnetic recording material. 12 refs., 3 figs., 1 tab.

Supercritical water gasification of Victorian brown coal: Experimental characterisation

Energy Technology Data Exchange (ETDEWEB)

Yamaguchi, Doki; Aye, Lu [Department of Civil and Environmental Engineering, The University of Melbourne, Vic 3010 (Australia); Sanderson, P. John; Lim, Seng [CSIRO Minerals, Clayton, Vic 3168 (Australia)

2009-05-15

Supercritical water gasification is an innovative thermochemical conversion method for converting wet feedstocks into hydrogen-rich gaseous products. The non-catalytic gasification characteristics of Victorian brown coal were investigated in supercritical water by using a novel immersion technique with quartz batch reactors. Various operating parameters such as temperature, feed concentration and reaction time were varied to investigate their effect on the gasification behaviour. Gas yields, carbon gasification efficiency and the total gasification efficiency increased with increasing temperature and reaction time, and decreasing feed concentration. The mole fraction of hydrogen in the product gases was lowest at 600 C, and increased to over 30 % at a temperature of 800 C. Varying parameters, especially reaction time, did not improve the coal utilisation for gas production significantly and the measured data showed a large deviation from the equilibrium level. (author)

Stress corrosion cracking and oxidation of austenitic stainless steel 316 L and model alloy in supercritical water reactor

International Nuclear Information System (INIS)

Saez-Maderuelo, A.; Gomez-Briceno, D.; Diego, G.

2015-01-01

In this work, an austenitic stainless steel type 316 L was tested in deaerated supercritical water at 400 deg. C and 500 deg. C and 25 MPa to determine how variations in water conditions influence its stress corrosion cracking behaviour and to make progress in the understanding of mechanisms involved in SCC processes in this environment. Moreover, the influence of plastic deformation in the resistance of the material to SCC was also studied at both temperatures. In addition to this, previous oxidation experiments at 400 deg. C and 500 deg. C and at 25 MPa were taken into account to gain some insight in this kind of processes. Furthermore, a cold worked model alloy based on the stainless steel 316 L with some variations in the chemical composition in order to simulate the composition of the grain boundary after irradiation was tested at 400 deg. C and 25 MPa in deaerated supercritical water. (authors)

Selective Oxidation and Reactive Wetting during Galvanizing of a CMnAl TRIP-Assisted Steel

Science.gov (United States)

Bellhouse, E. M.; McDermid, J. R.

2011-09-01

A transformation induced plasticity (TRIP)-assisted steel with 0.2 pct C, 1.5 pct Mn, and 1.5 pct Al was successfully galvanized using a thermal cycle previously shown to produce an excellent combination of strength and ductility. The steel surface chemistry and oxide morphology were determined as a function of process atmosphere oxygen partial pressure. For the 220 K (-53 °C) dew point (dp) + 20 pct H2 atmosphere, the oxide morphology was a mixture of films and nodules. For the 243 K (-30 °C) dp + 5 pct H2 atmosphere, nodules of MnO were found primarily at grain boundaries. For the 278 K (+5 °C) dp + 5 pct H2 atmosphere, nodules of metallic Fe were found on the surface as a result of alloy element internal oxidation. The steel surface chemistry and oxide morphology were then related to the reactive wetting behavior during continuous hot dip galvanizing. Good wetting was obtained using the two lower oxygen partial pressure process atmospheres [220 K dp and 243 K dp (-53 °C dp and -30 °C dp)]. An increase in the number of bare spots was observed when using the higher oxygen partial pressure process atmosphere (+5 °C dp) due to the increased thickness of localized oxide films.

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

International Nuclear Information System (INIS)

Gary M. Blythe

2002-01-01

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 in a stable form 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 will test previously identified, effective catalyst materials at a larger, pilot scale and in a commercial form, so as 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 first full reporting period for the subject Cooperative Agreement. During this period, most of the project efforts were related to project initiation and planning. There is no significant technical progress to report for the current period

Treatment of Row Leachate Using Catalytic Wet Oxidation Processes in Combination Hydrogen Peroxide, A Case Study of Isfahan Composting Factory Leachate

Directory of Open Access Journals (Sweden)

Behrouz Karimi

2013-08-01

Full Text Available Treatment of toxic organic compounds is one of the major applications of the Wet Air Oxidation (WAO processes. The process can be defined  as the oxidation of substances, either in the form of solutions or suspensions, with the use of an oxidant (oxygen or air at elevated pressure and temperature. The aim of this paper was to study of Catalytic Wet Oxidation (CWAO with hydrogen peroxide to improve removal efficiency of organic matter and ammonia mainly produced in Isfahan composting factory leachate. The experiment was carried out by adding 1.5 Lit pretreated leachate sample to 3 Lit autoclave reactor. Four parameters are considered: pressure (8–12 bar; temperature (100–300 °C; retention time (30–90 min; H2O2 (1–5 mL/L.The highest removal efficiencies of COD and BOD were achieved at 300°C; approximately 44% and 48% were destroyed, respectively. On the other hand, highest ammonium removal efficiency was achieved at 100 °C in which approximately 63.8% was removed. The efficiency of aqueous phase oxidation can be largely improved by the use of H2O2 as catalyst. Therefore, catalytic wet oxidation would provide an environmentally attractive option for control of organic and toxic wastes problems. Temperature was found to be the most important control variable of the wet oxidation process of leachate.

Relative permeabilities of supercritical CO2 and brine in carbon sequestration by a two-phase lattice Boltzmann method

Science.gov (United States)

Xie, Jian.-Fei.; He, S.; Zu, Y. Q.; Lamy-Chappuis, B.; Yardley, B. W. D.

2017-08-01

In this paper, the migration of supercritical carbon dioxide (CO2) in realistic sandstone rocks under conditions of saline aquifers, with applications to the carbon geological storage, has been investigated by a two-phase lattice Boltzmann method (LBM). Firstly the digital images of sandstone rocks were reproduced utilizing the X-ray computed microtomography (micro-CT), and high resolutions (up to 2.5 μm) were applied to the pore-scale LBM simulations. For the sake of numerical stability, the digital images were "cleaned" by closing the dead holes and removing the suspended particles in sandstone rocks. In addition, the effect of chemical reactions occurred in the carbonation process on the permeability was taken into account. For the wetting brine and non-wetting supercritical CO2 flows, they were treated as the immiscible fluids and were driven by pressure gradients in sandstone rocks. Relative permeabilities of brine and supercritical CO2 in sandstone rocks were estimated. Particularly the dynamic saturation was applied to improve the reliability of the calculations of the relative permeabilities. Moreover, the effects of the viscosity ratio of the two immiscible fluids and the resolution of digital images on the relative permeability were systematically investigated.

Final report on the oxidation of energetic materials in supercritical water. Final Air Force report

Energy Technology Data Exchange (ETDEWEB)

Buelow, S.J.; Allen, D.; Anderson, G.K. [and others

1995-04-03

The objective of this project was to determine the suitability of oxidation in supercritical fluids (SCO), particularly water (SCWO), for disposal of propellants, explosives, and pyrotechnics (PEPs). The SCO studies of PEPs addressed the following issues: The efficiency of destruction of the substrate. The products of destruction contained in the effluents. Whether the process can be conducted safely on a large scale. Whether energy recovery from the process is economically practicable. The information essential for process development and equipment design was also investigated, including issues such as practical throughput of explosives through a SCWO reactor, reactor materials and corrosion, and models for process design and optimization.

Flow method for rapid production of Batio3 nanoparticles in supercritical water

International Nuclear Information System (INIS)

Atashfaraz, M.; Shariati-Niassar, M.; Ohara, Satoshi; Takami, S.; Umetsu, M.; Naka, T.; Adschiri, T.

2006-01-01

Fine BaTiO 3 nanoparticles were obtained by hydrothermal synthesis under supercritical conditions with batch and flow type experimental methods. Mixture of barium hydroxide and titanium oxide starting solution was treated in the supercritical wafer at 400 d eg C and 30 MPa. The size of nanoparticles synthesized in the flow type experiment was smaller than that in the batch type. Rapid heating in a flow, reactor is effective to synthesize smaller size and narrower particle size distribution for the BaTiO 3 , nanoparticles. The mechanism for this result was discussed based on the solubility of titanium oxide

Bimetallic catalysts for continuous catalytic wet air oxidation of phenol.

Science.gov (United States)

Fortuny, A; Bengoa, C; Font, J; Fabregat, A

1999-01-29

Catalytic wet oxidation has proved to be effective at eliminating hazardous organic compounds, such as phenol, from waste waters. However, the lack of active long-life oxidation catalysts which can perform in aqueous phase is its main drawback. This study explores the ability of bimetallic supported catalysts to oxidize aqueous phenol solutions using air as oxidant. Combinations of 2% of CoO, Fe2O3, MnO or ZnO with 10% CuO were supported on gamma-alumina by pore filling, calcined and later tested. The oxidation was carried out in a packed bed reactor operating in trickle flow regime at 140 degrees C and 900 kPa of oxygen partial pressure. Lifetime tests were conducted for 8 days. The pH of the feed solution was also varied. The results show that all the catalysts tested undergo severe deactivation during the first 2 days of operation. Later, the catalysts present steady activity until the end of the test. The highest residual phenol conversion was obtained for the ZnO-CuO, which was significantly higher than that obtained with the 10% CuO catalyst used as reference. The catalyst deactivation is related to the dissolution of the metal oxides from the catalyst surface due to the acidic reaction conditions. Generally, the performance of the catalysts was better when the pH of the feed solution was increased.

Computational fluid dynamic model for glycerol gasification in supercritical water in a tee junction shaped cylindrical reactor

NARCIS (Netherlands)

Yukananto, Riza; Pozarlik, Artur K.; Brem, Gerrit

2018-01-01

Gasification in supercritical water is a very promising technology to process wet biomass into a valuable gas. Providing insight of the process behavior is therefore very important. In this research a computational fluid dynamic model is developed to investigate glycerol gasification in

A catalytic wet oxidation process for mixed waste volume reduction/recycling

International Nuclear Information System (INIS)

Dhooge, Patrick M.

1992-01-01

Mixed wastes have presented a challenge to treatment and destruction technologies. A recently developed catalytic wet oxidation method has promising characteristics for volume reduction and recycling of mixed wastes. The process utilizes iron (III) as an oxidant in the presence of homogeneous cocatalysts which increase organics' oxidation rates and the rate of oxidation of iron (II) by oxygen. The reaction is conducted in an aqueous mineral acid solution at temperatures of 373 - 573 deg K. The mineral acid should solvate a number of heavy metals, including U and Pu. Studies of reaction rates show that the process can oxidize a wide range of organic compounds including aromatics and chlorinated hydrocarbons. Rate constants in the range of 10 -7 to 10 -4 sec -1 , depending on the cocatalyst, acidity, type of anions, type of organic, temperature, and time. Activation energies ranged from 25. to 32. KJ/mole. Preliminary measurements of the extent of oxidation which could be obtained ranged from 80% for trichloroethylene to 99.8% for 1,2,4-trimethylbenzene; evidence was obtained that absorption by the fluorocarbon liners of the reaction bombs allowed some of the organics to escape exposure to the catalyst solution. The results indicate that complete oxidation of the organics used here, and presumably many others, can be achieved. (author)

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

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...

Reversible switching of wetting properties and erasable patterning of polymer surfaces using plasma oxidation and thermal treatment

Science.gov (United States)

Rashid, Zeeshan; Atay, Ipek; Soydan, Seren; Yagci, M. Baris; Jonáš, Alexandr; Yilgor, Emel; Kiraz, Alper; Yilgor, Iskender

2018-05-01

Polymer surfaces reversibly switchable from superhydrophobic to superhydrophilic by exposure to oxygen plasma and subsequent thermal treatment are demonstrated. Two inherently different polymers, hydrophobic segmented polydimethylsiloxane-urea copolymer (TPSC) and hydrophilic poly(methyl methacrylate) (PMMA) are modified with fumed silica nanoparticles to prepare superhydrophobic surfaces with roughness on nanometer to micrometer scale. Smooth TPSC and PMMA surfaces are also used as control samples. Regardless of their chemical structure and surface topography, all surfaces display completely reversible wetting behavior changing from hydrophobic to hydrophilic and back for many cycles upon plasma oxidation followed by thermal annealing. Influence of plasma power, plasma exposure time, annealing temperature and annealing time on the wetting behavior of polymeric surfaces are investigated. Surface compositions, textures and topographies are characterized by X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and white light interferometry (WLI), before and after oxidation and thermal annealing. Wetting properties of the surfaces are determined by measuring their static, advancing and receding water contact angle. We conclude that the chemical structure and surface topography of the polymers play a relatively minor role in reversible wetting behavior, where the essential factors are surface oxidation and migration of polymer molecules to the surface upon thermal annealing. Reconfigurable water channels on polymer surfaces are produced by plasma treatment using a mask and thermal annealing cycles. Such patterned reconfigurable hydrophilic regions can find use in surface microfluidics and optofluidics applications.

Method and apparatus for dissociating metals from metal compounds extracted into supercritical fluids

Science.gov (United States)

Wai, Chien M.; Hunt, Fred H.; Smart, Neil G.; Lin, Yuehe

2000-01-01

A method for dissociating metal-ligand complexes in a supercritical fluid by treating the metal-ligand complex with heat and/or reducing or oxidizing agents is described. Once the metal-ligand complex is dissociated, the resulting metal and/or metal oxide form fine particles of substantially uniform size. In preferred embodiments, the solvent is supercritical carbon dioxide and the ligand is a .beta.-diketone such as hexafluoroacetylacetone or dibutyldiacetate. In other preferred embodiments, the metals in the metal-ligand complex are copper, silver, gold, tungsten, titanium, tantalum, tin, or mixtures thereof. In preferred embodiments, the reducing agent is hydrogen. The method provides an efficient process for dissociating metal-ligand complexes and produces easily-collected metal particles free from hydrocarbon solvent impurities. The ligand and the supercritical fluid can be regenerated to provide an economic, efficient process.

Assessment and comparison of oxides grown on 304l ods steel and 304l ss in water environment in supercritical conditions

International Nuclear Information System (INIS)

Mihalache, M.; Dinu, A.; Fulger, M.; Zhou, Z.; Mihalache, M.

2013-01-01

In order to fulfil superior cladding for new reactor generation G IV, the austenitic 3 04 L stainless steel was improved by oxide dispersion strengthening (ODS), using two nano-oxides: titanium and yttrium oxides. The behaviour of the new material resulted, 304 ODS, in water at supercritical temperature of about 550 O C and 25 MPa pressure, was considered. The oxidation kinetics by weigh gain measurements for both materials have been estimated and compared. The weight gain of ODS samples is higher than basic austenitic steel up to 1320 hours. The oxides developed on the ODS samples in SCPW are layered and more uniform than in 304 L SS. The protectively character of oxide films was estimated by different techniques. The morphology of oxide surface, the layering and chemical formula of oxides films were investigated by scanning electron microscopy (SEM), Energy Dispersion X-Ray Spectrometry (EDS), electrochemical impedance spectrometry (EIS) and by Small Angle X-ray Diffraction (SAXD). 1. (authors)

Electrodeposition of germanium from supercritical fluids.

Science.gov (United States)

Ke, Jie; Bartlett, Philip N; Cook, David; Easun, Timothy L; George, Michael W; Levason, William; Reid, Gillian; Smith, David; Su, Wenta; Zhang, Wenjian

2012-01-28

Several Ge(II) and Ge(IV) compounds were investigated as possible reagents for the electrodeposition of Ge from liquid CH(3)CN and CH(2)F(2) and supercritical CO(2) containing as a co-solvent CH(3)CN (scCO(2)) and supercritical CH(2)F(2) (scCH(2)F(2)). For Ge(II) reagents the most promising results were obtained using [NBu(n)(4)][GeCl(3)]. However the reproducibility was poor and the reduction currents were significantly less than the estimated mass transport limited values. Deposition of Ge containing films was possible at high cathodic potential from [NBu(n)(4)][GeCl(3)] in liquid CH(3)CN and supercritical CO(2) containing CH(3)CN but in all cases they were heavily contaminated by C, O, F and Cl. Much more promising results were obtained using GeCl(4) in liquid CH(2)F(2) and supercritical CH(2)F(2). In this case the reduction currents were consistent with mass transport limited reduction and bulk electrodeposition produced amorphous films of Ge. Characterisation by XPS showed the presence of low levels of O, F and C, XPS confirmed the presence of Ge together with germanium oxides, and Raman spectroscopy showed that the as deposited amorphous Ge could be crystallised by the laser used in obtaining the Raman measurements.

Comparative study of the luminescence of structures with Ge nanocrystals formed by dry and wet oxidation of SiGe films

International Nuclear Information System (INIS)

RodrIguez, A; Ortiz, M I; Sangrador, J; RodrIguez, T; Avella, M; Prieto, A C; Torres, A; Jimenez, J; Kling, A; Ballesteros, C

2007-01-01

The luminescence emission of structures containing Ge nanocrystals embedded in a dielectric matrix obtained by dry and wet oxidation of polycrystalline SiGe layers has been studied as a function of the oxidation time and initial SiGe layer thickness. A clear relationship between the intensity of the luminescence, the structure of the sample, the formation of Ge nanocrystals and the oxidation process parameters that allows us to select the appropriate process conditions to get the most efficient emission has been established. The evolution of the composition and thickness of the growing oxides and the remaining SiGe layer during the oxidation processes has been characterized using Raman spectroscopy, x-ray diffraction, Fourier-transform infrared spectroscopy, Rutherford backscattering spectrometry and transmission electron microscopy. For dry oxidation, the luminescence appears suddenly, regardless of the initial SiGe layer thickness, when all the Si of the SiGe has been oxidized and the remaining layer of the segregated Ge starts to be oxidized forming Ge nanocrystals. Luminescence is observed as long as Ge nanocrystals are present. For wet oxidation, the luminescence appears from the first stages of the oxidation, and is related to the formation of Ge-rich nanoclusters trapped in the mixed (Si and Ge) growing oxide. A sharp increase of the luminescence intensity for long oxidation times is also observed, due to the formation of Ge nanocrystals by the oxidation of the layer of segregated Ge. For both processes the luminescence is quenched when the oxidation time is long enough to cause the full oxidation of the Ge nanocrystals. The intensity of the luminescence in the dry oxidized samples is about ten times higher than in the wet oxidized ones for equal initial thickness of the SiGe layer

Solvation in supercritical water

International Nuclear Information System (INIS)

Cochran, H.D.; Cummings, P.T.; Karaborni, S.

1991-01-01

The aim of this work is to determine the solvation structure in supercritical water composed with that in ambient water and in simple supercritical solvents. Molecular dynamics studies have been undertaken of systems that model ionic sodium and chloride, atomic argon, and molecular methanol in supercritical aqueous solutions using the simple point charge model of Berendsen for water. Because of the strong interactions between water and ions, ionic solutes are strongly attractive in supercritical water, forming large clusters of water molecules around each ion. Methanol is found to be a weakly-attractive solute in supercritical water. The cluster of excess water molecules surrounding a dissolved ion or polar molecule in supercritical aqueous solutions is comparable to the solvent clusters surrounding attractive solutes in simple supercritical fluids. Likewise, the deficit of water molecules surrounding a dissolved argon atom in supercritical aqueous solutions is comparable to that surrounding repulsive solutes in simple supercritical fluids. The number of hydrogen bonds per water molecule in supercritical water was found to be about one third the number in ambient water. The number of hydrogen bonds per water molecule surrounding a central particle in supercritical water was only mildly affected by the identify of the central particle--atom, molecule, or ion. These results should be helpful in developing a qualitative understanding of important processes that occur in supercritical water. 29 refs., 6 figs

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.

Supercritical Fluid Chromatography/Fourier Transform Infrared Spectroscopy Of Food Components

Science.gov (United States)

Calvey, Elizabeth M.; Page, Samuel W.; Taylor, Larry T.

1989-12-01

Supercritical fluid (SF) technologies are being investigated extensively for applications in food processing. The number of SF-related patents issued testifies to the level of interest. Among the properties of materials at temperatures and pressures above their critical points (supercritical fluids) is density-dependent solvating power. Supercritical CO2 is of particular interest to the food industry because of its low critical temperature (31.3°C) and low toxicity. Many of the components in food matrices react or degrade at elevated temperatures and may be adversely affected by high temperature extractions. Likewise, these components may not be amenable to GC analyses. Our SF research has been in the development of methods employing supercritical fluid chromatography (SFC) and extraction (SFE) coupled to a Fourier transform infrared (FT-IR) spectrometer to investigate food composition. The effects of processing techniques on the isomeric fatty acid content of edible oils and the analysis of lipid oxidation products using SFC/FT-IR with a flow-cell interface are described.

Destruction of chemical agent simulants in a supercritical water oxidation bench-scale reactor

Energy Technology Data Exchange (ETDEWEB)

Veriansyah, Bambang [Supercritical Fluid Research Laboratory, Clean Technology Research Center, Korea Institute of Science and Technology (KIST), 39-1 Hawolgok-dong, Seongbuk-gu, Seoul 136-791 (Korea, Republic of) and Department of Green Process and System Engineering, University of Science and Technology, 39-1 Hawolgok-dong, Seongbuk-gu, Seoul 136-791 (Korea, Republic of)]. E-mail: vaveri@kist.re.kr; Kim, Jae-Duck [Supercritical Fluid Research Laboratory, Clean Technology Research Center, Korea Institute of Science and Technology (KIST), 39-1 Hawolgok-dong, Seongbuk-gu, Seoul 136-791 (Korea, Republic of) and Department of Green Process and System Engineering, University of Science and Technology, 39-1 Hawolgok-dong, Seongbuk-gu, Seoul 136-791 (Korea, Republic of)]. E-mail: jdkim@kist.re.kr; Lee, Jong-Chol [Agency for Defense Development (ADD), P.O. Box 35-1, Yuseong-gu, Daejeon (Korea, Republic of)]. E-mail: jcleeadd@hanafos.com

2007-08-17

A new design of supercritical water oxidation (SCWO) bench-scale reactor has been developed to handle high-risk wastes resulting from munitions demilitarization. The reactor consists of a concentric vertical double wall in which SCWO reaction takes place inside an inner tube (titanium grade 2, non-porous) whereas pressure resistance is ensured by a Hastelloy C-276 external vessel. The performances of this reactor were investigated with two different kinds of chemical warfare agent simulants: OPA (a mixture of isopropyl amine and isopropyl alcohol) as the binary precursor for nerve agent of sarin and thiodiglycol [TDG (HOC{sub 2}H{sub 4}){sub 2}S] as the model organic sulfur heteroatom. High destruction rates based on total organic carbon (TOC) were achieved (>99.99%) without production of chars or undesired gases such as carbon monoxide and methane. The carbon-containing product was carbon dioxide whereas the nitrogen-containing products were nitrogen and nitrous oxide. Sulfur was totally recovered in the aqueous effluent as sulfuric acid. No corrosion was noticed in the reactor after a cumulative operation time of more than 250 h. The titanium tube shielded successfully the pressure vessel from corrosion.

Destruction of Energetic Materials in Supercritical Water

Science.gov (United States)

2002-06-25

controls and difficulties associated with controlling processes and obtaining permits can negate potential advantages . Supercritical water oxidation...for H2 and an Alltech CTR-1 column with a temperature ramp program from -10 °C to 180 °C was used for the other gases. A mass spectrometer (HP 5971

ABB wet flue gas desulfurization

Energy Technology Data Exchange (ETDEWEB)

Niijhawan, P.

1994-12-31

The wet limestone process for flue gas desulfurization (FGD) is outlined. The following topics are discussed: wet flue gas desulfurization, wet FGD characteristics, wet scrubbers, ABB wet FGD experience, wet FGD forced oxidation, advanced limestone FGD systems, key design elements, open spray tower design, spray tower vs. packed tower, important performance parameters, SO{sub 2} removal efficiency, influence by L/G, limestone utilization, wet FGD commercial database, particulate removal efficiencies, materials of construction, nozzle layout, spray nozzles, recycle pumps, mist elimination, horizontal flow demister, mist eliminator washing, reagent preparation system, spray tower FGDS power consumption, flue gas reheat options, byproduct conditioning system, and wet limestone system.

Supercritical Water Mixture (SCWM) Experiment

Science.gov (United States)

Hicks, Michael C.; Hegde, Uday G.

2012-01-01

The subject presentation, entitled, Supercritical Water Mixture (SCWM) Experiment, was presented at the International Space Station (ISS) Increment 33/34 Science Symposium. This presentation provides an overview of an international collaboration between NASA and CNES to study the behavior of a dilute aqueous solution of Na2SO4 (5% w) at near-critical conditions. The Supercritical Water Mixture (SCWM) investigation, serves as important precursor work for subsequent Supercritical Water Oxidation (SCWO) experiments. The SCWM investigation will be performed in DECLICs High Temperature Insert (HTI) for the purpose of studying critical fluid phenomena at high temperatures and pressures. The HTI includes a completely sealed and integrated test cell (i.e., Sample Cell Unit SCU) that will contain approximately 0.3 ml of the aqueous test solution. During the sequence of tests, scheduled to be performed in FY13, temperatures and pressures will be elevated to critical conditions (i.e., Tc = 374C and Pc = 22 MPa) in order to observe salt precipitation, precipitate agglomeration and precipitate transport in the presence of a temperature gradient without the influences of gravitational forces. This presentation provides an overview of the motivation for this work, a description of the DECLIC HTI hardware, the proposed test sequences, and a brief discussion of the scientific research objectives.

Extracting metals directly from metal oxides

International Nuclear Information System (INIS)

Wai, C.M.; Smart, N.G.; Phelps, C.

1997-01-01

A method of extracting metals directly from metal oxides by exposing the oxide to a supercritical fluid solvent containing a chelating agent is described. Preferably, the metal is an actinide or a lanthanide. More preferably, the metal is uranium, thorium or plutonium. The chelating agent forms chelates that are soluble in the supercritical fluid, thereby allowing direct removal of the metal from the metal oxide. In preferred embodiments, the extraction solvent is supercritical carbon dioxide and the chelating agent is selected from the group consisting of β-diketones, halogenated β-diketones, phosphinic acids, halogenated phosphinic acids, carboxylic acids, halogenated carboxylic acids, and mixtures thereof. In especially preferred embodiments, at least one of the chelating agents is fluorinated. The method provides an environmentally benign process for removing metals from metal oxides without using acids or biologically harmful solvents. The chelate and supercritical fluid can be regenerated, and the metal recovered, to provide an economic, efficient process. 4 figs

Extraction of metals and/or metalloids from acidic media using supercritical fluids and salts

International Nuclear Information System (INIS)

Wai, C.M.; Smart, N.G.; Lin, Y.

1998-01-01

A method is described for extracting metalloid and metal species from a solid or liquid material by exposing the material to a fluid solvent, particularly supercritical carbon dioxide, containing a chelating agent. The chelating agent forms chelates that are soluble in the fluid to allow removal of the species from the material. In preferred embodiments, the extraction solvent is supercritical carbon dioxide and the chelating agent comprises a trialkyl phosphate, a triaryl phosphate, a trialkylphosphine oxide, a triarylphosphine oxide, or mixtures thereof. The method provides an environmentally benign process for removing contaminants from industrial waste. The method is particularly useful for extracting actinides from acidic solutions, and the process can be aided by the addition of nitrate salts. The chelate and supercritical fluid can be regenerated, and the contaminant species recovered, to provide an economic, efficient process. 7 figs

Extraction of metals and/or metalloids from acidic media using supercritical fluids and salts

Science.gov (United States)

Wai, Chien M.; Smart, Neil G.; Lin, Yuehe

1998-01-01

A method of extracting metalloid and metal species from a solid or liquid material by exposing the material to a fluid solvent, particularly supercritical carbon dioxide, containing a chelating agent is described. The chelating agent forms chelates that are soluble in the fluid to allow removal of the species from the material. In preferred embodiments, the extraction solvent is supercritical carbon dioxide and the chelating agent comprises a trialkyl phosphate, a triaryl phosphate, a trialkylphosphine oxide, a triarylphosphine oxide, or mixtures thereof. The method provides an environmentally benign process for removing contaminants from industrial waste. The method is particularly useful for extracting actinides from acidic solutions, and the process can be aided by the addition of nitrate salts. The chelate and supercritical fluid can be regenerated, and the contaminant species recovered, to provide an economic, efficient process.

Titania aerogel prepared by low temperature supercritical drying

Czech Academy of Sciences Publication Activity Database

Štengl, Václav; Bakardjieva, Snejana; Šubrt, Jan; Szatmáry, Lórant

2006-01-01

Roč. 91, 1-3 (2006), s. 1-6 ISSN 1387-1811 R&D Projects: GA MŠk(CZ) 1M0577 Institutional research plan: CEZ:AV0Z40320502 Keywords : aerogels * titanium oxide * supercritical drying Subject RIV: CA - Inorganic Chemistry Impact factor: 2.796, year: 2006

Corrosion in Supercritical carbon Dioxide: Materials, Environmental Purity, Surface Treatments, and Flow Issues

Energy Technology Data Exchange (ETDEWEB)

Sridharan, Kumar; Anderson, Mark

2013-12-10

separately to high purity CO{sub 2}. Task 3: Evaluation of surface treatments on the corrosion performance of alloys in supercritical CO{sub 2}: Surface treatments can be very beneficial in improving corrosion resistance. Shot peening and yttrium and aluminum surface treatments will be investigated. Shot peening refines the surface grain sizes and promotes protective Cr-oxide layer formation. Both yttrium and aluminum form highly stable oxide layers (Y{sub 2}O{sub 3} and Al{sub 2}O{sub 3}), which can get incorporated in the growing Fe-oxide layer to form an impervious complex oxide to enhance corrosion resistance. Task 4: Study of flow-assisted corrosion of select alloys in supercritical CO{sub 2} under a selected set of test conditions: To study the effects of flow-assisted corrosion, tests will be conducted in a supercritical CO{sub 2} flow loop. An existing facility used for supercritical water flow studies at the proposing university will be modified for use in this task. The system is capable of flow velocities up to 10 m/s and can operate at temperatures and pressures of up to 650°C and 20 MPa, respectively. All above tasks will be performed in conjunction with detailed materials characterization and analysis using scanning electron microscopy/energy dispersive spectroscopy (SEM-EDS), x-ray diffraction (XRD), Auger electron spectroscopy (AES) techniques, and weight change measurements. Inlet and outlet gas compositions will be monitored using gas chromatography-mass spectrometry (GCMS).

Hysteresis losses in iron oxide nanoparticles prepared by glass crystallization or wet chemical precipitation

International Nuclear Information System (INIS)

Mueller, Robert; Dutz, Silvio; Hergt, Rudolf; Schmidt, Christopher; Steinmetz, Hanna; Zeisberger, Matthias; Gawalek, Wolfgang

2007-01-01

Ferrofluids were prepared from glass crystallized as well as wet precipitated iron oxide particles. Comparing hysteresis losses versus applied field amplitude from particles in immobilized state (powder) and in fluid state (ferrofluid) shows in some cases anomalous large losses at low magnetic fields. The influence of texture on the losses was investigated

Stable Organic Monolayers on Oxide-Free Silicon/Germanium in a Supercritical Medium: A New Route to Molecular Electronics.

Science.gov (United States)

Puniredd, Sreenivasa Reddy; Jayaraman, Sundaramurthy; Yeong, Sai Hooi; Troadec, Cedric; Srinivasan, M P

2013-05-02

Oxide-free Si and Ge surfaces have been passivated and modified with organic molecules by forming covalent bonds between the surfaces and reactive end groups of linear alkanes and aromatic species using single-step deposition in supercritical carbon dioxide (SCCO2). The process is suitable for large-scale manufacturing due to short processing times, simplicity, and high resistance to oxidation. It also allows the formation of monolayers with varying reactive terminal groups, thus enabling formation of nanostructures engineered at the molecular level. Ballistic electron emission microscopy (BEEM) spectra performed on the organic monolayer on oxide-free silicon capped by a thin gold layer reveals for the first time an increase in transmission of the ballistic current through the interface of up to three times compared to a control device, in contrast to similar studies reported in the literature suggestive of oxide-free passivation in SCCO2. The SCCO2 process combined with the preliminary BEEM results opens up new avenues for interface engineering, leading to molecular electronic devices.

Removal of plutonium from real time waste using supercritical fluid extraction

International Nuclear Information System (INIS)

Sujatha, K.; Sivaraman, N.; Kumar, R.; Srinivasan, T.G.; Vasudeva Rao, P.R.

2010-01-01

Supercritical fluid extraction (SFE) technique was carried out for the recovery of plutonium from cellulose waste matrix using supercritical carbon dioxide (SC-CO 2 ) modified with suitable ligands such as octylphenyl N,N-diisobutyl carbamoylmethyl phosphine oxide (φCMPO), tri-n-butyl phosphate (TBP), acetyl acetone, trifluoro acetyl acetone and theonyltrifluoroacetyl acetone (TTA). The maximum plutonium recovery was found to be 99.8% when SC-CO 2 modified with CMPO was employed. About 15mg of plutonium was recovered from waste. (author)

Studies on supercritical hydrothermal syntheses of uranium and lanthanide oxide particles and their reaction mechanisms

Science.gov (United States)

Hwang, DongKi; Tsukahara, Takehiko; Tanaka, Kosuke; Osaka, Masahiko; Ikeda, Yasuhisa

2015-11-01

In order to develop preparation method of raw metal oxide particles for low decontaminated MOX fuels by supercritical hydrothermal (SH) treatments, we have investigated behavior of aqueous solutions dissolving U(VI), Ln(III) (Ln: lanthanide = Ce, Pr, Nd, Sm, Tb), Cs(I), and Sr(II) nitrate or chloride compounds under SH conditions (temperature = 400-500 °C, pressure = 30-40 MPa). As a result, it was found that Ln(NO3)3 (Ln = Ce, Pr, Tb) compounds produce LnO2, that Ln(NO3)3 (Ln = Nd, Sm) compounds are hardly converted to their oxides, and that LnCl3 (Ln = Ce, Pr, Nd, Sm, Tb), CsNO3, and Sr(NO3)2 do not form their oxide compounds. Furthermore, HNO2 species were detected in the liquid phase obtained after treating HNO3 aqueous solutions containing Ln(NO3)3 (Ln = Ce, Pr, Tb) under SH conditions, and also NO2 and NO compounds were found to be produced by decomposition of HNO3. From these results, it was proposed that the Ln oxide (LnO2) particles are directly formed with oxidation of Ln(III) to Ln(IV) by HNO3 and HNO2 species in the SH systems. Moreover, the uranyl ions were found to form U3O8 and UO3 depending on the concentration of HNO3. From these results, it is expected that the raw metal oxide particles for low decontaminated MOX fuels are efficiently prepared by the SH method.

Wet oxidative degradation of cellulosic wastes 5- chemical and thermal properties of the final waste forms

International Nuclear Information System (INIS)

Eskander, S.B.; Saleh, H.M.

2002-01-01

In this study, the residual solution arising from the wet oxidative degradation of solid organic cellulosic materials, as one of the component of radioactive solid wastes, using hydrogen peroxide as oxidant. Were incorporated into ordinary Portland cement matrix. Leaching as well as thermal characterizations of the final solidified waste forms were evaluated to meet the final disposal requirements. Factors, such as the amount of the residual solution incorporated, types of leachant. Release of different radionuclides and freezing-thaw treatment, that may affect the leaching characterization. Were studied systematically from the data obtained, it was found that the final solid waste from containing 35% residual solution in tap water is higher than that in ground water or sea water. Based on the data obtained from thermal analysis, it could be concluded that incorporating the residual solution form the wet oxidative degradation of cellulosic materials has no negative effect on the hydration of cement materials and consequently on the thermal stability of the final solid waste from during the disposal process

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 c...

Ruthenium and Platinum Catalysts Supported on Ce, Zr, Pr-O Mixed Oxides Prepared by Soft Chemistry for Acetic Acid Wet Air Oxidation

Czech Academy of Sciences Publication Activity Database

Mikulová, Jana; Rossignol, S.; Barbier Jr., J.; Mesnard, D.; Kappenstein, C.; Duprez, D.

2007-01-01

Roč. 72, 1-2 (2007), s. 1-10 ISSN 0926-3373 Institutional research plan: CEZ:AV0Z40720504 Keywords : sol-gel * catalytic wet air oxidation * acetic acid Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 4.651, year: 2007

On the degradability of printing and dyeing wastewater by wet air oxidation.

Science.gov (United States)

Hu, X; Lei, L; Chen, G; Yue, P L

2001-06-01

A modified first-order kinetics model was used to study the wet air oxidation of printing and dyeing wastewater. The model simulations are in good agreement with experimental data. The results indicate that a certain fraction of organic pollutants in the printing and dyeing wastewater could not be removed even at elevated temperature and prolonged reaction time. The ratio of degradable organic matter is found independent of temperature and can be improved by using a catalyst.

Subcritical wet air oxidation of organic solvents and chelating agents of the nuclear fuel

International Nuclear Information System (INIS)

Bachir, Souley

1999-01-01

This document deals with the environment control, more specially organic solvents and chelating agents destruction, employed in the nuclear industry. This work details the subcritical wet air oxidation process. Another part of the document deals with the possible coupling between this process and the biodegradation technic in the framework of the sewage sludges treatment. (A.L.B.)

A novel technique for hydrogen production from hog-manure in supercritical partial oxidation (SCWPO)

Energy Technology Data Exchange (ETDEWEB)

Youssef, Emhemmed A.; Charpentier, Paul [Western Ontario Univ., London, ON (Canada). Dept. of Chemical and Biochemical Engineering; Nakhla, George [Western Ontario Univ., London, ON (Canada). Dept. of Chemical and Biochemical Engineering; Western Ontario Univ., London, ON (Canada). Dept. of Civil and Environmental Engineering; Elbeshbishy, Elsayed; Hafez, Hisham [Western Ontario Univ., London, ON (Canada). Dept. of Civil and Environmental Engineering

2010-07-01

In this study, the catalytic hydrogen production from hog manure using supercritical water partial oxidation was investigated in a batch reactor at a temperature of 500 C, and pressure of 28 MPa using several metallic catalysts. Hog manure was characterized by a total and soluble chemical oxygen demand (TCOD, SCOD) of 57000 and 28000 mg/L, total and volatile suspended solids (TSS, VSS) of 25000, 19000, and ammonia of 2400 mg/L, respectively. The order of H{sub 2} production was the following: Pd/AC > Ru/Al{sub 2}O{sub 3} > Ru/AC > AC > NaOH. The order of COD reduction efficiency was as follows: NaOH > Ru/AC > AC > Ru/Al{sub 2}O{sub 3} > Pd/AC. The behaviour of the volatile fatty acids (VFA's), ethanol, methanol, ammonia, H{sub 2}S, and Sulfate was investigated experimentally and discussed. A 35 % reduction in the H{sub 2} and CH{sub 4} yields was observed in the sequential gasification partial oxidation (oxidant at an 80 % of theoretical requirement) experiments compared to the gasification experiments (catalyst only). Moreover, this reduction in gas yields was coincided with a 45 % reduction in the liquid effluent chemical oxygen demand (COD), 60 % reduction of the ammonia concentration in the liquid effluent, and 20 % reduction in the H{sub 2}S concentration in the effluent gas. (orig.)

Materials processing using supercritical fluids

Directory of Open Access Journals (Sweden)

Orlović Aleksandar M.

2005-01-01

Full Text Available One of the most interesting areas of supercritical fluids applications is the processing of novel materials. These new materials are designed to meet specific requirements and to make possible new applications in Pharmaceuticals design, heterogeneous catalysis, micro- and nano-particles with unique structures, special insulating materials, super capacitors and other special technical materials. Two distinct possibilities to apply supercritical fluids in processing of materials: synthesis of materials in supercritical fluid environment and/or further processing of already obtained materials with the help of supercritical fluids. By adjusting synthesis parameters the properties of supercritical fluids can be significantly altered which further results in the materials with different structures. Unique materials can be also obtained by conducting synthesis in quite specific environments like reversed micelles. This paper is mainly devoted to processing of previously synthesized materials which are further processed using supercritical fluids. Several new methods have been developed to produce micro- and nano-particles with the use of supercritical fluids. The following methods: rapid expansion of supercritical solutions (RESS supercritical anti-solvent (SAS, materials synthesis under supercritical conditions and encapsulation and coating using supercritical fluids were recently developed.

Development of a lab-scale contaminated organic effluents treatment process using evaporation and supercritical water oxidation

Energy Technology Data Exchange (ETDEWEB)

Turc, H.A.; Joussot-Dubien, C

2004-07-01

The organic liquid waste produced in the ATALANTE facility have to be treated in order to reduce the fire and contamination risks. Therefore, the Mini-DELOS process has been developed, which combines a low pressure evaporator in a shielded enclosure and a continuous supercritical water oxidation (SCWO) reactor in a glovebox. Evaporation makes it possible to evacuate the main organic stream as decontaminated distillates to an industrial incinerator. The remaining residue, concentrating the radioactivity can be converted through SCWO into a contaminated aqueous effluent, fully compatible with the existing outlets of the facility. The preliminary results of the first year of active operation of the Mini- DELOS process are here presented. (authors)

Reaction mechanisms at 4H-SiC/SiO2 interface during wet SiC oxidation

Science.gov (United States)

Akiyama, Toru; Hori, Shinsuke; Nakamura, Kohji; Ito, Tomonori; Kageshima, Hiroyuki; Uematsu, Masashi; Shiraishi, Kenji

2018-04-01

The reaction processes at the interface between SiC with 4H structure (4H-SiC) and SiO2 during wet oxidation are investigated by electronic structure calculations within the density functional theory. Our calculations for 4H-SiC/SiO2 interfaces with various orientations demonstrate characteristic features of the reaction depending on the crystal orientation of SiC: On the Si-face, the H2O molecule is stable in SiO2 and hardly reacts with the SiC substrate, while the O atom of H2O can form Si-O bonds at the C-face interface. Two OH groups are found to be at least necessary for forming new Si-O bonds at the Si-face interface, indicating that the oxidation rate on the Si-face is very low compared with that on the C-face. On the other hand, both the H2O molecule and the OH group are incorporated into the C-face interface, and the energy barrier for OH is similar to that for H2O. By comparing the calculated energy barriers for these reactants with the activation energies of oxide growth rate, we suggest the orientation-dependent rate-limiting processes during wet SiC oxidation.

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...

One-pot reduction of 5-hydroxymethylfurfural via hydrogen transfer from supercritical methanol

DEFF Research Database (Denmark)

Hansen, Thomas Søndergaard; Barta, Katalin; Anastas, Paul T.

2012-01-01

Catalytic conversion of HMF to valuable chemicals was achieved over a Cu-doped porous metal oxide in supercritical methanol. The hydrotalcite catalyst precursor is prepared following simple synthetic procedures, using inexpensive and earth-abundant starting materials in aqueous solutions. The hyd......Catalytic conversion of HMF to valuable chemicals was achieved over a Cu-doped porous metal oxide in supercritical methanol. The hydrotalcite catalyst precursor is prepared following simple synthetic procedures, using inexpensive and earth-abundant starting materials in aqueous solutions....... The hydrogen equivalents needed for the reductive deoxygenation of HMF originate from the solvent itself upon its reforming. Dimethylfuran, dimethyltetrahydrofuran and 2-hexanol were obtained in good yields. At milder reaction temperatures, a combined yield (DMF + DMTHF) of 58% was achieved. Notably...

Reactivities of polystyrenic polymers with supercritical water under nitrogen or air. Identification and formation of degradation compounds

International Nuclear Information System (INIS)

Dubois, M.A.; Dozol, J.F.; Massiani, C.; Ambrosio, M.

1996-01-01

Supercritical water oxidation (SCWO) could offer a viable treatment alternative to destroy the organic structure of ion-exchange resins (IER) that are radioactive process wastes and which contain radioactivity. The GC/MS technique was used successfully to identify the low-concentration degradation compounds that are present in the cold liquid effluent after SCWO of polystyrenic IER at 380 C (25.5 MPa). The study of the behavior of these IER in supercritical water enhances the role of temperature and the role of supercritical water in the degradation process. With the exception of acetic acid, the identified compounds are aromatic. The functional groups are released during the heating time, and they do not interfere in the degradation process. The oxidation involves a complex set of reaction pathways. A mechanism including parallel and competitive reactions is proposed

Process options for treatment of organic containing ILWs by wet oxidation

International Nuclear Information System (INIS)

Holman, D.J.

1989-01-01

The process chemistry, applications and experience with several wet oxidation options are reviewed along with criteria for the selection of viable systems and plant designs, covering a range of organic wastes, including solvents, cellulosic filters, chelant decontamination reagents and ion exchange resins. The use of hydrogen peroxide to treat water-cooled reactor residues containing mixed inorganic and organic filter materials with ion exchange resins is examined in further detail along with treatment of secondary arisings. The technical and financial justifications for treatment are examined along with the engineering requirements to retro-fit the required plant to an existing cement encapsulation facility. (author)

Bench scale demonstration and conceptual engineering for DETOXSM catalyzed wet oxidation

International Nuclear Information System (INIS)

Moslander, J.; Bell, R.; Robertson, D.; Dhooge, P.; Goldblatt, S.

1994-01-01

Laboratory and bench scale studies of the DETOX SM catalyzed wet oxidation process have been performed with the object of developing the process for treatment of hazardous and mixed wastes. Reaction orders, apparent rates, and activation energies have been determined for a range of organic waste surrogates. Reaction intermediates and products have been analyzed. Metals' fates have been determined. Bench scale units have been designed, fabricated, and tested with solid and liquid organic waste surrogates. Results from the laboratory and bench scale studies have been used to develop conceptual designs for application of the process to hazardous and mixed wastes

Effects of the wet air on the properties of the lanthanum oxide and lanthanum aluminate thin films

International Nuclear Information System (INIS)

Jun, Jin Hyung; Choi, Doo Jin

2006-01-01

Lanthanum oxide and lanthanum aluminate thin films were deposited on Si substrates. The as-grown films were stored in wet ambient and dry ambient for days and annealed after storage and also the structural and the electrical properties of the films were investigated. As the storage time increased, the La 2 O 3 films stored in wet ambient showed rapid reaction with moisture and the properties degraded. In case of the LAO films, although the thickness of the film also increased during hydration, the properties of the film did not so much changed due to the role of the incorporated aluminum. The LAO films showed better hydration resistance characteristics and so more suitable for conventional wet cleaning process in semiconductor fabrication

Reactive turbulent flow CFD study in supercritical water oxidation process: application to a stirred double shell reactor; Etude par simulation numerique des ecoulements turbulents reactifs dans les reacteurs d'oxydation hydrothermale: application a un reacteur agite double enveloppe

Energy Technology Data Exchange (ETDEWEB)

Moussiere, S

2006-12-15

Supercritical water oxidation is an innovative process to treat organic liquid waste which uses supercritical water properties to mix efficiency the oxidant and the organic compounds. The reactor is a stirred double shell reactor. In the step of adaptation to nuclear constraints, the computational fluid dynamic modeling is a good tool to know required temperature field in the reactor for safety analysis. Firstly, the CFD modeling of tubular reactor confirms the hypothesis of an incompressible fluid and the use of k-w turbulence model to represent the hydrodynamic. Moreover, the EDC model is as efficiency as the kinetic to compute the reaction rate in this reactor. Secondly, the study of turbulent flow in the double shell reactor confirms the use of 2D axisymmetric geometry instead of 3D geometry to compute heat transfer. Moreover, this study reports that water-air mixing is not in single phase. The reactive turbulent flow is well represented by EDC model after adaptation of initial conditions. The reaction rate in supercritical water oxidation reactor is mainly controlled by the mixing. (author)

Precision Recess of AlGaN/GaN with Controllable Etching Rate Using ICP-RIE Oxidation and Wet Etching

NARCIS (Netherlands)

Sokolovskij, R.; Sun, J.; Santagata, F.; Iervolino, E.; Li, S.; Zhang, G.Y.; Sarro, P.M.; Zhang, G.Q.

2016-01-01

A method for highly controllable etching of AlGaN/GaN for the fabrication of high sensitivity HEMT based sensors is developed. The process consists of cyclic oxidation of nitride with O₂ plasma using ICP-RIE etcher followed by wet etching of the oxidized layer. Previously reported

Challenges of selecting materials for the process of biomass gasification in supercritical water

Energy Technology Data Exchange (ETDEWEB)

Boukis, N.; Habicht, W.; Hauer, E.; Dinjus, E. [Karlsruher Institut fuer Technologie (KIT), Karlsruhe (Germany). Inst. fuer Technische Chemie

2010-07-01

A new process for the gasification of wet biomass is the reaction in supercritical water. The product is a combustible gas, rich in hydrogen with a high calorific value. The reaction is performed under high temperatures - up to 700 C - and pressures up to 30 MPa. The combination of these physical conditions and the corrosive environment is very demanding for the construction materials of the reactor. Only few alloys exhibit the required mechanical properties, especially the mechanical strength at temperatures higher than 600 C. Ni-Base alloys like alloy 625 can be applied up to a temperature of 700 C and are common materials for application under supercritical water conditions. During gasification experiments with corn silage and other biomasses, corrosion of the reactor material alloy 625 appears. The gasification of an aqueous methanol solution in supercritical water at temperatures up to 600 C and 25 - 30 MPa pressure results in an product gas rich in hydrogen, carbon dioxide and some methane. Alloy 625 shows very low corrosion rates in this environment. It is obvious that the heteroatoms and salts present in biomass cause corrosion of the reactor material. (orig.)

A whole biodiesel conversion process combining isolation, cultivation and in situ supercritical methanol transesterification of native microalgae.

Science.gov (United States)

Jazzar, Souhir; Quesada-Medina, Joaquín; Olivares-Carrillo, Pilar; Marzouki, Mohamed Néjib; Acién-Fernández, Francisco Gabriel; Fernández-Sevilla, José María; Molina-Grima, Emilio; Smaali, Issam

2015-08-01

A coupled process combining microalgae production with direct supercritical biodiesel conversion using a reduced number of operating steps is proposed in this work. Two newly isolated native microalgae strains, identified as Chlorella sp. and Nannochloris sp., were cultivated in both batch and continuous modes. Maximum productivities were achieved during continuous cultures with 318mg/lday and 256mg/lday for Chlorella sp. and Nannochloris sp., respectively. Microalgae were further characterized by determining their photosynthetic performance and nutrient removal efficiency. Biodiesel was produced by catalyst-free in situ supercritical methanol transesterification of wet unwashed algal biomass (75wt.% of moisture). Maximum biodiesel yields of 45.62wt.% and 21.79wt.% were reached for Chlorella sp. and Nannochloris sp., respectively. The analysis of polyunsaturated fatty acids of Chlorella sp. showed a decrease in their proportion when comparing conventional and supercritical transesterification processes (from 37.4% to 13.9%, respectively), thus improving the quality of the biodiesel. Copyright © 2015 Elsevier Ltd. All rights reserved.

SUPERCRITICAL WATER PARTIAL OXIDATION PHASE I - PILOT-SCALE TESTING / FEASIBILITY STUDIES FINAL REPORT

Energy Technology Data Exchange (ETDEWEB)

SPRITZER,M; HONG,G

2005-01-01

Under Cooperative Agreement No. DE-FC36-00GO10529 for the Department of Energy, General Atomics (GA) is developing Supercritical Water Partial Oxidation (SWPO) as a means of producing hydrogen from low-grade biomass and other waste feeds. The Phase I Pilot-scale Testing/Feasibility Studies have been successfully completed and the results of that effort are described in this report. The Key potential advantages of the SWPO process is the use of partial oxidation in-situ to rapidly heat the gasification medium, resulting in less char formation and improved hydrogen yield. Another major advantage is that the high-pressure, high-density aqueous environment is ideal for reaching and gasifying organics of all types. The high water content of the medium encourages formation of hydrogen and hydrogen-rich products and is especially compatible with high water content feeds such as biomass materials. The high water content of the medium is also effective for gasification of hydrogen-poor materials such as coal. A versatile pilot plant for exploring gasification in supercritical water has been established at GA's facilities in San Diego. The Phase I testing of the SWPO process with wood and ethanol mixtures demonstrated gasification efficiencies of about 90%, comparable to those found in prior laboratory-scale SCW gasification work carreid out at the University of Hawaii at Manoa (UHM) as well as other biomass gasification experience with conventional gasifiers. As in the prior work at UHM, a significant amount of the hydrogen found in the gas phase products is derived from the water/steam matrix. The studies at UHM utilized an indirectly heated gasifier with an acitvated carbon catalyst. In contrast, the GA studies utilized a directly heated gasifier without catalyst, plus a surrogate waste fuel. Attainment of comparable gasification efficiencies without catalysis is an important advancement for the GA process, and opens the way for efficient hydrogen production from low

Investigation of the precipitation of Na2SO4 in supercritical water

DEFF Research Database (Denmark)

Voisin, T.; Erriguible, A.; Philippot, G.

2017-01-01

solubility in sub-and supercritical water is determined on a wide temperature range using a continuous set-up. Crystallite sizes formed after precipitation are measured with in situ synchrotron wide angle X-ray scattering (WAXS). Combining these experimental results, a numerical modeling of the precipitation......SuperCritical Water Oxidation process (SCWO) is a promising technology for treating toxic and/or complex chemical wastes with very good efficiency. Above its critical point (374 degrees C, 22.1 MPa), water exhibits particular properties and organic compounds can be easily dissolved and degraded...... with the addition of oxidizing agents. But these interesting properties imply a main drawback regarding inorganic compounds. Highly soluble at ambient temperature in water, these inorganics (such as salts) are no longer soluble in supercritical water and precipitate into solids, creating plugs in SCWO processes...

Data acquisition testing in supercritical water oxidation using machine cutting oils and metals

International Nuclear Information System (INIS)

Garcia, K.M.

1996-01-01

The Department of Energy, the Navy, and SERDP provided funding for an extensive series of testing of a Supercritical Water Oxidation (SCWO) system. The goal of the testing was to create performance data on the process when dealing with highly chlorinated wastes containing heavy metals, and radionuclides. The testing was performed in a MODAR vessel oxidizer. Performance was measured by the ability of the process to achieve greater than 99.99% destruction of the organic content, to partition the metals and radionuclide surrogates for mass balance, and survive the highly corrosive species in the effluent. The test data has shown that these goals were accomplished. 30 gal/day of highly chlorinated machine cutting oil was treated for 130 hrs. There were no significant corrosion or solids handling problems. This machine cutting oil, TRIM reg-sign SOL was chosen by DOE for its complex nature and has proven to be one of the more refractory organic feeds encountered by MODAR. The Navy provided 8 waste streams collected from their shore facilities operation. These paints varied in solids content with wastes such as paint chips, and adhesives. The ninth test run was with all 8 series of wastes combined. The MODAR system successfully treated all of these waste streams providing performance data on the ability of SCWO to treat difficult sludges

Supercritical fluid extraction of bi & multi-layer graphene sheets from graphite by using exfoliation technique

Science.gov (United States)

Xavier, Gauravi; Dave, Bhoomi; Khanna, Sakshum

2018-05-01

In recent times, researchers have turned to explore the possibility of using Supercritical Fluid (SCFs) system to penetrate into the inert-gaping of graphite and exfoliate it into a number of layer graphene sheets. The supercritical fluid holds excellent wetting surfaces with low interfacial tension and high diffusion coefficients. Although SCFs exfoliation approach looks promising to developed large scale & low-cost graphene sheet but has not received much attention. To arouse interest and reflection on this approach, this review is organized to summarize the recent progress in graphene production by SCF technology. Here we present the simplest route to obtained layers of graphene sheets by intercalating and exfoliating graphite using supercritical CO2 processing. The layers graphene nano-sheets were collected in dichloromethane (DCM) solution which prevents the restocking of sheets. The obtained graphene sheets show the desired characteristics and thus can be used in physical, chemical and biological sciences. Thus this method provides an effortless and eco-friendly approach for the synthesis of layers of graphene sheets.

Application of supercritical and subcritical fluids for the extraction of hazardous materials from soil

Directory of Open Access Journals (Sweden)

Skorupan Dara

2002-01-01

Full Text Available Subcritical and supercritical extractions are novel, non destructive techniques which can be applied for the removal of hazardous compounds from contaminated soil without any changes of the soil composition and structure. The aim of the presented review paper is to give information on up-to day results of this method commonly applied by several institutions worldwide. Interest in the application of SC CO2 has been more expressed in the last two decades, which may be related to its favorable characteristics (non-toxic, non-flammable, increase diffusion into small pores, low viscosity under SC conditions, low price and others. However, interest in wet oxidation (WO and especially in SCWO (the application of water under supercritical conditions with air has also increased in the last few years. Interest in H2O as a SC fluid, as well as in extraction with water under subcritical conditions may also be related to specific characteristics and the enhanced rate of extraction. Moreover, the solubility of some specific compounds present in soil can be easily changed by adjusting the pressure and temperature of extraction. The high price of the units designed to operate safely at a pressure and temperature much higher than the a critical one of the applied fluids is the main reason why, at present, there is no more broader application of such techniques for the removal hazardous materials from contaminated soil. In the present paper, among many literature citations and their overall review, some specific details related to the development of specific analytical methods under SC conditions are also considered.

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...... gas produced higher ethanol yields and cellulose, hemicelluloses, and lignin recoveries, than 15 min WO treatment at 195 °C. Also, recycling filtrate and use of higher oxygen gas pressure reduced recovery of materials. The use of filtrate could be inhibitory for the yeast, but also reduced lactic acid...

Predicting the Oxidation/Corrosion Performance of Structural Alloys in Supercritical CO₂

Energy Technology Data Exchange (ETDEWEB)

Wright, Ian [Wright HT Inc., Denver, CO (United States); Kung, Steven [Electric Power Research Inst. (EPRI), Charlotte, NC (United States); Shingledecker, John [Electric Power Research Inst. (EPRI), Charlotte, NC (United States)

2017-12-22

This project was the first research to address oxidation of alloys under supercritical CO₂ conditions relevant to a semi-open Allam Cycle system. The levels of impurities expected in the CO₂ for typical operation were determined by thermodynamic and mass balance calculations, and a test rig was assembled and used to run corrosion tests at temperatures from 650 to 750°C in CO₂ at 200 bar for up to 5,000h, with and without impurities. Oxidation rates were measured for seven alloys representing high-strength ferritic steels, standard austenitic steels, and Ni-based alloys with higher-temperature capabilities. The very thin, protective scales formed on the high-temperature alloys provided significant challenges in characterization and thickness measurement. The rates of mass gain and scale thickening were possibly slower when oxidizing impurities were present in the sCO₂, and the scale morphologies formed on the ferritic and austenitic steels were consistent with expectations, and similar to those formed in high-pressure steam, with some potential influences of C. Some surface hardening (possibly due to carbon uptake) was identified in ferritic steels Grade 91 and VM12, and appeared more severe in commercially-pure CO₂. Hardening was also observed in austenitic steel TP304H, but that in HR3C appeared anomalous, probably the result of work-hardening from specimen preparation. No hardening was found in Ni-base alloys IN617 and IN740H. An existing EPRI Oxide Exfoliation Model was modified for this application and used to evaluate the potential impact of the scales grown in sCO₂ on service lifetimes in compact heat exchanger designs. Results suggested that reduction in flow area by simple oxide growth as well as by accumulation of exfoliated scale may have a major effect on the design of small-channel heat exchangers. In addition, the specific oxidation behavior of each alloy strongly influences the

Solid catalyzed isoparaffin alkylation at supercritical fluid and near-supercritical fluid conditions

Science.gov (United States)

Ginosar, Daniel M.; Fox, Robert V.; Kong, Peter C.

2000-01-01

This invention relates to an improved method for the alkylation reaction of isoparaffins with olefins over solid catalysts including contacting a mixture of an isoparaffin, an olefin and a phase-modifying material with a solid acid catalyst member under alkylation conversion conditions at either supercritical fluid, or near-supercritical fluid conditions, at a temperature and a pressure relative to the critical temperature(T.sub.c) and the critical pressure(P.sub.c) of the reaction mixture. The phase-modifying phase-modifying material is employed to promote the reaction's achievement of either a supercritical fluid state or a near-supercritical state while simultaneously allowing for decreased reaction temperature and longer catalyst life.

Supercritical water oxidation test bed effluent treatment study

International Nuclear Information System (INIS)

Barnes, C.M.

1994-04-01

This report presents effluent treatment options for a 50 h Supercritical Water Test Unit. Effluent compositions are calculated for eight simulated waste streams, using different assumed cases. Variations in effluent composition with different reactor designs and operating schemes are discussed. Requirements for final effluent compositions are briefly reviewed. A comparison is made of two general schemes. The first is one in which the effluent is cooled and effluent treatment is primarily done in the liquid phase. In the second scheme, most treatment is performed with the effluent in the gas phase. Several unit operations are also discussed, including neutralization, mercury removal, and evaporation

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.

Catalytic and non-catalytic wet air oxidation of sodium dodecylbenzene sulfonate: Kinetics and biodegradability enhancement

Energy Technology Data Exchange (ETDEWEB)

Suarez-Ojeda, Maria Eugenia [Departament d' Enginyeria Quimica, Escola Tecnica Superior d' Enginyeria Quimica, Universitat Rovira i Virgili, Av. Paisos Catalans 26, 43007 Tarragona, Catalonia (Spain); Departament d' Enginyeria Quimica, Edifici Q-ETSE, Universitat Autonoma de Barcelona, 08193 Bellaterra, Barcelona, Catalonia (Spain); Kim, Jungkwon [Chemical Engineering and Analytical Sciences Department, University of Manchester, Manchester (United Kingdom); Carrera, Julian [Departament d' Enginyeria Quimica, Edifici Q-ETSE, Universitat Autonoma de Barcelona, 08193 Bellaterra, Barcelona, Catalonia (Spain); Metcalfe, Ian S. [Chemical Engineering and Advanced Materials Department, University of Newcastle upon Tyne, Newcastle upon Tyne (United Kingdom); Font, Josep [Departament d' Enginyeria Quimica, Escola Tecnica Superior d' Enginyeria Quimica, Universitat Rovira i Virgili, Av. Paisos Catalans 26, 43007 Tarragona, Catalonia (Spain)]. E-mail: jose.font@urv.cat

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 15bar of oxygen partial pressure (P{sub O{sub 2}}) and at 180, 200 and 220deg. 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{sub O{sub 2}} were 140-160deg. C and 2-9bar, 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 160deg. C and 2 bar of P{sub O{sub 2}}, 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{sub 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.

Catalytic and non-catalytic wet air oxidation of sodium dodecylbenzene sulfonate: Kinetics and biodegradability enhancement

International Nuclear Information System (INIS)

Suarez-Ojeda, Maria Eugenia; Kim, Jungkwon; Carrera, Julian; Metcalfe, Ian S.; Font, Josep

2007-01-01

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 15bar of oxygen partial pressure (P O 2 ) and at 180, 200 and 220deg. 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 O 2 were 140-160deg. C and 2-9bar, 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 160deg. C and 2 bar of P O 2 , 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

Methane dry reforming over Ni catalysts supported on Ce–Zr oxides prepared by a route involving supercritical fluids

Directory of Open Access Journals (Sweden)

Smirnova Marina Yu.

2017-12-01

Full Text Available Ce0.5Zr0.5O2 mixed oxides were prepared in a flow reactor in supercritical isopropanol with acetylacetone as a complexing agent. Variation of the nature of the Zr salt and the temperature of synthesis affected the phase composition, morphology and specific surface area of oxides. X-ray diffraction and Raman spectroscopy studies revealed formation of metastable t” and t’ phases. Oxides are comprised of agglomerates with sizes depending on the synthesis parameters. Loading NiO decreases the specific surface area without affecting X-ray particle sizes of supports. Such sintering was the most pronounced for a support with the highest specific surface area, which resulted in the lowest surface content of Ni as estimated by X-ray photoelectron spectroscopy and in the formation of flattened NiO particles partially embedded into the support. The catalytic activity and stability of these samples in the dry reforming of methane were determined by the surface concentration of Ni and the morphology of its particle controlled by the metal-support interaction, which also depends on the type of catalyst pretreatment. Samples based on ceria-zirconia oxides prepared under these conditions provide a higher specific catalytic activity as compared with the traditional Pechini route, which makes them promising for the practical application.

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.

Hot water extraction with in situ wet oxidation: Kinetics of PAHs removal from soil

International Nuclear Information System (INIS)

Dadkhah, Ali A.; Akgerman, Aydin

2006-01-01

Finding environmentally friendly and cost-effective methods to remediate soils contaminated with polycyclic aromatic hydrocarbons (PAHs) is currently a major concern of researchers. In this study, a series of small-scale semi-continuous extractions - with and without in situ wet oxidation - were performed on soils polluted with PAHs, using subcritical water (i.e. liquid water at high temperatures and pressures, but below the critical point) as the removal agent. Experiments were performed in a 300 mL reactor using an aged soil sample. To find the desorption isotherms and oxidation reaction rates, semi-continuous experiments with residence times of 1 and 2 h were performed using aged soil at 250 deg. C and hydrogen peroxide as oxidizing agent. In all combined extraction and oxidation flow experiments, PAHs in the remaining soil after the experiments were almost undetectable. In combined extraction and oxidation no PAHs could be detected in the liquid phase after the first 30 min of the experiments. Based on these results, extraction with hot water, if combined with oxidation, should reduce the cost of remediation and can be used as a feasible alternative technique for remediating contaminated soils and sediments

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.

Effective treatment of oily scum via catalytic wet persulfate oxidation process activated by Fe2.

Science.gov (United States)

Yuan, Xingzhong; Guan, Renpeng; Wu, Zhibin; Jiang, Longbo; Li, Yifu; Chen, Xiaohong; Zeng, Guangming

2018-04-05

Oily scum, a hazardous by-product of petroleum industry, need to be deposed urgently to reduce environmental risks. This paper introduces catalytic wet persulfate oxidation (CWPO) process in the treatment of oily scum to realize risk relief. Under the activation of heat and Fe 2+ , persulfate (PS) was decomposed into sulfate radicals and hydroxyl radicals, which played a major role on the degradation of petroleum hydrocarbons. The effects of wet air oxidation (WAO) and CWPO process on the degradation of oily scum were compared. In CWPO process, the total petroleum hydrocarbons (TPHs) content of oily scum was decreased from 92.63% to 16.75%, which was still up to 70.19% in WAO process. The degradation rate of TPHs in CWPO process was about 3.38 times higher than that in WAO process. The great performance of CWPO process was also confirmed by elemental analysis, which indicated that the C and H contents of oily scum were reduced significantly by CWPO process. These results indicated that CWPO process has high potential on the degradation of oily scum for environmental protection. Copyright © 2018 Elsevier Ltd. All rights reserved.

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...

Extraction with supercritical gases

Energy Technology Data Exchange (ETDEWEB)

Schneider, G M; Wilke, G; Stahl, E

1980-01-01

The contents of this book derives from a symposium on the 5th and 6th of June 1978 in the ''Haus der Technik'' in Essen. Contributions were made to separation with supercritical gases, fluid extraction of hops, spices and tobacco, physicochemical principles of extraction, phase equilibria and critical curves of binary ammonia-hydrocarbon mixtures, a quick method for the microanalytical evaluation of the dissolving power of supercritical gases, chromatography with supercritical fluids, the separation of nonvolatile substances by means of compressed gases in countercurrent processes, large-scale industrial plant for extraction with supercritical gases, development and design of plant for high-pressure extraction of natural products.

Metatranscriptomic and metagenomic description of the bacterial nitrogen metabolism in waste water wet oxidation effluents

Directory of Open Access Journals (Sweden)

Julien Crovadore

2017-10-01

Full Text Available Anaerobic digestion is a common method for reducing the amount of sludge solids in used waters and enabling biogas production. The wet oxidation process (WOX improves anaerobic digestion by converting carbon into methane through oxidation of organic compounds. WOX produces effluents rich in ammonia, which must be removed to maintain the activity of methanogens. Ammonia removal from WOX could be biologically operated by aerobic granules. To this end, granulation experiments were conducted in 2 bioreactors containing an activated sludge (AS. For the first time, the dynamics of the microbial community structure and the expression levels of 7 enzymes of the nitrogen metabolism in such active microbial communities were followed in regard to time by metagenomics and metatranscriptomics. It was shown that bacterial communities adapt to the wet oxidation effluent by increasing the expression level of the nitrogen metabolism, suggesting that these biological activities could be a less costly alternative for the elimination of ammonia, resulting in a reduction of the use of chemicals and energy consumption in sewage plants. This study reached a strong sequencing depth (from 4.4 to 7.6 Gb and enlightened a yet unknown diversity of the microorganisms involved in the nitrogen pathway. Moreover, this approach revealed the abundance and expression levels of specialised enzymes involved in nitrification, denitrification, ammonification, dissimilatory nitrate reduction to ammonium (DNRA and nitrogen fixation processes in AS. Keywords: Applied sciences, Biological sciences, Environmental science, Genetics, Microbiology

Aluminum oxide mask fabrication by focused ion beam implantation combined with wet etching

International Nuclear Information System (INIS)

Liu Zhengjun; Iltanen, Kari; Chekurov, Nikolai; Tittonen, Ilkka; Grigoras, Kestutis

2013-01-01

A novel aluminum oxide (Al 2 O 3 ) hard mask fabrication process with nanoscale resolution is introduced. The Al 2 O 3 mask can be used for various purposes, but in this work it was utilized for silicon patterning using cryogenic deep reactive ion etching (DRIE). The patterning of Al 2 O 3 is a two-step process utilizing focused ion beam (FIB) irradiation combined with wet chemical etching. Gallium (Ga + ) FIB maskless patterning confers wet etch selectivity between the irradiated region and the non-irradiated one on the Al 2 O 3 layer, and mask patterns can easily be revealed by wet etching. This method is a modification of Ga + FIB mask patterning for the silicon etch stop, which eliminates the detrimental lattice damage and doping of the silicon substrate in critical devices. The shallow surface gallium FIB irradiated Al 2 O 3 mask protects the underlying silicon from Ga + ions. The performance of the masking capacity was tested by drawing pairs consisting of a line and an empty space with varying width. The best result was seven such pairs for 1 μm. The smallest half pitch was 59 nm. This method is capable of arbitrary pattern generation. The fabrication of a freestanding single-ended tuning fork resonator utilizing the introduced masking method is demonstrated. (paper)

Destruction of an industrial wastewater by supercritical water oxidation in a transpiring wall reactor

International Nuclear Information System (INIS)

Bermejo, M.D.; Cocero, M.J.

2006-01-01

The supercritical water oxidation (SCWO) is a technology that takes advantage of the special properties of water in the surroundings of critical point of water to completely oxidize wastes in residence times lower than 1 min. The problems caused by the harsh operational conditions of the SCWO process are being solved by new reactor designs, such as the transpiring wall reactor (TWR). In this work, the operational parameters of a TWR have been studied for the treatment of an industrial wastewater. As a result, the process has been optimized for a feed flow of 16 kg/h with feed inlet temperatures higher than 300 deg. C and transpiring flow relation (R) between 0.2 and 0.6 working with an 8% (w/w) isopropanol (IPA) as a fuel. The experimental data and a mathematical model have been applied for the destruction of an industrial waste containing acetic acid and crotonaldehyde as main compounds. As the model predicted, removal efficiencies higher than 99.9% were obtained, resulting in effluents with 2 ppm total organic carbon (TOC) at feed flow of 16 kg/h, 320 deg. C of feed temperature and R = 0.32. An effluent TOC of 35 ppm under conditions feed flow of 18 kg/h, feed inlet temperatures of 290 deg. C, reaction temperatures of 570 deg. C and R = 0.6

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...... increase of substrate concentration reduced the ethanol yield significant as a result of insufficient mass transfer. It was also shown that the fermentation could be followed with an easy monitoring system based on the weight loss of the produced CO2. (C) 2004 Wiley Periodicals, Inc....

Surface chemistry and corrosion behavior of Inconel 625 and 718 in subcritical, supercritical, and ultrasupercritical water

Energy Technology Data Exchange (ETDEWEB)

Rodriguez, David; Merwin, Augustus; Karmiol, Zachary; Chidambaram, Dev, E-mail: dcc@unr.edu

2017-05-15

Highlights: • Mixtures of oxides containing Ni, Fe, Cr and Nb formed on the surface. • Short term exposure tests observed breakdown of native film. • Formation of a Fe rich oxide layer on Inconel 718 prevents mass loss. - Abstract: Corrosion behavior of Inconel 625 and 718 in subcritical, supercritical and ultrasupercritical water was studied as a function of temperature and time. The change in the chemistry of the as-received surface film on Inconel 625 and 718 after exposure to subcritical water at 325 °C and supercritical water at 425 °C and 527.5 °C for 2 h was studied. After exposure to 325 °C subcritical water, the CrO{sub 4}{sup 2−} based film formed; however minor quantities of NiFe{sub x}Cr{sub 2-x}O{sub 4} spinel compounds were observed. The oxide film formed on both alloys when exposed to supercritical water at 425 °C consisted of NiFe{sub x}Cr{sub 2-x}O{sub 4} spinel. The surface films on both alloys were identified as NiFe{sub 2}O{sub 4} when exposed to supercritical water at 527.5 °C. To characterize the fully developed oxide layer, studies were conducted at test solution temperatures of 527.5 and 600 °C. Samples were exposed to these temperatures for 24, 96, and 200 h. Surface chemistry was analyzed using X-ray diffraction, as well as Raman and X-ray photoelectron spectroscopies. Inconel 718 exhibited greater mass gain than Inconel 625 for all temperatures and exposure times. The differences in corrosion behavior of the two alloys are attributed to the lower content of chromium and increased iron content of Inconel 718 as compared to Inconel 625.

Surface chemistry and corrosion behavior of Inconel 625 and 718 in subcritical, supercritical, and ultrasupercritical water

International Nuclear Information System (INIS)

Rodriguez, David; Merwin, Augustus; Karmiol, Zachary; Chidambaram, Dev

2017-01-01

Highlights: • Mixtures of oxides containing Ni, Fe, Cr and Nb formed on the surface. • Short term exposure tests observed breakdown of native film. • Formation of a Fe rich oxide layer on Inconel 718 prevents mass loss. - Abstract: Corrosion behavior of Inconel 625 and 718 in subcritical, supercritical and ultrasupercritical water was studied as a function of temperature and time. The change in the chemistry of the as-received surface film on Inconel 625 and 718 after exposure to subcritical water at 325 °C and supercritical water at 425 °C and 527.5 °C for 2 h was studied. After exposure to 325 °C subcritical water, the CrO_4"2"− based film formed; however minor quantities of NiFe_xCr_2_-_xO_4 spinel compounds were observed. The oxide film formed on both alloys when exposed to supercritical water at 425 °C consisted of NiFe_xCr_2_-_xO_4 spinel. The surface films on both alloys were identified as NiFe_2O_4 when exposed to supercritical water at 527.5 °C. To characterize the fully developed oxide layer, studies were conducted at test solution temperatures of 527.5 and 600 °C. Samples were exposed to these temperatures for 24, 96, and 200 h. Surface chemistry was analyzed using X-ray diffraction, as well as Raman and X-ray photoelectron spectroscopies. Inconel 718 exhibited greater mass gain than Inconel 625 for all temperatures and exposure times. The differences in corrosion behavior of the two alloys are attributed to the lower content of chromium and increased iron content of Inconel 718 as compared to Inconel 625.

Development of an Accelerated Methodology to Study Degradation of Materials in Supercritical Water for Application in High Temperature Power Plants

Science.gov (United States)

Rodriguez, David

The decreasing supply of fossil fuel sources, coupled with the increasing concentration of green house gases has placed enormous pressure to maximize the efficiency of power generation. Increasing the outlet temperature of these power plants will result in an increase in operating efficiency. By employing supercritical water as the coolant in thermal power plants (nuclear reactors and coal power plants), the plant efficiency can be increased to 50%, compared to traditional reactors which currently operate at 33%. The goal of this dissertation is to establish techniques to characterize the mechanical properties and corrosion behavior of materials exposed to supercritical water. Traditionally, these tests have been long term exposure tests spanning months. The specific goal of this dissertation is to develop a methodology for accelerated estimation of corrosion rates in supercritical water that can be sued as a screening tool to select materials for long term testing. In this study, traditional methods were used to understand the degradation of materials in supercritical water and establish a point of comparison to the first electrochemical studies performed in supercritical water. Materials studied included austenitic steels (stainless steel 304, stainless steel 316 and Nitronic 50) and nickel based alloys (Inconel 625 and 718). Surface chemistry of the oxide layer was characterized using scanning electron microscopy, X-ray diffraction, FT-IR, Raman and X-ray photoelectron spectroscopies. Stainless steel 304 was subjected to constant tensile load creep tests in water at a pressure of 27 MPa and at temperatures of 200 °C, 315 °C and supercritical water at 450 °C for 24 hours. It was determined that the creep rate for stainless steel 304 exposed to supercritical water would be unacceptable for use in service. It was observed that the formation of hematite was favored in subcritical temperatures, while magnetite was formed in the supercritical region. Corrosion of

Catalytic wet air oxidation of chlorophenols over supported ruthenium catalysts

International Nuclear Information System (INIS)

Li Ning; Descorme, Claude; Besson, Michele

2007-01-01

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 3 wt.% 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 3 wt.% 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 (393 K) and lower total pressure (3 MPa). 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

Three-dimensional block copolymer nanostructures by the solvent-annealing-induced wetting in anodic aluminum oxide templates.

Science.gov (United States)

Chu, Chiang-Jui; Chung, Pei-Yun; Chi, Mu-Huan; Kao, Yi-Huei; Chen, Jiun-Tai

2014-09-01

Block copolymers have been extensively studied over the last few decades because they can self-assemble into well-ordered nanoscale structures. The morphologies of block copolymers in confined geometries, however, are still not fully understood. In this work, the fabrication and morphologies of three-dimensional polystyrene-block-polydimethylsiloxane (PS-b-PDMS) nanostructures confined in the nanopores of anodic aluminum oxide (AAO) templates are studied. It is discovered that the block copolymers can wet the nanopores using a novel solvent-annealing-induced nanowetting in templates (SAINT) method. The unique advantage of this method is that the problem of thermal degradation can be avoided. In addition, the morphologies of PS-b-PDMS nanostructures can be controlled by changing the wetting conditions. Different solvents are used as the annealing solvent, including toluene, hexane, and a co-solvent of toluene and hexane. When the block copolymer wets the nanopores in toluene vapors, a perpendicular morphology is observed. When the block copolymer wets the nanopores in co-solvent vapors (toluene/hexane = 3:2), unusual circular and helical morphologies are obtained. These three-dimensional nanostructures can serve as naontemplates for refilling with other functional materials, such as Au, Ag, ZnO, and TiO2 . © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Design requirements for the supercritical water oxidation test bed

International Nuclear Information System (INIS)

Svoboda, J.M.; Valentich, D.J.

1994-05-01

This report describes the design requirements for the supercritical water oxidation (SCWO) test bed that will be located at the Idaho National Engineering Laboratory (INEL). The test bed will process a maximum of 50 gph of waste plus the required volume of cooling water. The test bed will evaluate the performance of a number of SCWO reactor designs. The goal of the project is to select a reactor that can be scaled up for use in a full-size waste treatment facility to process US Department of Energy mixed wastes. EG ampersand G Idaho, Inc. will design and construct the SCWO test bed at the Water Reactor Research Test Facility (WRRTF), located in the northern region of the INEL. Private industry partners will develop and provide SCWO reactors to interface with the test bed. A number of reactor designs will be tested, including a transpiring wall, tube, and vessel-type reactor. The initial SCWO reactor evaluated will be a transpiring wall design. This design requirements report identifies parameters needed to proceed with preliminary and final design work for the SCWO test bed. A flow sheet and Process and Instrumentation Diagrams define the overall process and conditions of service and delineate equipment, piping, and instrumentation sizes and configuration Codes and standards that govern the safe engineering and design of systems and guidance that locates and interfaces test bed hardware are provided. Detailed technical requirements are addressed for design of piping, valves, instrumentation and control, vessels, tanks, pumps, electrical systems, and structural steel. The approach for conducting the preliminary and final designs and environmental and quality issues influencing the design are provided

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 ga...

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...... 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......-toxic carboxylic acids mainly (2.2-4.5 % on DS basis). Simultaneous saccharification and fermentation (SSF) of the treated waste at 10% DS by Saccharomyces cerevisae yielded average ethanol concentrations of 16.5 to 22 g l(-1) for enzyme loadings of 5 and 25 FPU g(-1) DS, respectively. The cellulose to ethanol...

Corrosion phenomena on alloy 625 in aqueous solutions containing hydrochloric acid and oxygen under subcritical and supercritical conditions

International Nuclear Information System (INIS)

Boukis, N.; Kritzer, P.

1997-01-01

Supercritical Water Oxidation (SCWO) is a very effective process to destroy hazardous aqueous wastes containing organic contaminants. The main target applications in the USA are the destruction of DOD and DOE wastes such as rocket fuels and explosives, warfare agents and organics present in low level radioactive liquid wastes. Alloy 625 is frequently used as reactor material for Supercritical Water Oxidation (SCWO) applications. This is due to the favorable combination of mechanical properties, corrosion resistance, price and availability. Nevertheless, the corrosion of alloy 625 like the corrosion of other Ni-base alloys during oxidation of hazardous organic waste containing chloride proceeds too fast and is a major problem in SCWO applications. In these experiments high pressure, high-temperature resistant tube reactors made of alloy 625 were used as specimens. They were exposed to SCWO conditions, without organics, at temperatures up to 500 C and pressures up to 37 MPa for up to 150 h. Simultaneously, coupons also made from alloy 625 are exposed inside the test tubes. The most important corrosion problem for alloy 625 is pitting and intercrystalline corrosion at temperatures near the critical temperature, i.e. in the preheater and cooling sections of the test tubes. Under certain conditions, stress corrosion cracking appears and leads to premature failure of the test reactors. The corrosion products were insoluble in supercritical water and formed thick layers in the supercritical part of the reactor. Under these layers only minor corrosion occurred. 33 refs

FY1995 generic supercritical water technology; 1995 nendo generic technology to shite no chorinkai riyo gijutsu

Energy Technology Data Exchange (ETDEWEB)

NONE

1997-03-01

For the establishment of the basis of supercritical fluid technology, we perform elucidation of the specific feature of the supercritical fluid as a reaction media and development of some new process. In this study, we first studied the fluid structure of SCF through in-situ spectroscopy and MD simulation. As a result, significant hydrogen bonding amongst water molecules and a solvation structure around the solute were observed in the supercritical state. This fluid structure has new features different from that of high temperature steam or liquid water. We found that this is closely related to the difference of bulk properties of SCF and local one around the solute. On the basis of these fundamental findings and with the better understanding of the specific features of SCF as a reaction media, development of some new process had been conducted more efficiently and successfully. The processes being developed in this study include 1) waste biomass and plastic conversion to recover chemicals, 2) hydrogenation of heavy oil for desulphurization through partial oxidation 1 and 3) hydrothermal synthesis of metal oxide fine particles. (NEDO)

Supercritical Water Reactors

International Nuclear Information System (INIS)

Bouchter, J.C.; Dufour, P.; Guidez, J.; Latge, C.; Renault, C.; Rimpault, G.

2014-01-01

The supercritical water reactor (SCWR) is one of the 6 concepts selected for the 4. generation of nuclear reactors. SCWR is a new concept, it is an attempt to optimize boiling water reactors by using the main advantages of supercritical water: only liquid phase and a high calorific capacity. The SCWR requires very high temperatures (over 375 C degrees) and very high pressures (over 22.1 MPa) to operate which allows a high conversion yield (44% instead of 33% for a PWR). Low volumes of coolant are necessary which makes the neutron spectrum shift towards higher energies and it is then possible to consider fast reactors operating with supercritical water. The main drawbacks of supercritical water is the necessity to use very high pressures which has important constraints on the reactor design, its physical properties (density, calorific capacity) that vary strongly with temperatures and pressures and its very high corrosiveness. The feasibility of the concept is not yet assured in terms of adequate materials that resist to corrosion, reactor stability, reactor safety, and reactor behaviour in accidental situations. (A.C.)

Effect of nitrogen doping on wetting and photoactive properties of laser processed zinc oxide-graphene oxide nanocomposite layers

Energy Technology Data Exchange (ETDEWEB)

György, E., E-mail: egyorgy@icmab.es [Consejo Superior de Investigaciones Cientificas, Instituto de Ciencia de Materiales de Barcelona (CSIC-ICMAB), Campus UAB, 08193 Bellaterra (Spain); National Institute for Lasers, Plasma and Radiation Physics, P. O. Box MG 36, 76900 Bucharest V (Romania); Pérez del Pino, A. [Consejo Superior de Investigaciones Cientificas, Instituto de Ciencia de Materiales de Barcelona (CSIC-ICMAB), Campus UAB, 08193 Bellaterra (Spain); Logofatu, C. [National Institute for Materials Physics, P. O. Box MG. 7, 77125 Bucharest (Romania); Duta, A.; Isac, L. [Transilvania University of Brasov, Research Centre for Renewable Energy Systems and Recycling, Eroilor 29, 500036, Brasov (Romania)

2014-07-14

Zinc oxide-graphene oxide nanocomposite layers were submitted to laser irradiation in air or controlled nitrogen atmosphere using a frequency quadrupled Nd:YAG (λ = 266 nm, τ{sub FWHM} ≅ 3 ns, ν = 10 Hz) laser source. The experiments were performed in air at atmospheric pressure or in nitrogen at a pressure of 2 × 10{sup 4} Pa. The effect of the irradiation conditions, incident laser fluence value, and number of subsequent laser pulses on the surface morphology of the composite material was systematically investigated. The obtained results reveal that nitrogen incorporation improves significantly the wetting and photoactive properties of the laser processed layers. The kinetics of water contact angle variation when the samples are submitted to laser irradiation in nitrogen are faster than that of the samples irradiated in air, the surfaces becoming super-hydrophilic under UV light irradiation.

Exfoliation Propensity of Oxide Scale in Heat Exchangers Used for Supercritical CO2 Power Cycles

Energy Technology Data Exchange (ETDEWEB)

Sabau, Adrian S [ORNL; Shingledecker, John P. [Electric Power Research Institute (EPRI); Kung, Steve [Electric Power Research Institute (EPRI); Wright, Ian G. [WrightHT, Inc.; Nash, Jim [Brayton Energy, LLC, Hampton, NH

2016-01-01

Supercritical CO2 (sCO2) Brayton cycle systems offer the possibility of improved efficiency in future fossil energy power generation plants operating at temperatures of 650 C and above. As there are few data on the oxidation/corrosion behavior of structural alloys in sCO2 at these temperatures, modeling to predict the propensity for oxide exfoliation is not well developed, thus hindering materials selection for these novel cycles. The ultimate goal of this effort is to provide needed data on scale exfoliation behavior in sCO2 for confident alloy selection. To date, a model developed by ORNL and EPRI for the exfoliation of oxide scales formed on boiler tubes in high-temperature, high-pressure steam has proven useful for managing exfoliation in conventional steam plants. A major input provided by the model is the ability to predict the likelihood of scale failure and loss based on understanding of the evolution of the oxide morphologies and the conditions that result in susceptibility to exfoliation. This paper describes initial steps taken to extend the existing model for exfoliation of steam-side oxide scales to sCO2 conditions. The main differences between high-temperature, high-pressure steam and sCO2 that impact the model involve (i) significant geometrical differences in the heat exchangers, ranging from standard pressurized tubes seen typically in steam-producing boilers to designs for sCO2 that employ variously-curved thin walls to create shaped flow paths for extended heat transfer area and small channel cross-sections to promote thermal convection and support pressure loads; (ii) changed operating characteristics with sCO2 due to the differences in physical and thermal properties compared to steam; and (iii) possible modification of the scale morphologies, hence properties that influence exfoliation behavior, due to reaction with carbon species from sCO2. The numerical simulations conducted were based on an assumed sCO2 operating schedule and several

Characterization of oxide scales grown on alloy 310S stainless steel after long term exposure to supercritical water at 500 °C

Energy Technology Data Exchange (ETDEWEB)

Behnamian, Yashar, E-mail: behnamia@ualberta.ca [Department of Chemical and Materials Engineering, University of Alberta, Edmonton, Alberta T6G 1H9 (Canada); Mostafaei, Amir [Department of Mechanical Engineering and Materials Science, University of Pittsburgh, Pittsburgh, PA 15261 (United States); Kohandehghan, Alireza [Department of Chemical and Materials Engineering, University of Alberta, Edmonton, Alberta T6G 1H9 (Canada); Amirkhiz, Babak Shalchi [Canmet MATERIALS, Natural Resources Canada, Hamilton, Ontario L8P 0A5 (Canada); Serate, Daniel [Department of Chemical and Materials Engineering, University of Alberta, Edmonton, Alberta T6G 1H9 (Canada); Zheng, Wenyue [Canmet MATERIALS, Natural Resources Canada, Hamilton, Ontario L8P 0A5 (Canada); Guzonas, David [Canadian Nuclear Laboratories, Chalk River Laboratories, Chalk River, Ontario K0J 1J0 (Canada); Chmielus, Markus [Department of Mechanical Engineering and Materials Science, University of Pittsburgh, Pittsburgh, PA 15261 (United States); Chen, Weixing, E-mail: Weixing@ualberta.ca [Department of Chemical and Materials Engineering, University of Alberta, Edmonton, Alberta T6G 1H9 (Canada); Luo, Jing Li, E-mail: Jingli.luo@ualberta.ca [Department of Chemical and Materials Engineering, University of Alberta, Edmonton, Alberta T6G 1H9 (Canada)

2016-10-15

The oxide scale grown of static capsules made of alloy 310S stainless steel was investigated by exposure to the supercritical water at 500 °C 25 MPa for various exposure times up to 20,000 h. Characterization techniques such as X-ray diffraction, scanning/transmission electron microscopy, energy dispersive spectroscopy, and fast Fourier transformation were employed on the oxide scales. The elemental and phase analyses indicated that long term exposure to the SCW resulted in the formation of scales identified as Fe{sub 3}O{sub 4} (outer layer), Fe-Cr spinel (inner layer), Cr{sub 2}O{sub 3} (transition layer) on the substrate, and Ni-enrichment (chrome depleted region) in the alloy 310S. It was found that the layer thickness and weight gain vs. exposure time followed parabolic law. The oxidation mechanism and scales grown on the alloy 310S stainless steel exposed to SCW are discussed. - Highlights: •Oxidation of alloy 310S stainless steel exposed to SCW (500 °C/25 MPa) •The layer thickness and weight gain vs. exposure time followed parabolic law. •Oxide layers including Fe{sub 3}O{sub 4} (outer), Fe-Cr spinel (inner) and Cr{sub 2}O{sub 3} (transition) •Ni element is segregated by the selective oxidation of Cr.

Supercritical fluids processing: emerging opportunities

International Nuclear Information System (INIS)

Kovaly, K.A.

1985-01-01

This publication on the emerging opportunities of supercritical fluids processing reveals the latest research findings and development trends in this field. These findings and development trends are highlighted, and the results of applications of technology to the business of supercritical fluids are reported. Applications of supercritical fluids to chemical intermediates, environmental applications, chemical reactions, food and biochemistry processing, and fuels processing are discussed in some detail

Surface Modification of SiO2 Microchannels with Biocompatible Polymer Using Supercritical Carbon Dioxide

Science.gov (United States)

Saito, Tatsuro; Momose, Takeshi; Hoshi, Toru; Takai, Madoka; Ishihara, Kazuhiko; Shimogaki, Yukihiro

2010-11-01

The surface of 500-mm-long microchannels in SiO2 microchips was modified using supercritical CO2 (scCO2) and a biocompatible polymer was coated on it to confer biocompatibility to the SiO2 surface. In this method, the SiO2 surface of a microchannel was coated with poly(ethylene glycol monomethacrylate) (PEGMA) as the biocompatible polymer using allyltriethoxysilane (ATES) as the anchor material in scCO2 as the reactive medium. Results were compared with those using the conventional wet method. The surface of a microchannel could not be modified by the wet method owing to the surface tension and viscosity of the liquid, but it was modified uniformly by the scCO2 method probably owing to the near-zero surface tension, low viscosity, and high diffusivity of scCO2. The effect of the surface modification by the scCO2 method to prevent the adsorption of protein was as high as that of the modification by the wet method. Modified microchips can be used in biochemical and medical analyses.

Corrosion behavior of ceramic-coated ZIRLO™ exposed to supercritical water

Science.gov (United States)

Mandapaka, Kiran K.; Cahyadi, Rico S.; Yalisove, Steven; Kuang, Wenjun; Sickafus, K.; Patel, Maulik K.; Was, Gary S.

2018-01-01

The corrosion behavior of ceramic coated ZIRLO™ tubing was evaluated in a supercritical water (SCW) environment to determine its behavior in high temperature water. Two coating architectures were analyzed; a 4 bi-layer TiAlN/TiN coating with Ti bond coat, and a TiN monolithic coating with Ti bond layer on ZIRLO™ tubes using cathodic arc physical vapor deposition (CA-PVD) technique. Femtosecond laser ablation was used to introduce reproducible defects in some of the coated tubes. On exposure to deaerated supercritical water at 542 °C for 48 h, coated tubes exhibited significantly higher weight gain compared to uncoated ZIRLO™. Examination revealed formation of a uniform ZrO2 layer beneath the coating of a thickness similar to that on the uncoated tube inner surface. The defects generated during the coating process acted as preferential paths for diffusion of oxygen resulting in the oxidation of substrate ZIRLO™. However, there was no delamination of the coating. There were insignificant differences in the oxidation weight gain between laser ablated and non-ablated tubes and the laser induced defects did not spread beyond their original size.

Electrochemistry in supercritical fluids

Science.gov (United States)

Branch, Jack A.; Bartlett, Philip N.

2015-01-01

A wide range of supercritical fluids (SCFs) have been studied as solvents for electrochemistry with carbon dioxide and hydrofluorocarbons (HFCs) being the most extensively studied. Recent advances have shown that it is possible to get well-resolved voltammetry in SCFs by suitable choice of the conditions and the electrolyte. In this review, we discuss the voltammetry obtained in these systems, studies of the double-layer capacitance, work on the electrodeposition of metals into high aspect ratio nanopores and the use of metallocenes as redox probes and standards in both supercritical carbon dioxide–acetonitrile and supercritical HFCs. PMID:26574527

Control of Alq3 wetting layer thickness via substrate surface functionalization.

Science.gov (United States)

Tsoi, Shufen; Szeto, Bryan; Fleischauer, Michael D; Veinot, Jonathan G C; Brett, Michael J

2007-06-05

The effects of substrate surface energy and vapor deposition rate on the initial growth of porous columnar tris(8-hydroxyquinoline)aluminum (Alq3) nanostructures were investigated. Alq3 nanostructures thermally evaporated onto as-supplied Si substrates bearing an oxide were observed to form a solid wetting layer, likely caused by an interfacial energy mismatch between the substrate and Alq3. Wetting layer thickness control is important for potential optoelectronic applications. A dramatic decrease in wetting layer thickness was achieved by depositing Alq3 onto alkyltrichlorosilane-derivatized Si/oxide substrates. Similar effects were noted with increasing deposition rates. These two effects enable tailoring of the wetting layer thickness.

Surface chemistry and corrosion behavior of Inconel 625 and 718 in subcritical, supercritical, and ultrasupercritical water

Science.gov (United States)

Rodriguez, David; Merwin, Augustus; Karmiol, Zachary; Chidambaram, Dev

2017-05-01

Corrosion behavior of Inconel 625 and 718 in subcritical, supercritical and ultrasupercritical water was studied as a function of temperature and time. The change in the chemistry of the as-received surface film on Inconel 625 and 718 after exposure to subcritical water at 325 °C and supercritical water at 425 °C and 527.5 °C for 2 h was studied. After exposure to 325 °C subcritical water, the CrO42- based film formed; however minor quantities of NiFexCr2-xO4 spinel compounds were observed. The oxide film formed on both alloys when exposed to supercritical water at 425 °C consisted of NiFexCr2-xO4 spinel. The surface films on both alloys were identified as NiFe2O4 when exposed to supercritical water at 527.5 °C. To characterize the fully developed oxide layer, studies were conducted at test solution temperatures of 527.5 and 600 °C. Samples were exposed to these temperatures for 24, 96, and 200 h. Surface chemistry was analyzed using X-ray diffraction, as well as Raman and X-ray photoelectron spectroscopies. Inconel 718 exhibited greater mass gain than Inconel 625 for all temperatures and exposure times. The differences in corrosion behavior of the two alloys are attributed to the lower content of chromium and increased iron content of Inconel 718 as compared to Inconel 625.

LARGE-SCALE MECURY CONTROL TECHNOLOGY TESTING FOR LIGNITE-FIRED UTILITIES-OXIDATION SYSTEMS FOR WET FGD

Energy Technology Data Exchange (ETDEWEB)

Michael J. Holmes; Steven A. Benson; Jeffrey S. Thompson

2004-03-01

The Energy & Environmental Research Center (EERC) is conducting a consortium-based effort directed toward resolving the mercury (Hg) control issues facing the lignite industry. Specifically, the EERC team--the EERC, EPRI, URS, ADA-ES, Babcock & Wilcox, the North Dakota Industrial Commission, SaskPower, and the Mercury Task Force, which includes Basin Electric Power Cooperative, Otter Tail Power Company, Great River Energy, Texas Utilities (TXU), Montana-Dakota Utilities Co., Minnkota Power Cooperative, BNI Coal Ltd., Dakota Westmoreland Corporation, and the North American Coal Company--has undertaken a project to significantly and cost-effectively oxidize elemental mercury in lignite combustion gases, followed by capture in a wet scrubber. This approach will be applicable to virtually every lignite utility in the United States and Canada and potentially impact subbituminous utilities. The oxidation process is proven at the pilot-scale and in short-term full-scale tests. Additional optimization is continuing on oxidation technologies, and this project focuses on longer-term full-scale testing. The lignite industry has been proactive in advancing the understanding of and identifying control options for Hg in lignite combustion flue gases. Approximately 1 year ago, the EERC and EPRI began a series of Hg-related discussions with the Mercury Task Force as well as utilities firing Texas and Saskatchewan lignites. This project is one of three being undertaken by the consortium to perform large-scale Hg control technology testing to address the specific needs and challenges to be met in controlling Hg from lignite-fired power plants. This project involves Hg oxidation upstream of a system equipped with an electrostatic precipitator (ESP) followed by wet flue gas desulfurization (FGD). The team involved in conducting the technical aspects of the project includes the EERC, Babcock & Wilcox, URS, and ADA-ES. The host sites include Minnkota Power Cooperative Milton R. Young

Extraction of Lepidium apetalum Seed Oil Using Supercritical Carbon Dioxide and Anti-Oxidant Activity of the Extracted Oil

Directory of Open Access Journals (Sweden)

Xuchong Tang

2011-12-01

Full Text Available The supercritical fluid extraction (SFE of Lepidium apetalum seed oil and its anti-oxidant activity were studied. The SFE process was optimized using response surface methodology (RSM with a central composite design (CCD. Independent variables, namely operating pressure, temperature, time and flow rate were evaluated. The maximum extraction of Lepidium apetalum seed oil by SFE-CO2 (about 36.3% was obtained when SFE-CO2 extraction was carried out under the optimal conditions of 30.0 MPa of pressure, 70 °C of temperature, 120 min of extraction time and 25.95 L/h of flow rate. GC-MS analysis showed the presence of four fatty acids in Lepidium apetalum seed oil, with a high content (91.0% of unsaturated fatty acid. The anti-oxidant activity of the oil was assessed by the 2,2-diphenyl-1-picrylhydrazyl (DPPH radical-scavenging assay and 2,2′-azino- bis(3-ethylbenzthiazoline-6-sulphonic acid diammonium salt (ABTS test. Lepidium apetalum seed oil possessed a notable concentration-dependent antioxidant activity, with IC50 values of 1.00 and 3.75 mg/mL, respectively.

Ceramic joining through reactive wetting of alumina with calcium ...

Indian Academy of Sciences (India)

phase analysis of the fractured joint surface clearly indicate reactive wetting of the alumina ceramics. This wetting enhances ... ally considered oxide materials for many applications. .... three cases but is more pronounced in the case of C12A7.

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...... of cellulose to glucose was 82.4%. Simultaneous saccharification and fermentation of pretreated solids resulted in a final ethanol concentration as high as 8.7 g/L, yielding 73% of the theoretical....

Long term steam oxidation of TP 347H FG in power plants

DEFF Research Database (Denmark)

Hansson, Anette Nørgaard; Korcakova, Leona; Hald, John

2005-01-01

The long term oxidation behaviour of TP 347H FG at ultra supercritical steam conditions was assessed by exposing the steel in test superheater loops in a Danish coal-fired power plant. The steamside oxide layer was investigated with scanning electron microscopy and energy dispersive Xray diffract......The long term oxidation behaviour of TP 347H FG at ultra supercritical steam conditions was assessed by exposing the steel in test superheater loops in a Danish coal-fired power plant. The steamside oxide layer was investigated with scanning electron microscopy and energy dispersive Xray...

Wetting of water on graphene nanopowders of different thicknesses

Science.gov (United States)

Bera, Bijoyendra; Shahidzadeh, Noushine; Mishra, Himanshu; Belyaeva, Liubov A.; Schneider, Grégory F.; Bonn, Daniel

2018-04-01

We study the wetting of graphene nanopowders by measuring the water adsorption in nanopowder flakes of different flake thicknesses. Chemical analysis shows that the graphene flakes, especially the thin ones, might exist in the partially oxidized state. We observe that the thinnest graphene nanopowder flakes do not adsorb water at all, independent of the relative humidity. Thicker flakes, on the other hand, do adsorb an increasing amount of water with increasing humidity. This allows us to assess their wetting behavior which is actually the result of the competition between the adhesive interactions of water and graphene and the cohesive interactions of water. Explicit calculation of these contributions from the van der Waals interactions confirms that the adhesive interactions between very thin flakes of graphene oxide and water are extremely weak, which makes the flakes superhydrophobic. "Liquid marble" tests with graphene nanopowder flakes confirm the superhydrophobicity. This shows that the origin of the much debated "wetting transparency" of graphene is due to the fact that a single graphene or graphene oxide layer does not contribute significantly to the adhesion between a wetting phase and the substrate.

Wetting of water on graphene nanopowders of different thicknesses

KAUST Repository

Bera, Bijoyendra; Shahidzadeh, Noushine; Mishra, Himanshu; Belyaeva, Liubov A.; Schneider, Gré gory F.; Bonn, Daniel

2018-01-01

We study the wetting of graphene nanopowders by measuring the water adsorption in nanopowder flakes of different flake thicknesses. Chemical analysis shows that the graphene flakes, especially the thin ones, might exist in the partially oxidized state. We observe that the thinnest graphene nanopowder flakes do not adsorb water at all, independent of the relative humidity. Thicker flakes, on the other hand, do adsorb an increasing amount of water with increasing humidity. This allows us to assess their wetting behavior which is actually the result of the competition between the adhesive interactions of water and graphene and the cohesive interactions of water. Explicit calculation of these contributions from the van der Waals interactions confirms that the adhesive interactions between very thin flakes of graphene oxide and water are extremely weak, which makes the flakes superhydrophobic. “Liquid marble” tests with graphene nanopowder flakes confirm the superhydrophobicity. This shows that the origin of the much debated “wetting transparency” of graphene is due to the fact that a single graphene or graphene oxide layer does not contribute significantly to the adhesion between a wetting phase and the substrate.

Wetting of water on graphene nanopowders of different thicknesses

KAUST Repository

Bera, Bijoyendra

2018-04-12

We study the wetting of graphene nanopowders by measuring the water adsorption in nanopowder flakes of different flake thicknesses. Chemical analysis shows that the graphene flakes, especially the thin ones, might exist in the partially oxidized state. We observe that the thinnest graphene nanopowder flakes do not adsorb water at all, independent of the relative humidity. Thicker flakes, on the other hand, do adsorb an increasing amount of water with increasing humidity. This allows us to assess their wetting behavior which is actually the result of the competition between the adhesive interactions of water and graphene and the cohesive interactions of water. Explicit calculation of these contributions from the van der Waals interactions confirms that the adhesive interactions between very thin flakes of graphene oxide and water are extremely weak, which makes the flakes superhydrophobic. “Liquid marble” tests with graphene nanopowder flakes confirm the superhydrophobicity. This shows that the origin of the much debated “wetting transparency” of graphene is due to the fact that a single graphene or graphene oxide layer does not contribute significantly to the adhesion between a wetting phase and the substrate.

Reactivity of dolomite in water-saturated supercritical carbon dioxide: Significance for carbon capture and storage and for enhanced oil and gas recovery

International Nuclear Information System (INIS)

Wang Xiuyu; Alvarado, Vladimir; Swoboda-Colberg, Norbert; Kaszuba, John P.

2013-01-01

Highlights: ► Dolomite reactivity with wet and dry supercritical CO 2 were evaluated. ► Dolomite does not react with dry CO 2 . ► H 2 O-saturated supercritical CO 2 dissolves dolomite and precipitates carbonate mineral. ► Temperature/reaction time control morphology and extent of carbonate mineralization. ► Reaction with wet CO 2 may impact trapping, caprock integrity, and CCS/EOR injectivity. - Abstract: Carbon dioxide injection in porous reservoirs is the basis for carbon capture and storage, enhanced oil and gas recovery. Injected carbon dioxide is stored at multiple scales in porous media, from the pore-level as a residual phase to large scales as macroscopic accumulations by the injection site, under the caprock and at reservoir internal capillary pressure barriers. These carbon dioxide saturation zones create regions across which the full spectrum of mutual CO 2 –H 2 O solubility may occur. Most studies assume that geochemical reaction is restricted to rocks and carbon dioxide-saturated formation waters, but this paradigm ignores injection of anhydrous carbon dioxide against brine and water-alternating-gas flooding for enhanced oil recovery. A series of laboratory experiments was performed to evaluate the reactivity of the common reservoir mineral dolomite with water-saturated supercritical carbon dioxide. Experiments were conducted at reservoir conditions (55 and 110 °C, 25 MPa) and elevated temperature (220 °C, 25 MPa) for approximately 96 and 164 h (4 and 7 days). Dolomite dissolves and new carbonate mineral precipitates by reaction with water-saturated supercritical carbon dioxide. Dolomite does not react with anhydrous supercritical carbon dioxide. Temperature and reaction time control the composition, morphology, and extent of formation of new carbonate minerals. Mineral dissolution and re-precipitation due to reaction with water-saturated carbon dioxide may affect the contact line between phases, the carbon dioxide contact angle, and the

Advanced Thermal Storage for Central Receivers with Supercritical Coolants

Energy Technology Data Exchange (ETDEWEB)

Kelly, Bruce D.

2010-06-15

The principal objective of the study is to determine if supercritical heat transport fluids in a central receiver power plant, in combination with ceramic thermocline storage systems, offer a reduction in levelized energy cost over a baseline nitrate salt concept. The baseline concept uses a nitrate salt receiver, two-tank (hot and cold) nitrate salt thermal storage, and a subcritical Rankine cycle. A total of 6 plant designs were analyzed, as follows: Plant Designation Receiver Fluid Thermal Storage Rankine Cycle Subcritical nitrate salt Nitrate salt Two tank nitrate salt Subcritical Supercritical nitrate salt Nitrate salt Two tank nitrate salt Supercritical Low temperature H2O Supercritical H2O Two tank nitrate salt Supercritical High temperature H2O Supercritical H2O Packed bed thermocline Supercritical Low temperature CO2 Supercritical CO2 Two tank nitrate salt Supercritical High temperature CO2 Supercritical CO2 Packed bed thermocline Supercritical Several conclusions have been drawn from the results of the study, as follows: 1) The use of supercritical H2O as the heat transport fluid in a packed bed thermocline is likely not a practical approach. The specific heat of the fluid is a strong function of the temperatures at values near 400 °C, and the temperature profile in the bed during a charging cycle is markedly different than the profile during a discharging cycle. 2) The use of supercritical CO2 as the heat transport fluid in a packed bed thermocline is judged to be technically feasible. Nonetheless, the high operating pressures for the supercritical fluid require the use of pressure vessels to contain the storage inventory. The unit cost of the two-tank nitrate salt system is approximately $24/kWht, while the unit cost of the high pressure thermocline system is nominally 10 times as high. 3) For the supercritical fluids, the outer crown temperatures of the receiver tubes are in the range of 700 to 800 °C. At temperatures of 700 °C and above

Technology with Supercritical Fluid. Part 2. Applications

International Nuclear Information System (INIS)

Marongiu, B.; De Giorgi, M. R.; Porcedda, S.; Cadoni, E.

1998-01-01

The present article is based on a bibliographical analysis of the main applications of the supercritical fluid in various fields, as: extraction from solid matrices, division of liquid charges, chromatography HPLC with supercritical eluent, chemical and biochemical reactions in supercritical solvents etc [it

Supercritical transitiometry of polymers.

Science.gov (United States)

Randzio, S L; Grolier, J P

1998-06-01

Employing supercritical fluids (SCFs) during polymers processing allows the unusual properties of SCFs to be exploited for making polymer products that cannot be obtained by other means. A new supercritical transitiometer has been constructed to permit study of the interactions of SCFs with polymers during processing under well-defined conditions of temperature and pressure. The supercritical transitiometer allows pressure to be exerted by either a supercritical fluid or a neutral medium and enables simultaneous determination of four basic parameters of a transition, i.e., p, T, Δ(tr)H and Δ(tr)V. This permits determination of the SCF effect on modification of the polymer structure at a given pressure and temperature and defines conditions to allow reproducible preparation of new polymer structures. Study of a semicrystalline polyethylene by this method has defined conditions for preparation of new microfoamed phases with good mechanical properties. The low densities and microporous structures of the new materials may make them useful for applications in medicine, pharmacy, or the food industry, for example.

Supercritical fluid technologies for ceramic-processing applications

International Nuclear Information System (INIS)

Matson, D.W.; Smith, R.D.

1989-01-01

This paper reports on the applications of supercritical fluid technologies for ceramic processing. The physical and chemical properties of these densified gases are summarized and related to their use as solvents and processing media. Several areas are identified in which specific ceramic processes benefit from the unique properties of supercritical fluids. The rapid expansion of supercritical fluid solutions provides a technique for producing fine uniform powders and thin films of widely varying materials. Supercritical drying technologies allow the formation of highly porous aerogel products with potentially wide application. Hydrothermal processes leading to the formation of large single crystals and microcrystalline powders can also be extended into the supercritical regime of water. Additional applications and potential applications are identified in the areas of extraction of binders and other additives from ceramic compacts, densification of porous ceramics, the formation of powders in supercritical micro-emulsions, and in preceramic polymer processing

Long term wet spent nuclear fuel storage

International Nuclear Information System (INIS)

1987-04-01

The meeting showed that there is continuing confidence in the use of wet storage for spent nuclear fuel and that long-term wet storage of fuel clad in zirconium alloys can be readily achieved. The importance of maintaining good water chemistry has been identified. The long-term wet storage behaviour of sensitized stainless steel clad fuel involves, as yet, some uncertainties. However, great reliance will be placed on long-term wet storage of spent fuel into the future. The following topics were treated to some extent: Oxidation of the external surface of fuel clad, rod consolidation, radiation protection, optimum methods of treating spent fuel storage water, physical radiation effects, and the behaviour of spent fuel assemblies of long-term wet storage conditions. A number of papers on national experience are included

Pressure drop and friction factor correlations of supercritical flow

International Nuclear Information System (INIS)

Fang Xiande; Xu Yu; Su Xianghui; Shi Rongrong

2012-01-01

Highlights: ► Survey and evaluation of friction factor models for supercritical flow. ► Survey of experimental study of supercritical flow. ► New correlation of friction factor for supercritical flow. - Abstract: The determination of the in-tube friction pressure drop under supercritical conditions is important to the design, analysis and simulation of transcritical cycles of air conditioning and heat pump systems, nuclear reactor cooling systems and some other systems. A number of correlations for supercritical friction factors have been proposed. Their accuracy and applicability should be examined. This paper provides a comprehensive survey of experimental investigations into the pressure drop of supercritical flow in the past decade and a comparative study of supercritical friction factor correlations. Our analysis shows that none of the existing correlations is completely satisfactory, that there are contradictions between the existing experimental results and thus more elaborate experiments are needed, and that the tube roughness should be considered. A new friction factor correlation for supercritical tube flow is proposed based on 390 experimental data from the available literature, including 263 data of supercritical R410A cooling, 45 data of supercritical R404A cooling, 64 data of supercritical carbon dioxide (CO 2 ) cooling and 18 data of supercritical R22 heating. Compared with the best existing model, the new correlation increases the accuracy by more than 10%.

Systems design of direct-cycle supercritical-water-cooled fast reactors

International Nuclear Information System (INIS)

Oka, Yoshiaki; Koshizuka, Seiichi; Jevremovic, Tatjana; Okano, Yashushi

1995-01-01

The system design of a direct-cycle supercritical-water-cooled fast reactor is presented. The supercritical water does not exhibit a change of phase. the recirculation system, steam separator, and dryer of a boiling water reactor (BWR) are unnecessary. Roughly speaking, the reactor pressure vessel and control rods are similar to those of a pressurized water reactor, the containment and emergency core cooling system are similar to a BWR, and the balance of plant is similar to a supercritical-pressure fossil-fired power plant (FPP). the electric power of the fast converter is 1,508 MW(electric). The number of coolant loops is only two because of the high coolant enthalpy. Containment volume is much reduced. The thermal efficiency is improved 24% over a BWR. The coolant void reactivity is negative by placing thin zirconium-hydride layers between seeds and blankets. The power costs would be much reduced compared with those of a light water reactor (LWR) and a liquid-metal fast breeder reactor. The concept is based on the huge amount of experience with the water coolant technology of LWRs and FPPs. The oxidation of stainless steel cladding is avoided by adopting a much lower coolant temperature than that of the FPP

Degradation Characteristics of Wood Using Supercritical Alcohols

Directory of Open Access Journals (Sweden)

Jeeban Poudel

2012-11-01

Full Text Available In this work, the characteristics of wood degradation using supercritical alcohols have been studied. Supercritical ethanol and supercritical methanol were used as solvents. The kinetics of wood degradation were analyzed using the nonisothermal weight loss technique with heating rates of 3.1, 9.8, and 14.5 °C/min for ethanol and 5.2, 11.3, and 16.3 °C/min for methanol. Three different kinetic analysis methods were implemented to obtain the apparent activation energy and the overall reaction order for wood degradation using supercritical alcohols. These were used to compare with previous data for supercritical methanol. From this work, the activation energies of wood degradation in supercritical ethanol were obtained as 78.0–86.0, 40.1–48.1, and 114 kJ/mol for the different kinetic analysis methods used in this work. The activation energies of wood degradation in supercritical ethanol were obtained as 78.0–86.0, 40.1–48.1, and 114 kJ/mol. This paper also includes the analysis of the liquid products obtained from this work. The characteristic analysis of liquid products on increasing reaction temperature and time has been performed by GC-MS. The liquid products were categorized according to carbon numbers and aromatic/aliphatic components. It was found that higher conversion in supercritical ethanol occurs at a lower temperature than that of supercritical methanol. The product analysis shows that the majority of products fall in the 2 to 15 carbon number range.

Activated carbon as catalyst for microwave-assisted wet peroxide oxidation of aromatic hydrocarbons.

Science.gov (United States)

Garcia-Costa, Alicia L; Lopez-Perela, Lucia; Xu, Xiyan; Zazo, Juan A; Rodriguez, Juan J; Casas, Jose A

2018-05-21

This paper addresses the removal of four aromatic hydrocarbons typically found in petrochemical wastewater: benzene (B), toluene (T), o-xylene (X), and naphthalene (N), by microwave-assisted catalytic wet peroxide oxidation (MW-CWPO) using activated carbon (AC) as catalyst. Under the studied conditions, complete pollutant elimination (B, 1.28 mM; T, 1.09 mM; X, 0.94 mM; and N, 0.78 mM) was achieved, with more than 90% TOC removal after only 15-min reaction time, working at 120 °C, pH 0  = 3, AC at 1 g L -1 , and H 2 O 2 at the stoichiometric dose. Furthermore, in the case of toluene, naphthalene, and xylene, the hydroxylation and breakdown of the ring is very rapid and toxic intermediates were not detected. The process follows two steps: (i) pollutant adsorption onto AC followed by (ii) adsorbed compounds oxidation. Thus, MW-CWPO with AC as catalyst appears a promising way for a fast and effective process for B, T, X, and N removal in aqueous phase.

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.

Capabilities and Limitations of an Association Theory for Chemicals in Liquid or Supercritical Solvents

DEFF Research Database (Denmark)

Tsivintzelis, Ioannis; Kontogeorgis, Georgios

2012-01-01

. The capabilities of the model are illustrated in the first two case studies: the phase behavior of mixtures used in the oxidation of 2-octanol in supercritical CO2 and the investigation of systems containing acetone, methanol, water, chloroform, and methyl acetate. In each case, both correlations of vapor...

Supercritical fluids in ionic liquids

NARCIS (Netherlands)

Kroon, M.C.; Peters, C.J.; Plechkova, N.V.; Seddon, K.R.

2014-01-01

Ionic liquids and supercritical fluids are both alternative environmentally benign solvents, but their properties are very different. Ionic liquids are non-volatile but often considered highly polar compounds, whereas supercritical fluids are non-polar but highly volatile compounds. The combination

PULSE RADIOLYSIS IN SUPERCRITICAL RARE GAS FLUIDS

International Nuclear Information System (INIS)

HOLROYD, R.

2007-01-01

Recently, supercritical fluids have become quite popular in chemical and semiconductor industries for applications in chemical synthesis, extraction, separation processes, and surface cleaning. These applications are based on: the high dissolving power due to density build-up around solute molecules, and the ability to tune the conditions of a supercritical fluid, such as density and temperature, that are most suitable for a particular reaction. The rare gases also possess these properties and have the added advantage of being supercritical at room temperature. Information about the density buildup around both charged and neutral species can be obtained from fundamental studies of volume changes in the reactions of charged species in supercritical fluids. Volume changes are much larger in supercritical fluids than in ordinary solvents because of their higher compressibility. Hopefully basic studies, such as discussed here, of the behavior of charged species in supercritical gases will provide information useful for the utilization of these solvents in industrial applications

Supercritical fluid chromatography

Science.gov (United States)

Vigdergauz, M. S.; Lobachev, A. L.; Lobacheva, I. V.; Platonov, I. A.

1992-03-01

The characteristic features of supercritical fluid chromatography (SCFC) are examined and there is a brief historical note concerning the development of the method. Information concerning the use of supercritical fluid chromatography in the analysis of objects of different nature is presented in the form of a table. The roles of the mobile and stationary phases in the separation process and the characteristic features of the apparatus and of the use of the method in physicochemical research are discussed. The bibliography includes 364 references.

Correlation of supercritical-fluid extraction recoveries with supercritical-fluid chromatographic retention data: A fundamental study

NARCIS (Netherlands)

Lou, X.W.; Janssen, J.G.M.; Cramers, C.A.M.G.

1995-01-01

The possibility of using supercritical-fluid chromatographic retention data for examining the effects of operational parameters, such as pressure and flow rate, on the extraction characteristics in supercritical-fluid extraction (SFE) was investigated. A model was derived for calculating the

Proteomic effects of wet cupping (Al-hijamah).

Science.gov (United States)

Almaiman, Amer A

2018-01-01

Wet cupping (Al-hijamah) is a therapeutic technique practiced worldwide as a part of the Unani system of medicine. It involves bloodletting from acupoints on a patient's skin to produce a therapeutic outcome. A thorough review of research articles on wet cupping with relevance to proteomics field that are indexed by Google Scholar, PubMed, and/or Science Direct databases was performed. Eight original research articles were summarized in this paper. Overall, wet cupping did not have a significant effect on C-reactive protein, Hsp-27, sister chromatid exchanges, and cell replication index. In contrast, wet cupping was found to produce higher oxygen saturation, eliminate lactate from subcutaneous tissues, remove blood containing higher levels of malondialdehyde and nitric oxide, and produce higher activity of myeloperoxidase. The proteomic effects of wet cupping therapy have not been adequately investigated. Thus, future studies on wet cupping that use systemic and sound protocols to avoid bias should be conducted.

Proteomic effects of wet cupping (Al-hijamah

Directory of Open Access Journals (Sweden)

Amer A. Almaiman

2018-01-01

Full Text Available Wet cupping (Al-hijamah is a therapeutic technique practiced worldwide as a part of the Unani system of medicine. It involves bloodletting from acupoints on a patient’s skin to produce a therapeutic outcome. A thorough review of research articles on wet cupping with relevance to proteomics field that are indexed by Google Scholar, PubMed, and/or Science Direct databases was performed. Eight original research articles were summarized in this paper. Overall, wet cupping did not have a significant effect on C-reactive protein, Hsp-27, sister chromatid exchanges, and cell replication index. In contrast, wet cupping was found to produce higher oxygen saturation, eliminate lactate from subcutaneous tissues, remove blood containing higher levels of malondialdehyde and nitric oxide, and produce higher activity of myeloperoxidase. The proteomic effects of wet cupping therapy have not been adequately investigated. Thus, future studies on wet cupping that use systemic and sound protocols to avoid bias should be conducted.

Supercritical CO 2 -philic nanoparticles suitable for determining the viability of carbon sequestration in shale

KAUST Repository

Xu, Yisheng

2015-01-01

© The Royal Society of Chemistry. A fracture spacing less than a decimeter is probably required for the successful sequestration of CO2 in shale. Tracer experiments using inert nanoparticles could determine if a fracturing this intense has been achieved. Here we describe the synthesis of supercritical CO2-philic nanoparticles suitable for this application. The nanoparticles are ~50 nm in diameter and consist of iron oxide (Fe3O4) and silica (SiO2) cores functionalized with a fluorescent polymeric corona. The nanoparticles stably disperse in supercritical carbon dioxide (scCO2) and are detectable to concentrations of 10 ppm. This journal is

Wetting properties of liquid lithium on lithium compounds

Energy Technology Data Exchange (ETDEWEB)

Krat, S.A., E-mail: stepan.krat@gmail.com [Center for Plasma Material Interactions, Department of Nuclear, Plasma, and Radiological Engineering, University Illinois at Urbana-Champaign, Urbana (United States); National Research Nuclear University MEPhI, Moscow (Russian Federation); Popkov, A.S. [Center for Plasma Material Interactions, Department of Nuclear, Plasma, and Radiological Engineering, University Illinois at Urbana-Champaign, Urbana (United States); National Research Nuclear University MEPhI, Moscow (Russian Federation); Gasparyan, Yu. M.; Pisarev, A.A. [National Research Nuclear University MEPhI, Moscow (Russian Federation); Fiflis, Peter; Szott, Matthew; Christenson, Michael; Kalathiparambil, Kishor; Ruzic, David N. [Center for Plasma Material Interactions, Department of Nuclear, Plasma, and Radiological Engineering, University Illinois at Urbana-Champaign, Urbana (United States)

2017-04-15

Highlights: • Contact angles of liquid lithium and Li{sub 3}N, Li{sub 2}O, Li{sub 2}CO{sub 3} were measured. • Liquid lithium wets lithium compounds at relatively low temperatures: Li{sub 3}N at 257 °C, Li{sub 2}O at 259 °C, Li{sub 2}CO{sub 3} at 323 °C. • Li wets Li{sub 2}O and Li{sub 3}N better than previously measured fusion-relevant materials (W, Mo, Ta, TZM, stainless steel). • Li wets Li{sub 2}CO{sub 3} better than most previously measured fusion-relevant materials (W, Mo, Ta). - Abstract: Liquid metal plasma facing components (LMPFC) have shown a potential to supplant solid plasma facing components materials in the high heat flux regions of magnetic confinement fusion reactors due to the reduction or elimination of concerns over melting, wall damage, and erosion. To design a workable LMPFC, one must understand how liquid metal interacts with solid underlying structures. Wetting is an important factor in such interaction, several designs of LMPFC require liquid metal to wet the underlying solid structures. The wetting of lithium compounds (lithium nitride, oxide, and carbonate) by 200 °C liquid lithium at various surface temperature from 230 to 330 °C was studied by means of contact angle measurements. Wetting temperatures, defined as the temperature above which the contact angle is less than 90°, were measured. The wetting temperature was 257 °C for nitride, 259 °C for oxide, and 323 °C for carbonate. Surface tensions of solid lithium compounds were calculated from the contact angle measurements.

Wet-Chemical Preparation of Silicon Tunnel Oxides for Transparent Passivated Contacts in Crystalline Silicon Solar Cells.

Science.gov (United States)

Köhler, Malte; Pomaska, Manuel; Lentz, Florian; Finger, Friedhelm; Rau, Uwe; Ding, Kaining

2018-05-02

Transparent passivated contacts (TPCs) using a wide band gap microcrystalline silicon carbide (μc-SiC:H(n)), silicon tunnel oxide (SiO 2 ) stack are an alternative to amorphous silicon-based contacts for the front side of silicon heterojunction solar cells. In a systematic study of the μc-SiC:H(n)/SiO 2 /c-Si contact, we investigated selected wet-chemical oxidation methods for the formation of ultrathin SiO 2 , in order to passivate the silicon surface while ensuring a low contact resistivity. By tuning the SiO 2 properties, implied open-circuit voltages of 714 mV and contact resistivities of 32 mΩ cm 2 were achieved using μc-SiC:H(n)/SiO 2 /c-Si as transparent passivated contacts.

The emission of nitrous oxide upon wetting a rice soil following a dry season fallow

Science.gov (United States)

Byrnes, B. H.; Holt, L. S.; Austin, E. R.

1993-12-01

A greenhouse experiment was conducted to measure nitrous oxide (N2O) emissions from a soil, which had been planted to flooded transplanted rice, as it was rewetted to simulate the end of a dry season fallow period. The pots of soil had been cropped to transplanted rice with two commonly used nitrogen (N) fertilizer treatments and a control, and the soil had been puddled before transplanting. Large amounts of nitrate N accumulated in the soils during the dry season fallow, and the N fertilizers applied to the previous crop had little effect on nitrate accumulation. There was little N2O emission during the nitrification period. With water additions meant to simulate rainfall events at the beginning of a wet season, the soil redox dropped slightly, and large amounts of N2O began to be emitted. Large emissions began 5 days after each of the two simulated rainy season watering events and stopped abruptly at soil saturation, even though considerable amounts of nitrate still remained in the soil after saturation. Total measured emissions amounted to 6 to 7 kg N2O-N ha-1 for the period. Although these measurements were made in a system which may have favored nitrate accumulation, they are the first known measurements of N2O made from a rice soil as it is wetted. Nitrous oxide emitted from the flooding of rice soils that have accumulated nitrate during a dry season fallow may be a major source of N2O additions to the atmosphere.

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

DEFF Research Database (Denmark)

Oleskowicz-Popiel, Piotr; Lisiecki, P.; Holm-Nielsen, J.B.

2008-01-01

was investigated using 2 1 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. (C) 2007...

Drying of supercritical carbon dioxide with membrane processes

NARCIS (Netherlands)

Lohaus, Theresa; Scholz, Marco; Koziara, Beata; Benes, Nieck Edwin; Wessling, Matthias

2015-01-01

In supercritical extraction processes regenerating the supercritical fluid represents the main cost constraint. Membrane technology has potential for cost efficient regeneration of water-loaded supercritical carbon dioxide. In this study we have designed membrane-based processes to dehydrate

Supercritical water natural circulation flow stability experiment research

Energy Technology Data Exchange (ETDEWEB)

Ma, Dongliang; Zhou, Tao; Li, Bing [North China Electric Power Univ., Beijing (China). School of Nuclear Science and Engineering; North China Electric Power Univ., Beijing (China). Inst. of Nuclear Thermalhydraulic Safety and Standardization; North China Electric Power Univ., Beijing (China). Beijing Key Lab. of Passive Safety Technology for Nuclear Energy; Huang, Yanping [Nuclear Power Institute of China, Chengdu (China). Science and Technology on Reactor System Design Technology Lab.

2017-12-15

The Thermal hydraulic characteristics of supercritical water natural circulation plays an important role in the safety of the Generation-IV supercritical water-cooled reactors. Hence it is crucial to conduct the natural circulation heat transfer experiment of supercritical water. The heat transfer characteristics have been studied under different system pressures in the natural circulation systems. Results show that the fluctuations in the subcritical flow rate (for natural circulation) is relatively small, as compared to the supercritical flow rate. By increasing the heating power, it is observed that the amplitude (and time period) of the fluctuation tends to become larger for the natural circulation of supercritical water. This tends to show the presence of flow instability in the supercritical water. It is possible to observe the flow instability phenomenon when the system pressure is suddenly reduced from the supercritical pressure state to the subcritical state. At the test outlet section, the temperature is prone to increase suddenly, whereas the blocking effect may be observed in the inlet section of the experiment.

Electrical and physical characterizations of the effects of oxynitridation and wet oxidation at the interface of SiO2/4H-SiC(0001) and (000\\bar{1})

Science.gov (United States)

Shiomi, Hiromu; Kitai, Hidenori; Tsujimura, Masatoshi; Kiuchi, Yuji; Nakata, Daisuke; Ono, Shuichi; Kojima, Kazutoshi; Fukuda, Kenji; Sakamoto, Kunihiro; Yamasaki, Kimiyohi; Okumura, Hajime

2016-04-01

The effects of oxynitridation and wet oxidation at the interface of SiO2/4H-SiC(0001) and (000\\bar{1}) were investigated using both electrical and physical characterization methods. Hall measurements and split capacitance-voltage (C-V) measurements revealed that the difference in field-effect mobility between wet oxide and dry oxynitride interfaces was mainly attributed to the ratio of the mobile electron density to the total induced electron density. The surface states close to the conduction band edge causing a significant trapping of inversion carriers were also evaluated. High-resolution Rutherford backscattering spectroscopy (HR-RBS) analysis and high-resolution elastic recoil detection analysis (HR-ERDA) were employed to show the nanometer-scale compositional profile of the SiC-MOS interfaces for the first time. These analyses, together with cathode luminescence (CL) spectroscopy and transmission electron microscopy (TEM), suggested that the deviations of stoichiometry and roughness at the interface defined the effects of oxynitridation and wet oxidation at the interface of SiO2/4H-SiC(0001) and (000\\bar{1}).

Antioxidant effects of supercritical fluid garlic extracts in canned artichokes.

Science.gov (United States)

Bravi, E; Marconi, O; Sileoni, V; Rollo, M R; Perretti, G

2016-10-01

The effects of adding supercritical carbon dioxide extracts of garlic (at two different concentrations of allicin) on select chemical indices in extra-virgin olive oil used to canned artichokes were studied. Tests were performed after processing and over a storage period of 1 year. A sensorial test was also conducted on the canned artichokes to establish the impact on flavor (in particular perceptions of rancidity and garlic flavor). Acidity, peroxide levels and p -anisidine values were measured as quality analytical parameters. Radical scavenging activity was also evaluated using the DPPH assay. The samples containing supercritical garlic extracts were compared with several other formulations, including control sample (prepared by mixing artichokes with powdered chili pepper and fresh garlic), artichokes with only garlic or only chili pepper, and artichokes treated with the synthetic antioxidant BHT. The results suggested that the allicin extract may be superior, or at least comparable, with BHT in preserving canned artichokes as demonstrated by its positive effects on oxidative stability and sensory profile.

Fiscal 1997 report on the results of the introductory R and D of the New Sunshine Project under a consignment from NEDO. Introductory R and D of the supercritical fluid use technology; 1997 nendo `New Sunshine keikaku` sendo kenkyu kaihatsu Shin Energy Sangyo Gijutsu Sogo Kaihatsu Kiko itaku. Chorinkai ryutai riyo gijutsu sendo kenkyu kaihatsu seika hokokusho

Energy Technology Data Exchange (ETDEWEB)

NONE

1998-03-01

The R and D of chemical reaction using supercritical fluids started in fiscal 1997. In the R and D of solvent reaction, as the research on polymer decomposition with supercritical water, studies were conducted of the mechanism of conversion reaction to chemical materials, cleavage mechanism of stable chemical bonds, and synthetic reaction in the supercritical state reaction field. In the research on oxidation reaction, as the study of complete oxidation in supercritical water for high efficiency energy recovery, studies of complete oxidation of liquid fuels, and complete oxidation of solid fuels. In the research on hydrogenation, studies of lightening of heavy oil in supercritical water, etc. In the R and D of the basic technology, studies of corrosion mechanism of metals in supercritical water, construction of the basic framework for technical database of supercritical fluids, etc. In the survey of technical trends and new research themes, the introductory R and D of element technology, etc. were conducted, and the results were described of the survey of technical trends and new research themes and the trend survey of overseas technology. 314 refs., 87 figs., 81 tabs.

Processing of high level waste: Spectroscopic characterization of redox reactions in supercritical water. 1998 annual progress report

International Nuclear Information System (INIS)

Arrington, C.A. Jr.

1998-01-01

'The author is engaged in a collaborative research effort with Los Alamos staff scientists Steven Buelow, Jeanne Robinson, and Bernie Foy all staff members in group CST-6. The work proposed by these LANL staff scientists is directed towards the destruction of complexants and oxidation of chromium and technetium by hydrothermal processing in near critical or supercritical aqueous solutions. The work addresses two areas of investigation related to ongoing efforts at LANL: (1) kinetic studies of oxidation-reduction reactions in supercritical water; (2) measurement of physical properties of ionic solutes in supercritical water. All of the work during this first year was carried out at Los Alamos National Lab. During the Summer program at LANL all equipment and supplies were provided through Dr. Buelow''s program at LANL. The author has now set up a Raman spectroscopy lab at Furman. Using departmental funds he purchased an optical bench, a laser, and a CCD detector, and a grant from the Dreyfus Foundation assisted in the purchase of a Raman spectrometer. He is now able to carry out experiments using the Raman system at Furman. The plan is to continue the Summer collaboration at LANL and carry out experiments at Furman during the academic year.'

高级氧化技术处理造纸废水的应用研究%Application of Advanced Oxidation Processes in Papermaking Wastewater Treatment

Institute of Scientific and Technical Information of China (English)

杨德敏; 王兵

2011-01-01

The advanced oxidation processes has attracted more and more extensive attention due to its higher ability to remove the refractory organic materials in wastewater. The mechanism and the application development in papermaking wastewater treatment of the advanced oxidation processes, such as Fenton reagent oxidation, supercritical water oxidation, photocatalytic oxidation, ultrasonic oxidation, electrocatalytic oxidation, ozone oxidization and wet oxidation, are summarized. The characteristic and existing problems as well as the developing tendency of different advanced oxidation processes are analyzed.%介绍了Fenton类氧化法、超临界水氧化法、光催化氧化法、超声氧化法、电催化氧化法、臭氧氧化法和湿式氧化法等高级氧化技术的作用机理及其在造纸废水处理中的应用进展,分析并指出了各种高级氧化技术的特点以及存在的问题和今后的主要发展方向.

Plastic reactor suitable for high pressure and supercritical fluid electrochemistry

DEFF Research Database (Denmark)

Branch, Jack; Alibouri, Mehrdad; Cook, David A.

2017-01-01

The paper describes a reactor suitable for high pressure, particularly supercritical fluid, electrochemistry and electrodeposition at pressures up to 30 MPa at 115◦C. The reactor incorporates two key, new design concepts; a plastic reactor vessel and the use of o-ring sealed brittle electrodes...... by the deposition of Bi. The application of the reactor to the production of nanostructures is demonstrated by the electrodeposition of ∼80 nm diameter Te nanowires into an anodic alumina on silicon template. Key advantages of the new reactor design include reduction of the number of wetted materials, particularly...... glues used for insulating electrodes, compatability with reagents incompatible with steel, compatability with microfabricated planar multiple electrodes, small volume which brings safety advantages and reduced reagent useage, and a significant reduction in experimental time....

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.

Corrosion properties of modified PNC1520 austenitic stainless steel in supercritical water as a fuel cladding candidate material for supercritical water reactor

International Nuclear Information System (INIS)

Nakazono, Yoshihisa; Iwai, Takeo; Abe, Hiroaki

2009-01-01

The supercritical water-cooled reactor (SCWR) has been designed and investigated because of its high thermal efficiency and plant simplification. There are some advantages including the use of a single phase coolant with high enthalpy. Supercritical Water (SCW) has never been used in nuclear power applications. There are numerous potential problems, particularly with materials. As the operating temperature of SCWR will be between 553 K and 893 K with a pressure of 25 MPa, the selection of materials is difficult and important. The PNC1520 austenitic stainless steel has been developed by Japan Atomic Energy Agency (JAEA) as a nuclear fuel cladding material for a Na-cooled fast breeder reactor. Austenitic Fe-base steels were selected for possible use in supercritical water systems because of their corrosion resistance and radiation resistance. The PNC1520 austenitic stainless steel was selected for possible use in supercritical water systems. The corrosion data of PNC1520 in SCW is required but does not exist. The purpose of the present study is to research the corrosion properties for PNC1520 austenitic stainless steel in SCW. The SCW corrosion test was performed for the standard PNC1520 (1520S) and the Ti-additional type of PNC1520 (1520T) by using a SCW autoclave. The 1520S and 1520T are the first trial production materials of SCWR cladding candidate material in our group. Corrosion and compatibility tests on the austenitic 1520S and 1520T steels in supercritical water were performed at 673, 773 and 600degC with exposures up to 1000 h. We have evaluated the amount of weight gain, weight loss and weight of scale after the corrosion test in SCW for 1520S and 1520T austenitic steels. After 1000 h corrosion test performed, the weight gains of both austenitic stainless steels were less than 2 g/m 2 at 400degC and 500degC. But 1520T weight increases more and weight loss than 1520S at 600degC. The SEM observation result of the surface after 1000 h corrosion of an test

Effects of Supercritical Environment on Hydrocarbon-fuel Injection

Institute of Scientific and Technical Information of China (English)

Bongchul Shin; Dohun Kim; Min Son; Jaye Koo

2017-01-01

In this study,the effects of environment conditions on decane were investigated.Decane was injected in subcritical and supercritical ambient conditions.The visualization chamber was pressurized to 1.68 MPa by using nitrogen gas at a temperature of 653 K for subcritical ambient conditions.For supercritical ambient conditions,the visualization chamber was pressurized to 2.52 MPa by using helium at a temperature of 653 K.The decane injection in the pressurized chamber was visualized via a shadowgraph technique and gradient images were obtained by a post processing method.A large variation in density gradient was observed at jet interface in the case of subcritical injection in subcritical ambient conditions.Conversely,for supercritical injection in supercritical ambient conditions,a small density gradient was observed at the jet interface.In a manner similar to that observed in other cases,supercritical injection in subcritical ambient conditions differed from supercritical ambient conditions such as sphere shape liquid.Additionally,there were changes in the interface,and the supercritical injection core width was thicker than that in the subcritical injection.Furthermore,in cases with the same injection conditions,the change in the supercritical ambient normalized core width was smaller than the change in the subcritical ambient normalized core width owing to high specific heat at the supercritical injection and small phase change at the interface.Therefore,the interface was affected by the changing ambient condition.Given that the effect of changing the thermodynamic properties of propellants could be essential for a variable thrust rocket engine,the effects of the ambient conditions were investigated experimentally.

Effects of supercritical environment on hydrocarbon-fuel injection

Science.gov (United States)

Shin, Bongchul; Kim, Dohun; Son, Min; Koo, Jaye

2017-04-01

In this study, the effects of environment conditions on decane were investigated. Decane was injected in subcritical and supercritical ambient conditions. The visualization chamber was pressurized to 1.68 MPa by using nitrogen gas at a temperature of 653 K for subcritical ambient conditions. For supercritical ambient conditions, the visualization chamber was pressurized to 2.52 MPa by using helium at a temperature of 653 K. The decane injection in the pressurized chamber was visualized via a shadowgraph technique and gradient images were obtained by a post processing method. A large variation in density gradient was observed at jet interface in the case of subcritical injection in subcritical ambient conditions. Conversely, for supercritical injection in supercritical ambient conditions, a small density gradient was observed at the jet interface. In a manner similar to that observed in other cases, supercritical injection in subcritical ambient conditions differed from supercritical ambient conditions such as sphere shape liquid. Additionally, there were changes in the interface, and the supercritical injection core width was thicker than that in the subcritical injection. Furthermore, in cases with the same injection conditions, the change in the supercritical ambient normalized core width was smaller than the change in the subcritical ambient normalized core width owing to high specific heat at the supercritical injection and small phase change at the interface. Therefore, the interface was affected by the changing ambient condition. Given that the effect of changing the thermodynamic properties of propellants could be essential for a variable thrust rocket engine, the effects of the ambient conditions were investigated experimentally.

Geothermal energy production with supercritical fluids

Science.gov (United States)

Brown, Donald W.

2003-12-30

There has been invented a method for producing geothermal energy using supercritical fluids for creation of the underground reservoir, production of the geothermal energy, and for heat transport. Underground reservoirs are created by pumping a supercritical fluid such as carbon dioxide into a formation to fracture the rock. Once the reservoir is formed, the same supercritical fluid is allowed to heat up and expand, then is pumped out of the reservoir to transfer the heat to a surface power generating plant or other application.

FY 1998 'The New Sunshine Project' leading R and D. Report on the results of the leading R and D of supercritical fluid utilization technology; 1998 nendo 'New Sunshine Keikaku' sendo kenkyu kaihatsu. Chorinkai ryutai riyo gijutsu sendo kenkyu kaihatsu seika hokokusho

Energy Technology Data Exchange (ETDEWEB)

NONE

1999-03-01

The paper reported the FY 1998 achievement of the supercritical fluid utilization leading R and D which started in FY 1997 on a 3-year plan. In the R and D, solvolysis reaction, oxidation reaction and hydrogenation reaction were taken up in the chemical process using supercritical fluid. In the study of solvolysis reaction, the basic data were obtained on decomposition conditions of thermoplastic and thermosetting plastics in supercritical water. Further, concerning the synthesis of environmental friendly type carbonate using CO2, a conversion rate of almost 100% was obtained. About the oxidation reaction, conditions were found out for burning low grade coal in supercritical water without emitting acid gas. This is considered to lead to a possibility of the supercritical water power generation. Relating to the hydrogenation reaction, a study was made on lightening technology of heavy distillate using supercritical water, and the conditions for effective emission of methane and hydrogen were found out. As to the base technology, a study was made of metal materials with high corrosion resistance against supercritical water. (NEDO)

Bio-oil production from biomass via supercritical fluid extraction

Energy Technology Data Exchange (ETDEWEB)

Durak, Halil, E-mail: halildurak@yyu.edu.tr [Yuzuncu Yıl University, Vocational School of Health Services, 65080, Van (Turkey)

2016-04-18

Supercritical fluid extraction is used for producing bio-fuel from biomass. Supercritical fluid extraction process under supercritical conditions is the thermally disruption process of the lignocellulose or other organic materials at 250-400 °C temperature range under high pressure (4-5 MPa). Supercritical fluid extraction trials were performed in a cylindrical reactor (75 mL) in organic solvents (acetone, ethanol) under supercritical conditions with (calcium hydroxide, sodium carbonate) and without catalyst at the temperatures of 250, 275 and 300 °C. The produced liquids at 300 °C in supercritical liquefaction were analyzed and characterized by elemental, GC-MS and FT-IR. 36 and 37 different types of compounds were identified by GC-MS obtained in acetone and ethanol respectively.

Bio-oil production from biomass via supercritical fluid extraction

International Nuclear Information System (INIS)

Durak, Halil

2016-01-01

Supercritical fluid extraction is used for producing bio-fuel from biomass. Supercritical fluid extraction process under supercritical conditions is the thermally disruption process of the lignocellulose or other organic materials at 250-400 °C temperature range under high pressure (4-5 MPa). Supercritical fluid extraction trials were performed in a cylindrical reactor (75 mL) in organic solvents (acetone, ethanol) under supercritical conditions with (calcium hydroxide, sodium carbonate) and without catalyst at the temperatures of 250, 275 and 300 °C. The produced liquids at 300 °C in supercritical liquefaction were analyzed and characterized by elemental, GC-MS and FT-IR. 36 and 37 different types of compounds were identified by GC-MS obtained in acetone and ethanol respectively.

Enhancing power cycle efficiency for a supercritical Brayton cycle power system using tunable supercritical gas mixtures

Science.gov (United States)

Wright, Steven A.; Pickard, Paul S.; Vernon, Milton E.; Radel, Ross F.

2017-08-29

Various technologies pertaining to tuning composition of a fluid mixture in a supercritical Brayton cycle power generation system are described herein. Compounds, such as Alkanes, are selectively added or removed from an operating fluid of the supercritical Brayton cycle power generation system to cause the critical temperature of the fluid to move up or down, depending upon environmental conditions. As efficiency of the supercritical Brayton cycle power generation system is substantially optimized when heat is rejected near the critical temperature of the fluid, dynamically modifying the critical temperature of the fluid based upon sensed environmental conditions improves efficiency of such a system.

Greenhouse gas microbiology in wet and dry straw crust covering pig slurry

DEFF Research Database (Denmark)

Hansen, Rikke Ruth; Nielsen, Daniel Aagren; Schramm, Andreas

2009-01-01

was observed in all crusted treatments exposed to anoxia, and this was probably a result of denitrification based on NO2- and NO3- that had accumulated in the crust during oxic conditions. To reduce overall greenhouse gas emissions, floating crust should be managed to optimize conditions for methanotrophs....... microbiology had an effect on the emission of the potent greenhouse gases CH4 and nitrous oxide (N2O) when crust moisture was manipulated ("Dry", "Moderate", and "Wet"). The dry crust had the deepest oxygen penetration (45 mm as compared to 20 mm in the Wet treatment) as measured with microsensors, the highest...... oxidizing bacteria were undetectable and methane oxidizing bacteria were only sparsely present in the "Wet" treatment. A change to anoxia did not affect the CH4 emission indicating the virtual absence of aerobic methane oxidation in the investigated 2-months old crusts. However, an increase in N2O emission...

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

International Nuclear Information System (INIS)

Shi, Jianzhong; Wang, Xiuqing; Wang, Xiaoyin

2014-01-01

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 2 O 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

Synthesis of nano-crystalline NiFe2O4 powders in subcritical and supercritical ethanol

Czech Academy of Sciences Publication Activity Database

Ćosović, A.; Žák, Tomáš; Glisić, S.; Sokić, M.; Lazarević, S.; Ćosović, V.; Orlović, A.

2016-01-01

Roč. 113, JUL (2016), s. 96-105 ISSN 0896-8446 R&D Projects: GA MŠk(CZ) ED1.1.00/02.0068 Institutional support: RVO:68081723 Keywords : supercritical * subcritical * nano-crystalline powders * nickel ferrite * metal oxide * magnetic properties Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.991, year: 2016

Oxidization and stress corrosion cracking initiation of austenitic alloys in supercritical water

International Nuclear Information System (INIS)

Behnamian, Y.; Li, M.; Luo, J.L.; Chen, W.X.; Zheng, W.; Guzonas, D.A.

2012-01-01

This study determined the stress corrosion cracking behaviour of austenitic alloys in pure supercritical water. Austenitic stainless steels 310S, 316L, and Inconel 625 were tested as static capsule samples at 500 o C for up to 5000 h. After that period, crack initiations were readily observed in all samples, signifying susceptibility to stress corrosion cracking. The microcracks in 316L stainless steel and Inconel 625 were almost intergranular, whereas transgranular microcrack initiation was observed in 310S stainless steel. (author)

Oxidization and stress corrosion cracking initiation of austenitic alloys in supercritical water

Energy Technology Data Exchange (ETDEWEB)

Behnamian, Y.; Li, M.; Luo, J.L.; Chen, W.X. [Univ. of Alberta, Dept. of Chemical and Materials Engineering, Edmonton, Alberta (Canada); Zheng, W. [Materials Technology Laboratory, NRCan, Ottawa, Ontario (Canada); Guzonas, D.A. [Atomic Energy of Canada Limited, Chalk River, Ontario (Canada)

2012-07-01

This study determined the stress corrosion cracking behaviour of austenitic alloys in pure supercritical water. Austenitic stainless steels 310S, 316L, and Inconel 625 were tested as static capsule samples at 500{sup o}C for up to 5000 h. After that period, crack initiations were readily observed in all samples, signifying susceptibility to stress corrosion cracking. The microcracks in 316L stainless steel and Inconel 625 were almost intergranular, whereas transgranular microcrack initiation was observed in 310S stainless steel. (author)

Supercritical Fluids Processing of Biomass to Chemicals and Fuels

Energy Technology Data Exchange (ETDEWEB)

Olson, Norman K. [Iowa State Univ., Ames, IA (United States)

2011-09-28

The main objective of this project is to develop and/or enhance cost-effective methodologies for converting biomass into a wide variety of chemicals, fuels, and products using supercritical fluids. Supercritical fluids will be used both to perform reactions of biomass to chemicals and products as well as to perform extractions/separations of bio-based chemicals from non-homogeneous mixtures. This work supports the Biomass Program’s Thermochemical Platform Goals. Supercritical fluids are a thermochemical approach to processing biomass that, while aligned with the Biomass Program’s interests in gasification and pyrolysis, offer the potential for more precise and controllable reactions. Indeed, the literature with respect to the use of water as a supercritical fluid frequently refers to “supercritical water gasification” or “supercritical water pyrolysis.”

Transport properties of supercritical carbon dioxide

NARCIS (Netherlands)

Lavanchy, F.; Fourcade, E.; de Koeijer, E.A.; Wijers, J.G.; Meyer, T.; Keurentjes, J.T.F.; Kemmere, M.F.; Meyer, T.

2005-01-01

Recently, supercritical fluids have emerged as more sustainable alternatives for the organic solvents often used in polymer processes. This is the first book emphasizing the potential of supercritical carbon dioxide for polymer processes from an engineering point of view. It develops a

Development of a novel wet oxidation process for hazardous and mixed wastes

International Nuclear Information System (INIS)

Dhooge, P.M.

1994-01-01

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. The over all objective of the effort described here is to develop a novel catalytic wet oxidation process for the treatment of these multi-component wastes, with the aim of providing a versatile, non-thermal method which will destroy hazardous organic compounds while simultaneously containing and concentrating toxic and radioactive metals for recovery or disposal in a readily stabilized matrix. The DETOX process uses a unique combination of metal catalysts to increase the rate of oxidation of organic materials. The metal catalysts are in the form of salts dissolved in a dilute acid solution. A typical catalyst composition is 60% ferric chloride, 3--4% hydrochloric acid, 0.13% platinum ions, and 0.13% ruthenium ions in a water solution. The catalyst solution is maintained at 423--473 K. Wastes are introduced into contact with the solution, where their organic portion is oxidized to carbon dioxide and water. If the organic portion is chlorinated, hydrogen chloride will be produced as a product. The process is a viable alternative to incineration for the treatment of organic mixed wastes. Estimated costs for waste treatment using the process are from $2.50/kg to $25.00/kg, depending on the size of the unit and the amount of waste processed. Process units can be mobile for on-site treatment of wastes. Results from phase 1 and 2, design and engineering studies, are described

Corrosion of austenitic and ferritic-martensitic steels exposed to supercritical carbon dioxide

International Nuclear Information System (INIS)

Tan, L.; Anderson, M.; Taylor, D.; Allen, T.R.

2011-01-01

Highlights: → Oxidation is the primary corrosion phenomenon for the steels exposed to S-CO 2 . → The austenitic steels showed significantly better corrosion resistance than the ferritic-martensitic steels. → Alloying elements (e.g., Mo and Al) showed distinct effects on oxidation behavior. - Abstract: Supercritical carbon dioxide (S-CO 2 ) is a potential coolant for advanced nuclear reactors. The corrosion behavior of austenitic steels (alloys 800H and AL-6XN) and ferritic-martensitic (FM) steels (F91 and HCM12A) exposed to S-CO 2 at 650 deg. C and 20.7 MPa is presented in this work. Oxidation was identified as the primary corrosion phenomenon. Alloy 800H had oxidation resistance superior to AL-6XN. The FM steels were less corrosion resistant than the austenitic steels, which developed thick oxide scales that tended to exfoliate. Detailed microstructure characterization suggests the effect of alloying elements such as Al, Mo, Cr, and Ni on the oxidation of the steels.

Reactive wetting by liquid sodium on thin Au platin

International Nuclear Information System (INIS)

Kawaguchi, Munemichi; Hamada, Hirotsugu

2014-01-01

For practical use of an under-sodium viewer, the behavior of sodium wetting is investigated by modeling the reactive and non-reactive wetting of metallic-plated steels by liquid sodium to simulate sodium wetting. The non-reactive wetting simulation results showed good agreement with Tanner's law, in which the time dependencies of the droplet radius and contact angle are expressed as R N ∝ t 1/10 and θ∝ t -3/10 , respectively; therefore, the model was considered suitable for the simulation. To simulate reactive wetting, the model of fluid flow induced by the interfacial reaction was incorporated into the simulation of non-reactive wetting. The reactive wetting simulation results, such as the behavior of the precursor liquid film and central droplet, showed good agreement with sodium wetting experiments using thin Au plating at 250°C. An important result of the reactive wetting simulation is that the gradient of the reaction energy at the interface appeared on the new interface around the triple line, and that fluid flow was induced. This interfacial reactivity during sodium wetting of thin Au plating was enhanced by the reaction of sodium and nickel oxide through pinholes in the plating. (author)

Supercritical boiler material selection using fuzzy analytic network process

Directory of Open Access Journals (Sweden)

Saikat Ranjan Maity

2012-08-01

Full Text Available The recent development of world is being adversely affected by the scarcity of power and energy. To survive in the next generation, it is thus necessary to explore the non-conventional energy sources and efficiently consume the available sources. For efficient exploitation of the existing energy sources, a great scope lies in the use of Rankin cycle-based thermal power plants. Today, the gross efficiency of Rankin cycle-based thermal power plants is less than 28% which has been increased up to 40% with reheating and regenerative cycles. But, it can be further improved up to 47% by using supercritical power plant technology. Supercritical power plants use supercritical boilers which are able to withstand a very high temperature (650-720˚C and pressure (22.1 MPa while producing superheated steam. The thermal efficiency of a supercritical boiler greatly depends on the material of its different components. The supercritical boiler material should possess high creep rupture strength, high thermal conductivity, low thermal expansion, high specific heat and very high temperature withstandability. This paper considers a list of seven supercritical boiler materials whose performance is evaluated based on seven pivotal criteria. Given the intricacy and difficulty of this supercritical boiler material selection problem having interactions and interdependencies between different criteria, this paper applies fuzzy analytic network process to select the most appropriate material for a supercritical boiler. Rene 41 is the best supercritical boiler material, whereas, Haynes 230 is the worst preferred choice.

Thermodynamic Optimization of Supercritical CO{sub 2} Brayton Cycles

Energy Technology Data Exchange (ETDEWEB)

Rhim, Dong-Ryul; Park, Sung-Ho; Kim, Su-Hyun; Yeom, Choong-Sub [Institute for Advanced Engineering, Yongin (Korea, Republic of)

2015-05-15

The supercritical CO{sub 2} Brayton cycle has been studied for nuclear applications, mainly for one of the alternative power conversion systems of the sodium cooled fast reactor, since 1960's. Although the supercritical CO{sub 2} Brayton cycle has not been expected to show higher efficiency at lower turbine inlet temperature over the conventional steam Rankine cycle, the higher density of supercritical CO{sub 2} like a liquid in the supercritical region could reduce turbo-machinery sizes, and the potential problem of sodium-water reaction with the sodium cooled fast reactor might be solved with the use of CO{sub 2} instead of water. The supercritical CO{sub 2} recompression Brayton cycle was proposed for the better thermodynamic efficiency than for the simple supercritical CO{sub 2} Brayton cycle. Thus this paper presents the efficiencies of the supercritical CO{sub 2} recompression Brayton cycle along with several decision variables for the thermodynamic optimization of the supercritical CO{sub 2} recompression Brayton cycle. The analytic results in this study show that the system efficiency reaches its maximum value at a compressor outlet pressure of 200 bars and a recycle fraction of 30 %, and the lower minimum temperature approach at the two heat exchangers shows higher system efficiency as expected.

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

International Nuclear Information System (INIS)

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

2010-01-01

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 deg. C and ((Al-Fe)PILC/H 2 O 2 ) at 50 deg. 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 deg. 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.

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.

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.

Fundamental Understanding of Crack Growth in Structural Components of Generation IV Supercritical Light Water Reactors

Energy Technology Data Exchange (ETDEWEB)

Iouri I. Balachov; Takao Kobayashi; Francis Tanzella; Indira Jayaweera; Palitha Jayaweera; Petri Kinnunen; Martin Bojinov; Timo Saario

2004-11-17

This work contributes to the design of safe and economical Generation-IV Super-Critical Water Reactors (SCWRs) by providing a basis for selecting structural materials to ensure the functionality of in-vessel components during the entire service life. During the second year of the project, we completed electrochemical characterization of the oxide film properties and investigation of crack initiation and propagation for candidate structural materials steels under supercritical conditions. We ranked candidate alloys against their susceptibility to environmentally assisted degradation based on the in situ data measure with an SRI-designed controlled distance electrochemistry (CDE) arrangement. A correlation between measurable oxide film properties and susceptibility of austenitic steels to environmentally assisted degradation was observed experimentally. One of the major practical results of the present work is the experimentally proven ability of the economical CDE technique to supply in situ data for ranking candidate structural materials for Generation-IV SCRs. A potential use of the CDE arrangement developed ar SRI for building in situ sensors monitoring water chemistry in the heat transport circuit of Generation-IV SCWRs was evaluated and proved to be feasible.

Supercritical CO2 impregnation of polyethylene components for medical purposes

Directory of Open Access Journals (Sweden)

Gamse Thomas

2007-01-01

Full Text Available Modem hip and knee endoprosthesis are produced in titanium and to reduce the friction at the contact area polymer parts, mainly ultra-high molecular weight polyethylene (UHMW-PE, are installed. The polyethylene is impregnated with a-tocopherol (vitamin E before processing for remarkable decrease of oxidative degradation. Cross linked UHMW-PE offers much higher stability, but a-tocopherol cannot be added before processing, because a-tocopherol hinders the cross linking process accompanied by a heavy degradation of the vitamin. The impregnation of UHMW-PE with a-tocopherol has to be performed after the cross linking process and an accurate concentration has to be achieved over the cross section of the whole material. In the first tests UHMW-PE-cubes were stored in pure a-tocopherol under inert atmosphere at temperatures from 100 to 150 °C resulting in a high mass fraction of a-tocopherol in the edge zones and no constant concentration over the cross section. For better distribution and for regulating the mass fraction of a-tocopherol in the cross linked UHMW-PE material supercritical CO2 impregnation tests were investigated. Again UHMW-PE-cubes were impregnated in an autoclave with a-tocopherol dissolved in supercritical CO2 at different pressures and temperatures with variable impregnation times and vitamin E concentrations. Based on the excellent results of supercritical CO2 impregnation standard hip and knee cups were stabilized nearly homogeneously with varying mass fraction of a-tocopherol.

Wettability impact on supercritical CO2 capillary trapping: Pore-scale visualization and quantification

Science.gov (United States)

Hu, Ran; Wan, Jiamin; Kim, Yongman; Tokunaga, Tetsu K.

2017-08-01

How the wettability of pore surfaces affects supercritical (sc) CO2 capillary trapping in geologic carbon sequestration (GCS) is not well understood, and available evidence appears inconsistent. Using a high-pressure micromodel-microscopy system with image analysis, we studied the impact of wettability on scCO2 capillary trapping during short-term brine flooding (80 s, 8-667 pore volumes). Experiments on brine displacing scCO2 were conducted at 8.5 MPa and 45°C in water-wet (static contact angle θ = 20° ± 8°) and intermediate-wet (θ = 94° ± 13°) homogeneous micromodels under four different flow rates (capillary number Ca ranging from 9 × 10-6 to 8 × 10-4) with a total of eight conditions (four replicates for each). Brine invasion processes were recorded and statistical analysis was performed for over 2000 images of scCO2 saturations, and scCO2 cluster characteristics. The trapped scCO2 saturation under intermediate-wet conditions is 15% higher than under water-wet conditions under the slowest flow rate (Ca ˜ 9 × 10-6). Based on the visualization and scCO2 cluster analysis, we show that the scCO2 trapping process in our micromodels is governed by bypass trapping that is enhanced by the larger contact angle. Smaller contact angles enhance cooperative pore filling and widen brine fingers (or channels), leading to smaller volumes of scCO2 being bypassed. Increased flow rates suppress this wettability effect.

Supercritical Fluid Chromatographic Separation of Dimethylpolysiloxane Polymer

Energy Technology Data Exchange (ETDEWEB)

Pyo, Dong Jin; Lim, Chang Hyun [Kangwon National University, Chuncheon (Korea, Republic of)

2005-02-15

Water was used as a polar modifier and a μ-porasil column as a saturator column. The μ-porasil column was inserted between the pump outlet and the injection valve. During the passage of the supercritical fluid mobile phase through the silica column, a polar modifier (water) can be dissolved in the pressurized supercritical fluid. Dimethylpolysiloxane polymer has been known as more polar polymer than polystyrene polymer. Dimethylpolysiloxane polymer has never been separated using water modified mobile phase. In this paper, using a μ-porasil column as a saturator column, excellent supercritical fluid chromatograms of dimethylpolysiloxane oligomers were obtained. The use of compressed (dense) gases and supercritical fluids as chromatographic mobile phases in conjunction with liquid chromatographic (LC)-type packed columns was first reported by Klesper et al. in 1962. During its relatively short history, supercritical fluid chromatography (SFC) has become an attractive alternative to GC and LC in certain industrially important applications. SFC gives the advantage of high efficiency and allows the analysis of nonvolatile or thermally labile mixtures.

Supercritical Fluid Chromatographic Separation of Dimethylpolysiloxane Polymer

International Nuclear Information System (INIS)

Pyo, Dong Jin; Lim, Chang Hyun

2005-01-01

Water was used as a polar modifier and a μ-porasil column as a saturator column. The μ-porasil column was inserted between the pump outlet and the injection valve. During the passage of the supercritical fluid mobile phase through the silica column, a polar modifier (water) can be dissolved in the pressurized supercritical fluid. Dimethylpolysiloxane polymer has been known as more polar polymer than polystyrene polymer. Dimethylpolysiloxane polymer has never been separated using water modified mobile phase. In this paper, using a μ-porasil column as a saturator column, excellent supercritical fluid chromatograms of dimethylpolysiloxane oligomers were obtained. The use of compressed (dense) gases and supercritical fluids as chromatographic mobile phases in conjunction with liquid chromatographic (LC)-type packed columns was first reported by Klesper et al. in 1962. During its relatively short history, supercritical fluid chromatography (SFC) has become an attractive alternative to GC and LC in certain industrially important applications. SFC gives the advantage of high efficiency and allows the analysis of nonvolatile or thermally labile mixtures

Introduction to supercritical fluids a spreadsheet-based approach

CERN Document Server

Smith, Richard; Peters, Cor

2013-01-01

This text provides an introduction to supercritical fluids with easy-to-use Excel spreadsheets suitable for both specialized-discipline (chemistry or chemical engineering student) and mixed-discipline (engineering/economic student) classes. Each chapter contains worked examples, tip boxes and end-of-the-chapter problems and projects. Part I covers web-based chemical information resources, applications and simplified theory presented in a way that allows students of all disciplines to delve into the properties of supercritical fluids and to design energy, extraction and materials formation systems for real-world processes that use supercritical water or supercritical carbon dioxide. Part II takes a practical approach and addresses the thermodynamic framework, equations of state, fluid phase equilibria, heat and mass transfer, chemical equilibria and reaction kinetics of supercritical fluids. Spreadsheets are arranged as Visual Basic for Applications (VBA) functions and macros that are completely (source code) ...

Supercritical Water Gasification of Biomass in a Ceramic Reactor: Long-Time Batch Experiments

Directory of Open Access Journals (Sweden)

Daniele Castello

2017-10-01

Full Text Available Supercritical water gasification (SCWG is an emerging technology for the valorization of (wet biomass into a valuable fuel gas composed of hydrogen and/or methane. The harsh temperature and pressure conditions involved in SCWG (T > 375 °C, p > 22 MPa are definitely a challenge for the manufacturing of the reactors. Metal surfaces are indeed subject to corrosion under hydrothermal conditions, and expensive special alloys are needed to overcome such drawbacks. A ceramic reactor could be a potential solution to this issue. Finding a suitable material is, however, complex because the catalytic effect of the material can influence the gas yield and composition. In this work, a research reactor featuring an internal alumina inlay was utilized to conduct long-time (16 h batch tests with real biomasses and model compounds. The same experiments were also conducted in batch reactors made of stainless steel and Inconel 625. The results show that the three devices have similar performance patterns in terms of gas production, although in the ceramic reactor higher yields of C2+ hydrocarbons were obtained. The SEM observation of the reacted alumina surface revealed a good resistance of such material to supercritical conditions, even though some intergranular corrosion was observed.

FY 1998 'The New Sunshine Project' leading R and D. Report on the results of the leading R and D of supercritical fluid utilization technology; 1998 nendo 'New Sunshine Keikaku' sendo kenkyu kaihatsu. Chorinkai ryutai riyo gijutsu sendo kenkyu kaihatsu seika hokokusho

Energy Technology Data Exchange (ETDEWEB)

NONE

1999-03-01

The paper reported the FY 1998 achievement of the supercritical fluid utilization leading R and D which started in FY 1997 on a 3-year plan. In the R and D, solvolysis reaction, oxidation reaction and hydrogenation reaction were taken up in the chemical process using supercritical fluid. In the study of solvolysis reaction, the basic data were obtained on decomposition conditions of thermoplastic and thermosetting plastics in supercritical water. Further, concerning the synthesis of environmental friendly type carbonate using CO2, a conversion rate of almost 100% was obtained. About the oxidation reaction, conditions were found out for burning low grade coal in supercritical water without emitting acid gas. This is considered to lead to a possibility of the supercritical water power generation. Relating to the hydrogenation reaction, a study was made on lightening technology of heavy distillate using supercritical water, and the conditions for effective emission of methane and hydrogen were found out. As to the base technology, a study was made of metal materials with high corrosion resistance against supercritical water. (NEDO)

Simulation of Thermal Hydraulic at Supercritical Pressures with APROS

Energy Technology Data Exchange (ETDEWEB)

Kurki, Joona [VTT Technical Research Centre of Finland, P.O. Box 1000, FI02044 VTT (Finland)

2008-07-01

The proposed concepts for the fourth generation of nuclear reactors include a reactor operating with water at thermodynamically supercritical state, the Supercritical Water Reactor (SCWR). For the design and safety demonstrations of such a reactor, the possibility to accurately simulate the thermal hydraulics of the supercritical coolant is an absolute prerequisite. For this purpose, the one-dimensional two-phase thermal hydraulics solution of APROS process simulation software was developed to function at the supercritical pressure region. Software modifications included the redefinition of some parameters that have physical significance only at the subcritical pressures, improvement of the steam tables, and addition of heat transfer and friction correlations suitable for the supercritical pressure region. (author)

Wettability effect on capillary trapping of supercritical CO2 at pore-scale: micromodel experiment and numerical modeling

Science.gov (United States)

Hu, R.; Wan, J.

2015-12-01

Wettability of reservoir minerals along pore surfaces plays a controlling role in capillary trapping of supercritical (sc) CO2 in geologic carbon sequestration. The mechanisms controlling scCO2 residual trapping are still not fully understood. We studied the effect of pore surface wettability on CO2 residual saturation at the pore-scale using engineered high pressure and high temperature micromodel (transparent pore networks) experiments and numerical modeling. Through chemical treatment of the micromodel pore surfaces, water-wet, intermediate-wet, and CO2-wet micromodels can be obtained. Both drainage and imbibition experiments were conducted at 8.5 MPa and 45 °C with controlled flow rate. Dynamic images of fluid-fluid displacement processes were recorded using a microscope with a CCD camera. Residual saturations were determined by analysis of late stage imbibition images of flow path structures. We performed direct numerical simulations of the full Navier-Stokes equations using a volume-of-fluid based finite-volume framework for the primary drainage and the followed imbibition for the micromodel experiments with different contact angles. The numerical simulations agreed well with our experimental observations. We found that more scCO2 can be trapped within the CO2-wet micromodel whereas lower residual scCO2 saturation occurred within the water-wet micromodels in both our experiments and the numerical simulations. These results provide direct and consistent evidence of the effect of wettability, and have important implications for scCO2 trapping in geologic carbon sequestration.

Thermodynamic study contribution of U-Fe and U-Ga alloys by high temperature mass spectroscopy, and of the wetting of yttrium oxide by uranium

International Nuclear Information System (INIS)

Gardie, P.

1992-01-01

High temperature thermodynamic properties study of U-Fe and U-Ga alloys, and wetting study of yttrium oxide by uranium are presented. High temperature mass spectrometry coupled to a Knudsen effusion multi-cell allows to measure iron activity in U-Fe alloys and of gallium in U-Ga alloys, the U activity is deduced from Gibbs-Duhem equation. Wetting of the system U/Y_2O_3_-_x is studied between 1413 K and 1973 K by the put drop method visualized by X-rays. This technique also furnishes density, surface tension of U and of U-Fe alloys put on Y_2O_3_-_x. A new model of the interfacial oxygen action on wetting is done for the system U/Y_2O_3_-_x. (A.B.)

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.

Multi-Phase Equilibrium and Solubilities of Aromatic Compounds and Inorganic Compounds in Sub- and Supercritical Water: A Review.

Science.gov (United States)

Liu, Qinli; Ding, Xin; Du, Bowen; Fang, Tao

2017-11-02

Supercritical water oxidation (SCWO), as a novel and efficient technology, has been applied to wastewater treatment processes. The use of phase equilibrium data to optimize process parameters can offer a theoretical guidance for designing SCWO processes and reducing the equipment and operating costs. In this work, high-pressure phase equilibrium data for aromatic compounds+water systems and inorganic compounds+water systems are given. Moreover, thermodynamic models, equations of state (EOS) and empirical and semi-empirical approaches are summarized and evaluated. This paper also lists the existing problems of multi-phase equilibria and solubility studies on aromatic compounds and inorganic compounds in sub- and supercritical water.

Development studies for a novel wet oxidation process. Phase 2

International Nuclear Information System (INIS)

1994-07-01

DETOX 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

Superior corrosion resistance properties of TiN-based coatings on Zircaloy tubes in supercritical water

Energy Technology Data Exchange (ETDEWEB)

Khatkhatay, Fauzia [Department of Electrical and Computer Engineering, Texas A and M University, College Station, TX 77843-3128 (United States); Jiao, Liang [Materials Science and Engineering Program, Texas A and M University, College Station, TX 77843-3003 (United States); Jian, Jie [Department of Electrical and Computer Engineering, Texas A and M University, College Station, TX 77843-3128 (United States); Zhang, Wenrui [Materials Science and Engineering Program, Texas A and M University, College Station, TX 77843-3003 (United States); Jiao, Zhijie [Nuclear Engineering and Radiological Sciences, University of Michigan, Ann Arbor, MI 48109-2104 (United States); Gan, Jian; Zhang, Hongbin [Idaho National Laboratory, Idaho Falls, ID 83415-6188 (United States); Zhang, Xinghang [Materials Science and Engineering Program, Texas A and M University, College Station, TX 77843-3003 (United States); Department of Mechanical Engineering, Texas A and M University, College Station, TX 77843-3123 (United States); Wang, Haiyan, E-mail: wangh@ece.tamu.edu [Department of Electrical and Computer Engineering, Texas A and M University, College Station, TX 77843-3128 (United States); Materials Science and Engineering Program, Texas A and M University, College Station, TX 77843-3003 (United States)

2014-08-01

Thin films of TiN and Ti{sub 0.35}Al{sub 0.65}N nanocomposite were deposited on polished Zircaloy-4 tubes. After exposure to supercritical water for 48 h, the coated tubes are remarkably intact, while the bare uncoated tube shows severe oxidation and breakaway corrosion. X-ray diffraction patterns, secondary electron images, backscattered electron images, and energy dispersive X-ray spectroscopy data from the tube surfaces and cross-sections show that a protective oxide, formed on the film surface, effectively prevents further oxidation and corrosion to the Zircaloy-4 tubes. This result demonstrates the effectiveness of thin film ceramics as protective coatings under extreme environments.

Supercritical fluid technology: concepts and pharmaceutical applications.

Science.gov (United States)

Deshpande, Praful Balavant; Kumar, G Aravind; Kumar, Averineni Ranjith; Shavi, Gopal Venkatesh; Karthik, Arumugam; Reddy, Meka Sreenivasa; Udupa, Nayanabhirama

2011-01-01

In light of environmental apprehension, supercritical fluid technology (SFT) exhibits excellent opportunities to accomplish key objectives in the drug delivery sector. Supercritical fluid extraction using carbon dioxide (CO(2)) has been recognized as a green technology. It is a clean and versatile solvent with gas-like diffusivity and liquid-like density in the supercritical phase, which has provided an excellent alternative to the use of chemical solvents. The present commentary provides an overview of different techniques using supercritical fluids and their future opportunity for the drug delivery industry. Some of the emerging applications of SFT in pharmaceuticals, such as particle design, drug solubilization, inclusion complex, polymer impregnation, polymorphism, drug extraction process, and analysis, are also covered in this review. The data collection methods are based on the recent literature related to drug delivery systems using SFT platforms. SFT has become a much more versatile and environmentally attractive technology that can handle a variety of complicated problems in pharmaceuticals. This cutting-edge technology is growing predominantly to surrogate conventional unit operations in relevance to the pharmaceutical production process. Supercritical fluid technology has recently drawn attention in the field of pharmaceuticals. It is a distinct conception that utilizes the solvent properties of supercritical fluids above their critical temperature and pressure, where they exhibit both liquid-like and gas-like properties, which can enable many pharmaceutical applications. For example, the liquid-like properties provide benefits in extraction processes of organic solvents or impurities, drug solubilization, and polymer plasticization, and the gas-like features facilitate mass transfer processes. It has become a much more versatile and environmentally attractive technology that can handle a variety of complicated problems in pharmaceuticals. This review is

Cobalt sulfide aerogel prepared by anion exchange method with enhanced pseudocapacitive and water oxidation performances

Science.gov (United States)

Gao, Qiuyue; Shi, Zhenyu; Xue, Kaiming; Ye, Ziran; Hong, Zhanglian; Yu, Xinyao; Zhi, Mingjia

2018-05-01

This work introduces the anion exchange method into the sol-gel process for the first time to prepare a metal sulfide aerogel. A porous Co9S8 aerogel with a high surface area (274.2 m2 g‑1) and large pore volume (0.87 cm3 g‑1) has been successfully prepared by exchanging cobalt citrate wet gel in thioacetamide and subsequently drying in supercritical ethanol. Such a Co9S8 aerogel shows enhanced supercapacitive performance and catalytic activity toward oxygen evolution reaction (OER) compared to its oxide aerogel counterpart. High specific capacitance (950 F g‑1 at 1 A g‑1), good rate capability (74.3% capacitance retention from 1 to 20 A g‑1) and low onset overpotential for OER (220 mV) were observed. The results demonstrated here have implications in preparing various sulfide chalcogels.

Ni/MgAlO regeneration for catalytic wet air oxidation of an azo-dye in trickle-bed reaction

International Nuclear Information System (INIS)

Vallet, Ana; Ovejero, Gabriel; Rodríguez, Araceli; Peres, José A.; García, Juan

2013-01-01

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 −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

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.

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.

A comparison of the mechanisms of photooxidative degradation of organic molecules on irradiated semiconductor powders and in aerated supercritical water

Energy Technology Data Exchange (ETDEWEB)

Fox, Marye Anne [Department of Chemistry and Biochemistry, University of Texas at Austin, Austin, TX (United States)

1995-08-01

It is the purpose of this paper to survey evidence that suggests that control of the local environment is important in both heterogeneous TiO{sub 2} photocatalysis and in thermal oxidation reactions taking place in supercritical fluids, i.e. that the expected influences of these very different methods for microcompartmentalization do indeed influence the observed reaction kinetics in an easily observable way. Variations in reaction kinetics and the photophysical properties are described for (1) small semiconductor clusters, including their altered photocatalytic activity in and on inert supports; and (2) molecular probes dispersed within the self-aggregating clusters formed within supercritical water

Indium tin oxide films prepared via wet chemical route

International Nuclear Information System (INIS)

Legnani, C.; Lima, S.A.M.; Oliveira, H.H.S.; Quirino, W.G.; Machado, R.; Santos, R.M.B.; Davolos, M.R.; Achete, C.A.; Cremona, M.

2007-01-01

In this work, indium tin oxide (ITO) films were prepared using a wet chemical route, the Pechini method. This consists of a polyesterification reaction between an α-hydroxicarboxylate complex (indium citrate and tin citrate) with a polyalcohol (ethylene glycol) followed by a post annealing at 500 deg. C. A 10 at.% of doping of Sn 4+ ions into an In 2 O 3 matrix was successfully achieved through this method. In order to characterize the structure, the morphology as well as the optical and electrical properties of the produced ITO films, they were analyzed using different experimental techniques. The obtained films are highly transparent, exhibiting transmittance of about 85% at 550 nm. They are crystalline with a preferred orientation of [222]. Microscopy discloses that the films are composed of grains of 30 nm average size and 0.63 nm RMS roughness. The films' measured resistivity, mobility and charge carrier concentration were 5.8 x 10 -3 Ω cm, 2.9 cm 2 /V s and - 3.5 x 10 20 /cm 3 , respectively. While the low mobility value can be related to the small grain size, the charge carrier concentration value can be explained in terms of the high oxygen concentration level resulting from the thermal treatment process performed in air. The experimental conditions are being refined to improve the electrical characteristics of the films while good optical, chemical, structural and morphological qualities already achieved are maintained

Supercritical Airfoil Coordinates

Data.gov (United States)

National Aeronautics and Space Administration — Rectangular Supercritical Wing (Ricketts) - design and measured locations are provided in an Excel file RSW_airfoil_coordinates_ricketts.xls . One sheet is with Non...

Theoretical models for supercritical fluid extraction.

Science.gov (United States)

Huang, Zhen; Shi, Xiao-Han; Jiang, Wei-Juan

2012-08-10

For the proper design of supercritical fluid extraction processes, it is essential to have a sound knowledge of the mass transfer mechanism of the extraction process and the appropriate mathematical representation. In this paper, the advances and applications of kinetic models for describing supercritical fluid extraction from various solid matrices have been presented. The theoretical models overviewed here include the hot ball diffusion, broken and intact cell, shrinking core and some relatively simple models. Mathematical representations of these models have been in detail interpreted as well as their assumptions, parameter identifications and application examples. Extraction process of the analyte solute from the solid matrix by means of supercritical fluid includes the dissolution of the analyte from the solid, the analyte diffusion in the matrix and its transport to the bulk supercritical fluid. Mechanisms involved in a mass transfer model are discussed in terms of external mass transfer resistance, internal mass transfer resistance, solute-solid interactions and axial dispersion. The correlations of the external mass transfer coefficient and axial dispersion coefficient with certain dimensionless numbers are also discussed. Among these models, the broken and intact cell model seems to be the most relevant mathematical model as it is able to provide realistic description of the plant material structure for better understanding the mass-transfer kinetics and thus it has been widely employed for modeling supercritical fluid extraction of natural matters. Copyright © 2012 Elsevier B.V. All rights reserved.

Thermal stability of biodiesel in supercritical methanol

Energy Technology Data Exchange (ETDEWEB)

Hiroaki Imahara; Eiji Minami; Shusaku Hari; Shiro Saka [Kyoto University, Kyoto (Japan). Department of Socio-Environmental Energy Science

2008-01-15

Non-catalytic biodiesel production technologies from oils/fats in plants and animals have been developed in our laboratory employing supercritical methanol. Due to conditions in high temperature and high pressure of the supercritical fluid, thermal stability of fatty acid methyl esters and actual biodiesel prepared from various plant oils was studied in supercritical methanol over a range of its condition between 270{sup o}C/17 MPa and 380{sup o}C/56 MPa. In addition, the effect of thermal degradation on cold flow properties was studied. As a result, it was found that all fatty acid methyl esters including poly-unsaturated ones were stable at 270{sup o}C/17 MPa, but at 350{sup o}C/43 MPa, they were partly decomposed to reduce the yield with isomerization from cis-type to trans-type. These behaviors were also observed for actual biodiesel prepared from linseed oil, safflower oil, which are high in poly-unsaturated fatty acids. Cold flow properties of actual biodiesel, however, remained almost unchanged after supercritical methanol exposure at 270{sup o}C/17 MPa and 350{sup o}C/43 MPa. For the latter condition, however, poly-unsaturated fatty acids were sacrificed to be decomposed and reduced in yield. From these results, it was clarified that reaction temperature in supercritical methanol process should be lower than 300{sup o}C, preferably 270{sup o}C with a supercritical pressure higher than 8.09 MPa, in terms of thermal stabilization for high-quality biodiesel production. 9 refs., 3 figs., 4 tabs.

Converting SDAP into gypsum in a wet limestone scrubber

Energy Technology Data Exchange (ETDEWEB)

Fogh, F [Faelleskemikerne, Elsamprojekt A/S, Fredericia (Denmark)

1996-12-01

The ELSAM power pool has an installed electrical capacity of approx. 5 GW{sub e}, mainly firing import coal. The major base load units are equipped with desulphurization units and three different desulphurization technologies are used: the wet limestone gypsum process, the spray dry absorption process and a sulphuric acid process. Gypsum and sulphuric acid are commercialized, whereas it has been difficult to utilize the spray dry absorption product (SDAP). The main constituents of SDAP are calcium sulphide, calcium chloride, hydrated lime and impurities mainly originating from fly ash. Sulphide can be oxidized into sulphate in acidic solution - the reaction is utilized in the wet limestone gypsum process - and the possibility of using any spare capacity in the wet limestone gypsum units to oxidize the sulphide content of SDAP into sulphate and produce usable gypsum has been investigated in the laboratory and in a 400 MW{sub e} equivalent wet limestone unit. The limestone inhibition effect of the addition of SDAP is currently being studied in the laboratory in order to determine the effect of different SDAP types (plant/coal sources) on limestone reactivity before further long-term full-scale tests are performed and permanent use of the process planned. (EG)

Advanced Supercritical Carbon Dioxide Brayton Cycle Development

Energy Technology Data Exchange (ETDEWEB)

Anderson, Mark [Univ. of Wisconsin, Madison, WI (United States); Sienicki, James [Argonne National Lab. (ANL), Argonne, IL (United States); Moisseytsev, Anton [Argonne National Lab. (ANL), Argonne, IL (United States); Nellis, Gregory [Univ. of Wisconsin, Madison, WI (United States); Klein, Sanford [Univ. of Wisconsin, Madison, WI (United States)

2015-10-21

Fluids operating in the supercritical state have promising characteristics for future high efficiency power cycles. In order to develop power cycles using supercritical fluids, it is necessary to understand the flow characteristics of fluids under both supercritical and two-phase conditions. In this study, a Computational Fluid Dynamic (CFD) methodology was developed for supercritical fluids flowing through complex geometries. A real fluid property module was implemented to provide properties for different supercritical fluids. However, in each simulation case, there is only one species of fluid. As a result, the fluid property module provides properties for either supercritical CO₂ (S-CO₂) or supercritical water (SCW). The Homogeneous Equilibrium Model (HEM) was employed to model the two-phase flow. HEM assumes two phases have same velocity, pressure, and temperature, making it only applicable for the dilute dispersed two-phase flow situation. Three example geometries, including orifices, labyrinth seals, and valves, were used to validate this methodology with experimental data. For the first geometry, S-CO₂ and SCW flowing through orifices were simulated and compared with experimental data. The maximum difference between the mass flow rate predictions and experimental measurements is less than 5%. This is a significant improvement as previous works can only guarantee 10% error. In this research, several efforts were made to help this improvement. First, an accurate real fluid module was used to provide properties. Second, the upstream condition was determined by pressure and density, which determines supercritical states more precise than using pressure and temperature. For the second geometry, the flow through labyrinth seals was studied. After a successful validation, parametric studies were performed to study geometric effects on the leakage rate. Based on these parametric studies, an optimum design strategy for the see

Supercritical water oxidation of colored smoke, dye, and pyrotechnic compositions. Final report: Pilot plant conceptual design

Energy Technology Data Exchange (ETDEWEB)

LaJeunesse, C.A.; Chan, Jennifer P.; Raber, T.N.; Macmillan, D.C.; Rice, S.F.; Tschritter, K.L.

1993-11-01

The existing demilitarization stockpile contains large quantities of colored smoke, spotting dye, and pyrotechnic munitions. For many years, these munitions have been stored in magazines at locations within the continental United States awaiting completion of the life-cycle. The open air burning of these munitions has been shown to produce toxic gases that are detrimental to human health and harmful to the environment. Prior efforts to incinerate these compositions have also produced toxic emissions and have been unsuccessful. Supercritical water oxidation (SCWO) is a rapidly developing hazardous waste treatment method that can be an alternative to incineration for many types of wastes. The primary advantage SCWO affords for the treatment of this selected set of obsolete munitions is that toxic gas and particulate emissions will not occur as part of the effluent stream. Sandia is currently designing a SCWO reactor for the US Army Armament Research, Development & Engineering Center (ARDEC) to destroy colored smoke, spotting dye, and pyrotechnic munitions. This report summarizes the design status of the ARDEC reactor. Process and equipment operation parameters, process flow equations or mass balances, and utility requirements for six wastes of interest are developed in this report. Two conceptual designs are also developed with all process and instrumentation detailed.

Treatment of toxic and hazardous organic wastes by wet oxidation process with oxygenated water at low temperature; Trattamento dei rifiuti tossici e nocivi organici mediante il processo di ossidazione ad umido con acqua ossigenata a bassa temperatura

Energy Technology Data Exchange (ETDEWEB)

Piccinno, T; Salluzzo, A; Nardi, L [ENEA - Dipartimento Ciclo del Combustibile, Centro Ricerche Energia, Casaccia (Italy); Gili, M; Luce, A; Troiani, F [ENEA - Dipartimento Ciclo del Combustibile, Centro Ricerche Energia, Saluggia (Italy); Cornacchia, G [ENEA - Dipartimento Ciclo del Combustibile, Centro Ricerche Energia, Trisaia (Italy)

1989-11-15

The wet oxidation process using air or molecular oxygen is a well-known process from long time. It is suitable to oxidize several types of waste refractory to the usual biological, thermal and chemical treatments. The drastic operating conditions (high pressures and temperatures) prevented its industrial development. In the last years a new interest was assigned to the process for the treatment of nuclear wastes (organic resins and exhaust organic wastes); the treatment is carried out at widely reduced operating conditions (atmospheric pressure and boiling temperature) by means of metallic catalysts and hydrogen peroxide. With some limits, the wet oxidation with hydrogen peroxide at low temperature can be applied to conventional waste waters containing toxic organic compounds. In the present report are summarized the activities developed at ENEA Fuel Cycle Department by the task force 'Deox' constituted by laboratory and plant specialists in order to verify the application of the wet oxidation process to the treatment of the toxic wastes. (author)

FY 1999 Advanced research and development project under New Sunshine Project. Study on supercritical solvolysis reaction; 1999 nendo chorinkai ryutai riyo gijutsu sendo kenkyu kaihatsu seika hokokusho

Energy Technology Data Exchange (ETDEWEB)

NONE

2000-03-01

The research and development project is implemented for the chemical processes which utilize supercritical fluids, in order to establish the basic technologies for the environment-friendly chemical processes. For the solvolysis, the conditions under which plastics are hydrolyzed in supercritical water are investigated, and the basic data are obtained for the optimum conditions under which thermoplastic resins are hydrolyzed. The mechanisms involved in hydrolysis of polymers in supercritical water are elucidated to some extent. The environment-friendly process for synthesizing polycarbonate in supercritical carbon dioxide gas is investigated, and the continuous flow sheets are established for securing almost 100% conversion in the presence of an inexpensive catalyst. For the oxidation, the tests are conducted to burn low-grade coal in supercritical water, and the conditions under which it is burnt without releasing acid and toxic gases are found. For the hydrogenation, heavy fuel oil is treated in supercritical water to produce the lighter products. The conditions under which light oils and gases are produced are clarified, and the basic data are obtained for producing light gases from the resultant coke as the by-product. (NEDO)

Fast infrared spectroscopy in supercritical fluids

International Nuclear Information System (INIS)

Sun, X.

2000-05-01

Chapter 1: Introduction. A brief introduction to supercritical fluids is given, illustrating why supercritical fluids are unique solvents and why there is a wide application of supercritical fluids in industry and laboratories. Potential ways for solvation in supercritical fluids to affect reactivity are briefly reviewed. A general introduction to the photochemistry of organometallic complexes is also given. Chapter 2: Time resolved vibrational spectroscopy. Time resolved resonance Raman is introduced and compared with Time-resolved infrared spectroscopy (TRIR). The different approaches of TRIR, including microsecond, nanosecond, and ultrafast (picosecond and femtosecond) systems are discussed. The advantages and disadvantages of these systems are also compared. The TRIR apparatus using an IR diode laser used for work in this thesis are described in detail. Experimental procedures for supercritical fluid TRIR experiments are described with emphasis on handling the IR cell for supercritical fluids and preparation of supercritical fluid solutions. Chapter 3: Photochemistry of group VIB hexacarbonyl compounds in supercritical noble gases and CO 2 solutions. A systematic TRIR study of the photolysis of M(CO) 6 in supercritical Ar, Kr, Xe, and CO 2 and the observation of M(CO) 5 L (M = Cr, Mo, and W; L = Ar (W only), Kr, Xe, and CO 2 ) is described. The second-order rate constants for the reaction of M(CO) 5 L with CO have been evaluated and the reactivity for each metal is Kr > Xe ∼ CO 2 . For M(CO) 5 Kr, M(CO) 5 Xe, or M(CO) 5 (CO 2 ), the reactivity is Cr ∼ Mo > W. In supercritical Kr doped with either Xe or CO 2 , the M(CO) 5 moiety interacts with Xe or CO 2 in preference to Kr. The effect of solvent density on the rate of the reaction of W(CO) 5 (CO 2 ) with CO has been investigated. The reaction of W(CO) 5 (CO 2 ) with CO in scCO 2 is predominantly a dissociative process. The activation energies for the reaction of W(CO) 5 Xe and W(CO) 5 (CO 2 ) with CO and

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.

Simulation Analysis of Sludge Disposal and Volatile Fatty Acids Production from Gravity Pressure Reactor via Wet Air Oxidation

International Nuclear Information System (INIS)

Park, Gwon Woo; Seo, Tae Wan; Lee, Hong-Cheol; Hwang, In-Ju

2016-01-01

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

Supercritical Water Mixture (SCWM) Experiment in the High Temperature Insert-Reflight (HTI-R)

Science.gov (United States)

Hicks, Michael C.; Hegde, Uday G.; Garrabos, Yves; Lecoutre, Carole; Zappoli, Bernard

2013-01-01

Current research on supercritical water processes on board the International Space Station (ISS) focuses on salt precipitation and transport in a test cell designed for supercritical water. This study, known as the Supercritical Water Mixture Experiment (SCWM) serves as a precursor experiment for developing a better understanding of inorganic salt precipitation and transport during supercritical water oxidation (SCWO) processes for the eventual application of this technology for waste management and resource reclamation in microgravity conditions. During typical SCWO reactions any inorganic salts present in the reactant stream will precipitate and begin to coat reactor surfaces and control mechanisms (e.g., valves) often severely impacting the systems performance. The SCWM experiment employs a Sample Cell Unit (SCU) filled with an aqueous solution of Na2SO4 0.5-w at the critical density and uses a refurbished High Temperature Insert, which was used in an earlier ISS experiment designed to study pure water at near-critical conditions. The insert, designated as the HTI-Reflight (HTI-R) will be deployed in the DECLIC (Device for the Study of Critical Liquids and Crystallization) Facility on the International Space Station (ISS). Objectives of the study include measurement of the shift in critical temperature due to the presence of the inorganic salt, assessment of the predominant mode of precipitation (i.e., heterogeneously on SCU surfaces or homogeneously in the bulk fluid), determination of the salt morphology including size and shapes of particulate clusters, and the determination of the dominant mode of transport of salt particles in the presence of an imposed temperature gradient. Initial results from the ISS experiments will be presented and compared to findings from laboratory experiments on the ground.

Development of a test facility for analyzing supercritical fluid blowdown

International Nuclear Information System (INIS)

Roberto, Thiago D.; Alvim, Antonio C.M.

2015-01-01

The generation IV nuclear reactors under development mostly use supercritical fluids as the working fluid because higher temperatures improve the thermal efficiency. Supercritical fluids are used by modern nuclear power plants to achieve thermal efficiencies of around 45%. With water as the supercritical working fluid, these plants operate at a high temperature and pressure. However, experiments on supercritical water are limited by technical and financial difficulties. These difficulties can be overcome by using model fluids, which have more feasible supercritical conditions and exhibit a lower critical pressure and temperature. Experimental research is normally used to determine the conditions under which model fluids represent supercritical fluids under steady-state conditions. A fluid-to-fluid scaling approach has been proposed to determine model fluids that can represent supercritical fluids in a transient state. This paper presents an application of fractional scale analysis to determine the simulation parameters for a depressurization test facility. Carbon dioxide (CO 2 ) and R134a gas were considered as the model fluids because their critical point conditions are more feasible than those of water. The similarities of water (prototype), CO 2 (model) and R134a (model) for depressurization in a pressure vessel were analyzed. (author)

Study on corrosion behavior of candidate materials in 650℃ supercritical water

International Nuclear Information System (INIS)

Ma Shuli; Luo Ying; Zhang Qiang; Wang Hao; Qiu Shaoyu

2014-01-01

The general corrosion behavior of three candidate materials (347, HR3C and In-718) was investigated in 650 ℃/25 MPa deionized water. Morphology and composition of the surface oxide film with different exposure time were observed through FEG-SEM and EDS. The phase constitute was analyzed by GIXRD. For all the test materials, the weight loss follows typical parabolic law and the weight loss of 347 shows more than 40 times higher than that of HR3C and In-718. The oxide film of three alloys mainly consists of Ni(Cr, Fe) 2 O 4 . In-718 shows severe pitting and the oxide film of 347 appears significant spalling, while HR3C has compact oxide film. In the high temperature supercritical water, the high Cr content may enhance the general corrosion property of the alloys, while addition of Nb may be detrimental to the pitting resistance of alloys. (authors)

27.12 MHz plasma generation in supercritical carbon dioxide

International Nuclear Information System (INIS)

Kawashima, Ayato; Toyota, Hiromichi; Nomura, Shinfuku; Takemori, Toshihiko; Mukasa, Shinobu; Maehara, Tsunehiro; Yamashita, Hiroshi

2007-01-01

An experiment was conducted for generating high-frequency plasma in supercritical carbon dioxide; it is expected to have the potential for applications in various types of practical processes. It was successfully generated at 6-20 MPa using electrodes mounted in a supercritical cell with a gap of 1 mm. Emission spectra were then measured to investigate the physical properties of supercritical carbon dioxide plasma. The results indicated that while the emission spectra for carbon dioxide and carbon monoxide could be mainly obtained at a low pressure, the emission spectra for atomic oxygen could be obtained in the supercritical state, which increased with the pressure. The temperature of the plasma in supercritical state was estimated to be approximately 6000-7000 K on the assumption of local thermodynamic equilibrium and the calculation results of thermal equilibrium composition in this state showed the increase of atomic oxygen by the decomposition of CO 2

Radiolytic and electron-transfer reactions in supercritical CO2

International Nuclear Information System (INIS)

Bartels, D. M.; Dimitrijevic, N. M.; Jonah, C. D.; Takahashi, K.

2000-01-01

Using supercritical fluids as solvents is useful for both practical and theoretical reasons. It has been proposed to use supercritical CO 2 as a solvent for synthesis because it eliminates the air pollution arising from other solvents. The properties of supercritical fluids can be easily varied with only modest changes in temperature and density, so they provide a way of testing theories of chemical reactions. It has also been proposed to use supercritical fluids for the treatment of hazardous mixed waste. For these reasons the authors have studied the production of radiolytic species in supercritical CO 2 and have measured their reactivity as a function of density. They have shown that the C 2 O 4 + is formed. They also have shown that the electron transfer reactions of dimethylaniline to C 2 O 4 + and CO 2 (e - ) to benzoquinone are diffusion controlled over a considerable density range

Supercritical fields and bald black holes

Energy Technology Data Exchange (ETDEWEB)

Irvine, J M

1975-01-01

The instability of a many-fermion ground state against particle-hole excitations is reviewed and the existence of supercritical electromagnetic and strong interaction fields is briefly discussed. The nature of associated phase changes and in particular the change in conservation laws which accompanies the phase changes is outlined. Finally, the supercritical gravitational field is considered and weight given to the argument that ''black holes have no hair.''

Making Activated Carbon by Wet Pressurized Pyrolysis

Science.gov (United States)

Fisher, John W.; Pisharody, Suresh; Wignarajah, K.; Moran, Mark

2006-01-01

A wet pressurized pyrolysis (wet carbonization) process has been invented as a means of producing activated carbon from a wide variety of inedible biomass consisting principally of plant wastes. The principal intended use of this activated carbon is room-temperature adsorption of pollutant gases from cooled incinerator exhaust streams. Activated carbon is highly porous and has a large surface area. The surface area depends strongly on the raw material and the production process. Coconut shells and bituminous coal are the primary raw materials that, until now, were converted into activated carbon of commercially acceptable quality by use of traditional production processes that involve activation by use of steam or carbon dioxide. In the wet pressurized pyrolysis process, the plant material is subjected to high pressure and temperature in an aqueous medium in the absence of oxygen for a specified amount of time to break carbon-oxygen bonds in the organic material and modify the structure of the material to obtain large surface area. Plant materials that have been used in demonstrations of the process include inedible parts of wheat, rice, potato, soybean, and tomato plants. The raw plant material is ground and mixed with a specified proportion of water. The mixture is placed in a stirred autoclave, wherein it is pyrolized at a temperature between 450 and 590 F (approximately between 230 and 310 C) and a pressure between 1 and 1.4 kpsi (approximately between 7 and 10 MPa) for a time between 5 minutes and 1 hour. The solid fraction remaining after wet carbonization is dried, then activated at a temperature of 500 F (260 C) in nitrogen gas. The activated carbon thus produced is comparable to commercial activated carbon. It can be used to adsorb oxides of sulfur, oxides of nitrogen, and trace amounts of hydrocarbons, any or all of which can be present in flue gas. Alternatively, the dried solid fraction can be used, even without the activation treatment, to absorb

Supercritical synthesis and in situ deposition of PbS nanocrystals with oleic acid passivation for quantum dot solar cells

Energy Technology Data Exchange (ETDEWEB)

Tavakoli, M.M. [Department of Materials Science and Engineering, Sharif University of Technology, 14588 Tehran (Iran, Islamic Republic of); Simchi, A., E-mail: simchi@sharif.edu [Department of Materials Science and Engineering, Sharif University of Technology, 14588 Tehran (Iran, Islamic Republic of); Institute for Nanoscience and Nanotechnology, Sharif University of Technology, 14588 Tehran (Iran, Islamic Republic of); Aashuri, H. [Department of Materials Science and Engineering, Sharif University of Technology, 14588 Tehran (Iran, Islamic Republic of)

2015-04-15

Colloidal quantum dot solar cells have recently attracted significant attention due to their low-processing cost and surging photovoltaic performance. In this paper, a novel, reproducible, and simple solution-based process based on supercritical fluid toluene is presented for in situ growth and deposition PbS nanocrystals with oleic-acid passivation. A lead precursor containing sulfur was mixed with oleic acid in toluene and processed in a supercritical fluid condition at different temperatures of 140, 270 and 330 °C for 20 min. The quantum dots were deposited on a fluorine-doped tin oxide glass substrate inside the supercritical reactor. Transmission electron microscopy, X-ray diffraction, absorption and dynamic light scattering showed that the nanocrystals processed at the supercritical condition (330 °C) are fully crystalline with a narrow size distribution of ∼3 nm with an absorption wavelength of 915 nm (bandgap of 1.3 eV). Fourier transform infrared spectroscopy indicated that the PbS quantum dots are passivated by oleic acid molecules during the growth. Photovoltaic characteristics of Schottky junction solar cells showed an improvement over devices prepared by spin-coating. - Highlights: • Supercritical fluid processing and in situ deposition of PbS QDs are presented. • The prepared nanocrystals are mono-dispersed with an optical bandgap of 1.3 eV. • Photovoltaic performance of the in situ deposited nanocrystals is reported. • An improved PV performance compared to spin coated Schottky solar cells is shown.

Petroleum Refinery Effluents Treatment by Advanced Oxidation Process with Methanol

Energy Technology Data Exchange (ETDEWEB)

Shoucheng, Wen [Yangtze Univ., HuBei Jingzhou (China)

2014-02-15

Petroleum refinery effluents are waste originating from industries primarily engaged in refining crude oil. It is a very complex compound of various oily wastes, water, heavy metals and so on. Conventional processes are unable to effectively remove the chemical oxygen demand (COD) of petroleum refinery effluents. Supercritical water oxidation (SCWO) was proposed to treat petroleum refinery effluents. In this paper, methanol was used to investigate co-oxidative effect of methanol on petroleum refinery effluents treatment. The results indicated that supercritical water oxidation is an effective process for petroleum refinery effluents treatment. Adding methanol caused an increase in COD removal. When reaction temperature is 440 .deg. C, residence time is 20 min, OE is 0.5 and initial COD is 40000 mg/L, and COD removal increases 8.5%.

Petroleum Refinery Effluents Treatment by Advanced Oxidation Process with Methanol

International Nuclear Information System (INIS)

Shoucheng, Wen

2014-01-01

Petroleum refinery effluents are waste originating from industries primarily engaged in refining crude oil. It is a very complex compound of various oily wastes, water, heavy metals and so on. Conventional processes are unable to effectively remove the chemical oxygen demand (COD) of petroleum refinery effluents. Supercritical water oxidation (SCWO) was proposed to treat petroleum refinery effluents. In this paper, methanol was used to investigate co-oxidative effect of methanol on petroleum refinery effluents treatment. The results indicated that supercritical water oxidation is an effective process for petroleum refinery effluents treatment. Adding methanol caused an increase in COD removal. When reaction temperature is 440 .deg. C, residence time is 20 min, OE is 0.5 and initial COD is 40000 mg/L, and COD removal increases 8.5%

Supercritical Synthesis of Biodiesel

Directory of Open Access Journals (Sweden)

Michel Vaultier

2012-07-01

Full Text Available The synthesis of biodiesel fuel from lipids (vegetable oils and animal fats has gained in importance as a possible source of renewable non-fossil energy in an attempt to reduce our dependence on petroleum-based fuels. The catalytic processes commonly used for the production of biodiesel fuel present a series of limitations and drawbacks, among them the high energy consumption required for complex purification operations and undesirable side reactions. Supercritical fluid (SCF technologies offer an interesting alternative to conventional processes for preparing biodiesel. This review highlights the advances, advantages, drawbacks and new tendencies involved in the use of supercritical fluids (SCFs for biodiesel synthesis.

Enhanced Control of Mercury and other HAPs by Innovative Modifications to Wet FGD Processes

International Nuclear Information System (INIS)

Hargrove, O.W.; Carey, T.R.; Richardson, C.F.; Skarupa, R.C.; Meserole, F.B.; Rhudy, R.G.; Brown, Thomas D.

1997-01-01

The overall objective of this project was to learn more about controlling emissions of hazardous air pollutants (HAPs) from coal-fired power plants that are equipped with wet flue gas desulfurization (FGD) systems. The project was included by FETC as a Phase I project in its Mega-PRDA program. Phase I of this project focused on three research areas. These areas in order of priority were: (1) Catalytic oxidation of vapor-phase elemental mercury; (2) Enhanced particulate-phase HAPs removal by electrostatic charging of liquid droplets; and (3) Enhanced mercury removal by addition of additives to FGD process liquor. Mercury can exist in two forms in utility flue gas--as elemental mercury and as oxidized mercury (predominant form believed to be HgCl 2 ). Previous test results have shown that wet scrubbers effectively remove the oxidized mercury from the gas but are ineffective in removing elemental mercury. Recent improvements in mercury speciation techniques confirm this finding. Catalytic oxidation of vapor-phase elemental mercury is of interest in cases where a wet scrubber exists or is planned for SO 2 control. If a loW--cost process could be developed to oxidize all of the elemental mercury in the flue gas, then the maximum achievable mercury removal across the existing or planned wet scrubber would increase. Other approaches for improving control of HAPs included a method for improving particulate removal across the FGD process and the use of additives to increase mercury solubility. This paper discusses results related only to catalytic oxidation of elemental mercury

Supercritical heat transfer phenomena in nuclear system

International Nuclear Information System (INIS)

Seo, Kyoung Woo; Kim, Moo Hwan; Anderson, Mark H.; Corradini, Michael L.

2005-01-01

A supercritical water (SCW) power cycle has been considered as one of the viable candidates for advanced fission reactor designs. However, the dramatic variation of thermo-physical properties with a modest change of temperature near the pseudo-critical point make existing heat transfer correlations such as the Dittus-Boelter correlation not suitably accurate to calculate the heat transfer in supercritical fluid. Several other correlations have also been suggested but none of them are able to predict the heat transfer over a parameter range, needed for reactor thermal-hydraulics simulation and design. This has prompted additional research to understand the characteristic of supercritical fluid heat transfer

Synthesis of higher diamondoids by pulsed laser ablation plasmas in supercritical CO2

International Nuclear Information System (INIS)

Nakahara, Sho; Stauss, Sven; Kato, Toru; Terashima, Kazuo; Sasaki, Takehiko

2011-01-01

Pulsed laser ablation (wavelength 532 nm; fluence 18 J/cm 2 ; pulse width 7 ns; repetition rate 10 Hz) of highly oriented pyrolytic graphite was conducted in adamantane-dissolved supercritical CO 2 with and without cyclohexane as a cosolvent. Micro-Raman spectroscopy of the products revealed the presence of hydrocarbons possessing sp 3 -hybridized carbons similar to diamond structures. The synthesis of diamantane and other possible diamondoids consisting of up to 12 cages was confirmed by gas chromatography-mass spectrometry. Furthermore, gas chromatography-mass spectrometry measurements of samples before and after pyrolysis treatment indicate the synthesis of the most compact decamantane, namely, superadamantane. It is thought that oxidant species originating from CO 2 during pulsed laser ablation might lead to the selective dissociation of C-H bonds, enabling the synthesis of low H/C ratio molecules. Therefore, laser ablation in supercritical CO 2 is proposed as a practical method for synthesizing diamondoids.

Effect of supercritical fluid density on nanoencapsulated drug particle size using the supercritical antisolvent method.

Science.gov (United States)

Kalani, Mahshid; Yunus, Robiah

2012-01-01

The reported work demonstrates and discusses the effect of supercritical fluid density (pressure and temperature of supercritical fluid carbon dioxide) on particle size and distribution using the supercritical antisolvent (SAS) method in the purpose of drug encapsulation. In this study, paracetamol was encapsulated inside L-polylactic acid, a semicrystalline polymer, with different process parameters, including pressure and temperature, using the SAS process. The morphology and particle size of the prepared nanoparticles were determined by scanning electron microscopy and transmission electron microscopy. The results revealed that increasing temperature enhanced mean particle size due to the plasticizing effect. Furthermore, increasing pressure enhanced molecular interaction and solubility; thus, particle size was reduced. Transmission electron microscopy images defined the internal structure of nanoparticles. Thermal characteristics of nanoparticles were also investigated via differential scanning calorimetry. Furthermore, X-ray diffraction pattern revealed the changes in crystallinity structure during the SAS process. In vitro drug release analysis determined the sustained release of paracetamol in over 4 weeks.

Supercritical fluid extraction of uranium and thorium from nitric acid medium using organophosphorous compounds

Energy Technology Data Exchange (ETDEWEB)

Pitchaiah, K.C.; Sujatha, K.; Rao, C.V.S. Brahmmananda; Subramaniam, S.; Sivaraman, N.; Rao, P.R. Vasudeva [Indira Gandhi Centre for Atomic Research, Kalpakkam (India). Chemistry Group

2015-06-01

In recent years, Supercritical Fluid Extraction (SFE) technique has been widely used for the extraction of metal ions. In the present study, extraction of uranium from nitric acid medium was investigated using supercritical carbon dioxide (Sc-CO{sub 2}) containing various organophosphorous compounds such as trialkyl phosphates e.g. tri-iso-amyl phosphate (TiAP), tri-sec-butyl phosphate (TsBP) and tri-n-butyl phosphate (TBP), dialkylalkyl phosphonates, e.g. diamylamyl phosphonate (DAAP) and dibutyl butyl phosphonate (DBBP), dialkyl hydrogen phosphonates, e.g. dioctyl hydrogen phosphonate (DOHP), dioctylphosphineoxide (DOPO), trioctyl phosphine oxide (TOPO), n-octylphenyl N,N-diisobutyl carbamoylmethylphosphine oxide (CMPO) and di-2-ethyl-hexyl phosphoric acid (HDEHP). Some of these ligands have been investigated for the first time in the supercritical phase for the extraction of uranium. The extraction efficiency of uranium was studied with TiAP, DAAP and DBBP as a function of nitric acid concentration; the kinetics of the equilibration period (static extraction) and transportation of the metal complex (dynamic extraction) was investigated. The influence of pressure and temperature on the extraction behaviour of uranium with DAAP was studied from 4 N HNO{sub 3}. The extraction efficiency of uranium from 4 N nitric acid medium was found to increase in the order of phosphates < phosphonates < HDEHP < TOPO < CMPO. In the case of phosphates and phosphonates, the maximum extraction of uranium was found to be from 4 N HNO{sub 3} medium. The acidic extractants, HDEHP and DOHP showed relatively higher extraction at lower acidities. The relative extraction of uranium and thorium from their mixture was also examined using Sc-CO{sub 2} containing phosphates, phosphonates and TOPO. The ligand, TsBP provided better fractionation between uranium and thorium compared to trialkyl phosphates, dialkyl alkyl phosphonates and TOPO.

Nanotechnology and supercritical fluids | Hamidreza | Journal of ...

African Journals Online (AJOL)

Supercritical fluid (SCF) technology has become an important tool of materials processing in the last two decades. Supercritical CO2 and H2O are extensively being used in the preparation of a great variety of nanomaterials. The interest in the preparation and application of nanometer size materials is increasing since they ...

Supercritical fluid technology for energy and environmental applications

CERN Document Server

Anikeev, Vladimir

2014-01-01

Supercritical Fluid Technology for Energy and Environmental Applications covers the fundamental principles involved in the preparation and characterization of supercritical fluids (SCFs) used in the energy production and other environmental applications. Energy production from diversified resources - including renewable materials - using clean processes can be accomplished using technologies like SCFs. This book is focused on critical issues scientists and engineers face in applying SCFs to energy production and environmental protection, the innovative solutions they have found, and the challenges they need to overcome. The book also covers the basics of sub- and supercritical fluids, like the thermodynamics of phase and chemical equilibria, mathematical modeling, and process calculations. A supercritical fluid is any substance at a temperature and pressure above its critical point where distinct liquid and gas phases do not exist. At this state the compound demonstrates unique properties, which can be "fine...

Microstructural investigation of the oxide formed on TP 347H FG during long-term steam oxidation

DEFF Research Database (Denmark)

Hansson, Anette Nørgaard; Danielsen, Hilmar Kjartansson; Grumsen, Flemming Bjerg

2010-01-01

The long-term oxidation behaviour of TP347H FG in ultra supercritical steam conditions was assessed by exposing the steel in test superheater loops in a Danish coal-fired power plant and characterising the oxide layer with reflective light and electron microscopy. Double layered oxide scales formed...... during steam oxidation. TEM investigations reveal that the inner oxide layer consists of particles of metallic Ni/Fe and Fe-Cr spinel in the interior of the former alloy grains and a compact layer of Fe-Cr spinel and Cr2O3 along the former alloy grain boundaries. The morphology suggests that the inner...

Selective chelation and extraction of lanthanides and actinides with supercritical fluids

International Nuclear Information System (INIS)

Brauer, R.D.; Carleson, T.E.; Harrington, J.D.; Jean, F.; Jiang, H.; Lin, Y.; Wai, C.M.

1994-01-01

This report is made up of three independent papers: (1) Supercritical Fluid Extraction of Thorium and Uranium with Fluorinated Beta-Diketones and Tributyl Phosphate, (2) Supercritical Fluid Extraction of Lanthanides with Beta-Diketones and Mixed Ligands, and (3) A Group Contribution Method for Predicting the Solubility of Solid Organic Compounds in Supercritical Carbon Dioxide. Experimental data are presented demonstrating the successful extraction of thorium and uranium using fluorinated beta-diketones to form stable complexes that are extracted with supercritical carbon dioxide. The conditions for extracting the lanthanide ions from liquid and solid materials using supercritical carbon dioxide are presented. In addition, the Peng-Robison equation of state and thermodynamic equilibrium are used to predict the solubilities of organic solids in supercritical carbon dioxide from the sublimation pressure, critical properties, and a centric factor of the solid of interest

Supercritical carbon dioxide for textile applications and recent developments

Science.gov (United States)

Eren, H. A.; Avinc, O.; Eren, S.

2017-10-01

In textile industry, supercritical carbon dioxide (scCO2), possessing liquid-like densities, mostly find an application on textile dyeing processes such as providing hydrophobic dyes an advantage on dissolving. Their gas-like low viscosities and diffusion properties can result in shorter dyeing periods in comparison with the conventional water dyeing process. Supercritical carbon dioxide dyeing is an anhydrous dyeing and this process comprises the usage of less energy and chemicals when compared to conventional water dyeing processes leading to a potential of up to 50% lower operation costs. The advantages of supercritical carbon dioxide dyeing method especially on synthetic fiber fabrics hearten leading textile companies to alter their dyeing method to this privileged waterless dyeing technology. Supercritical carbon dioxide (scCO2) waterless dyeing is widely known and applied green method for sustainable and eco-friendly textile industry. However, not only the dyeing but also scouring, desizing and different finishing applications take the advantage of supercritical carbon dioxide (scCO2). In this review, not only the principle, advantages and disadvantages of dyeing in supercritical carbon dioxide but also recent developments of scCO2 usage in different textile processing steps such as scouring, desizing and finishing are explained and commercial developments are stated and summed up.

Effect of surface modification on the corrosion resistivity in supercritical water

International Nuclear Information System (INIS)

Penttila, S.; Horvath, A.; Toivonen, A.; Zolnai, Z.

2011-01-01

This paper summarizes the results of high temperature corrosion studies of the candidate austenitic alloys at relevant operating conditions for SCWR. The high temperature and pressure above the thermodynamic critical point of water result in higher oxidation rate which might be critical for thin-wall components like fuel cladding. The goal of this work was to study the effect of surface preparation on the oxidation rate on Ti-stabilized austenitic alloy 1.4970. Surfaces were prepared with ion implantation using He"+- and N"+-ions. Samples were immersed in supercritical water at 650"oC/25 MPa, for up to 2000 hours. Added to this, conventional surface treatments were conducted for austenitic alloy 316L tube samples in order to study the effect of cold work in sample surface on corrosion resistance. The corrosion rate was evaluated by measuring the weight change of the samples. The compositions of the oxide layers were analyzed using scanning electron microscope (SEM) in conjunction with Energy Dispersive Spectroscopy (EDS). (author)

Pore-scale observation and 3D simulation of wettability effects on supercritical CO2 - brine immiscible displacement in drainage

Science.gov (United States)

Hu, R.; Wan, J.; Chen, Y.

2016-12-01

Wettability is a factor controlling the fluid-fluid displacement pattern in porous media and significantly affects the flow and transport of supercritical (sc) CO2 in geologic carbon sequestration. Using a high-pressure micromodel-microscopy system, we performed drainage experiments of scCO2 invasion into brine-saturated water-wet and intermediate-wet micromodels; we visualized the scCO2 invasion morphology at pore-scale under reservoir conditions. We also performed pore-scale numerical simulations of the Navier-Stokes equations to obtain 3D details of fluid-fluid displacement processes. Simulation results are qualitatively consistent with the experiments, showing wider scCO2 fingering, higher percentage of scCO2 and more compact displacement pattern in intermediate-wet micromodel. Through quantitative analysis based on pore-scale simulation, we found that the reduced wettability reduces the displacement front velocity, promotes the pore-filling events in the longitudinal direction, delays the breakthrough time of invading fluid, and then increases the displacement efficiency. Simulated results also show that the fluid-fluid interface area follows a unified power-law relation with scCO2 saturation, and show smaller interface area in intermediate-wet case which suppresses the mass transfer between the phases. These pore-scale results provide insights for the wettability effects on CO2 - brine immiscible displacement in geologic carbon sequestration.

Industrial applications and current trends in supercritical fluid technologies

OpenAIRE

Gamse Thomas

2005-01-01

Supercritical fluids have a great potential for wide fields of processes Although CO2 is still one of the most used supercritical gases, for special purposes propane or even fluorinated-chlorinated fluids have also been tested. The specific characteristics of supercritical fluids behaviour were analyzed such as for example the solubilities of different components and the phase equilibria between the solute and solvent. The application at industrial scale (decaffeinating of tea and coffee, hop...

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.

Steamside Oxidation Behavior of Experimental 9%Cr Steels

Energy Technology Data Exchange (ETDEWEB)

Dogan, O.N.; Holcomb, G.R.; Alman, D.E.; Jablonski, P.D.

2007-10-01

Reducing emissions and increasing economic competitiveness require more efficient steam power plants that utilize fossil fuels. One of the major challenges in designing these plants is the availability of materials that can stand the supercritical and ultra-supercritical steam conditions at a competitive cost. There are several programs around the world developing new ferritic and austenitic steels for superheater and reheater tubes exposed to the advanced steam conditions. The new steels must possess properties better than current steels in terms of creep strength, steamside oxidation resistance, fireside corrosion resistance, and thermal fatigue resistance. This paper introduces a series of experimental 9%Cr steels containing Cu, Co, and Ti. Stability of the phases in the new steels is discussed and compared to the phases in the commercially available materials. The steels were tested under both the dry and moist conditions at 650ºC for their cyclical oxidation resistance. Results of oxidation tests are presented. Under the moist conditions, the experimental steels exhibited significantly less mass gain compared to the commercial P91 steel. Microstructural characterization of the scale revealed different oxide compositions.

Supercritical fluid analytical methods

International Nuclear Information System (INIS)

Smith, R.D.; Kalinoski, H.T.; Wright, B.W.; Udseth, H.R.

1988-01-01

Supercritical fluids are providing the basis for new and improved methods across a range of analytical technologies. New methods are being developed to allow the detection and measurement of compounds that are incompatible with conventional analytical methodologies. Characterization of process and effluent streams for synfuel plants requires instruments capable of detecting and measuring high-molecular-weight compounds, polar compounds, or other materials that are generally difficult to analyze. The purpose of this program is to develop and apply new supercritical fluid techniques for extraction, separation, and analysis. These new technologies will be applied to previously intractable synfuel process materials and to complex mixtures resulting from their interaction with environmental and biological systems

Thermal aspects of mixed oxide fuel in application to supercritical water-cooled nuclear reactors

Energy Technology Data Exchange (ETDEWEB)

Grande, L.; Peiman, W.; Rodriguez-Prado, A.; Villamere, B.; Mikhael, S.; Allison, L.; Pioro, I., E-mail: lisa.grande@mycampus.uoit.ca, E-mail: igor.pioro@uoit.ca [Univ. of Ontario Inst. of Tech., Faculty of Energy Systems and Nuclear Science, Oshawa, Ontario (Canada)

2010-07-01

SuperCritical Water-cooled nuclear Reactors (SCWRs) are a renewed technology being developed as one of the Generation IV reactor concepts. This reactor type uses a light water coolant at temperatures and pressures above its critical point. These elevated operating conditions will improve Nuclear Power Plant (NPP) thermal efficiencies by 10 - 15% compared to those of current NPPs. Also, SCWRs will have the ability to utilize a direct cycle, thus decreasing NPP capital and operational costs. The SCWR core has 2 configurations: 1) Pressure Vessel (PV) -type enclosing a fuel assembly and 2) Pressure Tube (PT) -type consisting of individual pressurized channels containing fuel bundles. Canada and Russia are developing PT-type SCWRs. In particular, the Canadian SCWR reactor has an output of 1200 MW{sub el} and will operate at a pressure of 25 MPa with inlet and outlet fuel-channel temperatures of 350 and 625°C, respectively. These extreme operating conditions require alternative fuels and materials to be investigated. Current CANadian Deuterium Uranium (CANDU) nuclear reactor fuel-channel design is based on the use of uranium dioxide (UO{sub 2}) fuel; zirconium alloy sheath (clad) bundle, pressure and calandria tubes. Alternative fuels should be considered to supplement depleting world uranium reserves. This paper studies general thermal aspects of using Mixed OXide (MOX) fuel in an Inconel-600 sheath in a generic PT-type SCWR. The bulk fluid, sheath and fuel centerline temperatures along with the Heat Transfer Coefficient (HTC) profiles were calculated at uniform and non-uniform Axial Heat Flux Profiles (AHFPs). (author)

Structural behavior of supercritical fluids under confinement

Science.gov (United States)

Ghosh, Kanka; Krishnamurthy, C. V.

2018-01-01

The existence of the Frenkel line in the supercritical regime of a Lennard-Jones (LJ) fluid shown through molecular dynamics (MD) simulations initially and later corroborated by experiments on argon opens up possibilities of understanding the structure and dynamics of supercritical fluids in general and of the Frenkel line in particular. The location of the Frenkel line, which demarcates two distinct physical states, liquidlike and gaslike within the supercritical regime, has been established through MD simulations of the velocity autocorrelation (VACF) and radial distribution function (RDF). We, in this article, explore the changes in the structural features of supercritical LJ fluid under partial confinement using atomistic walls. The study is carried out across the Frenkel line through a series of MD simulations considering a set of thermodynamics states in the supercritical regime (P =5000 bar, 240 K ≤T ≤1500 K ) of argon well above the critical point. Confinement is partial, with atomistic walls located normal to z and extending to "infinity" along the x and y directions. In the "liquidlike" regime of the supercritical phase, particles are found to be distributed in distinct layers along the z axis with layer spacing less than one atomic diameter and the lateral RDF showing amorphous-like structure for specific spacings (packing frustration) and non-amorphous-like structure for other spacings. Increasing the rigidity of the atomistic walls is found to lead to stronger layering and increased structural order. For confinement with reflective walls, layers are found to form with one atomic diameter spacing and the lateral RDF showing close-packed structure for the smaller confinements. Translational order parameter and excess entropy assessment confirms the ordering taking place for atomistic wall and reflective wall confinements. In the "gaslike" regime of the supercritical phase, particle distribution along the spacing and the lateral RDF exhibit features

Corrosion mechanism of a Ni-based alloy in supercritical water: Impact of surface plastic deformation

International Nuclear Information System (INIS)

Payet, Mickaël; Marchetti, Loïc; Tabarant, Michel; Chevalier, Jean-Pierre

2015-01-01

Highlights: • The dissolution of Ni and Fe cations occurs during corrosion of Ni-based alloys in SCW. • The nature of the oxide layer depends locally on the alloy microstructure. • The corrosion mechanism changes when cold-work increases leading to internal oxidation. - Abstract: Ni–Fe–Cr alloys are expected to be a candidate material for the generation IV nuclear reactors that use supercritical water at temperatures up to 600 °C and pressures of 25 MPa. The corrosion resistance of Alloy 690 in these extreme conditions was studied considering the surface finish of the alloy. The oxide scale could suffer from dissolution or from internal oxidation. The presence of a work-hardened zone reveals the competition between the selective oxidation of chromium with respect to the oxidation of nickel and iron. Finally, corrosion mechanisms for Ni based alloys are proposed considering the effects of plastically deformed surfaces and the dissolution.

Molecular Simulation Study of Montmorillonite in Contact with Variably Wet Supercritical Carbon Dioxide

KAUST Repository

Kadoura, Ahmad Salim

2017-03-07

We perform grand canonical Monte Carlo simulations to study the detailed molecular mechanism of intercalation behavior of CO2 in Na-, Ca-, and Mg- montmorillonite exposed to variably hydrated supercritical CO2 at 323.15 K and 90 bar, The simulations indicate that the intercalation of CO2 strongly depends on the relative humidity (RH). The intercalation of CO2 in the dehydrated interlayer is inhibited, followed by the swelling of the interlayer region due to uptake of water and CO2 as the RH increases. In all of the hydrated clay samples, the amount of the intercalated CO2 generally decreases as a function of increasing RH, which is attributed mainly to the weakening of the interaction between CO2 and clay. At low RH values, Ca- and Mg- montmorillonite are relatively more efficient in capturing CO2. The amount of CO2 trapped in all clay samples shows similar values above RH of similar to 60%. Molecular dynamics simulations show that the diffusion coefficient of each species generally increases with increasing RH due to the associated expansion of the interlayer distance of the clay. For all the hydrated samples, the diffusion coefficients of CO2 and water in the interlayers are mostly comparable due to the fact that CO2 molecules are well solvated. The diffusion of CO2 in each hydration state is mostly independent of the type of cation in accordance with the fact that CO2 molecules hardly migrate into the first hydration shell of the interlayer cations.

Au/Graphene Oxide Nanocomposite Synthesized in Supercritical CO2 Fluid as Energy Efficient Lubricant Additive.

Science.gov (United States)

Meng, Yuan; Su, Fenghua; Chen, Yangzhi

2017-11-15

Au nanoparticles are successfully decorated onto graphene oxide (GO) sheets with the aid of supercritical carbon dioxide (ScCO 2 ) fluid. The synthesized nanocomposite (Sc-Au/GO) was characterized by X-ray diffraction (XRD), Raman spectroscopy, thermal gravimetric analysis (TGA), and transmission electron microscopy (TEM). The characterization results show that the Au nanoparticles are featured with face-centered cubic crystal structure and disperse well on the GO nanosheet surfaces with average diameters of 4-10 nm. The tribological behaviors of Sc-Au/GO as lubricating additive in PAO6 oil were investigated using a ball-on-disc friction tester, and a control experiment by respectively adding GO, nano-Au particles, and Au/GO produced in the absence of ScCO 2 was performed as well. It is found that Sc-Au/GO exhibits the best lubricating performances among all the samples tested. When 0.10 wt % Sc-Au/GO is dispersed into PAO6 oil, the friction coefficient and wear rate are respectively reduced by 33.6% and 72.8% as compared to that of the pure PAO6 oil, indicating that Sc-Au/GO is an energy efficient lubricant additive. A possible lubricating mechanism of Sc-Au/GO additive in PAO6 oil has been tentatively proposed on the basis of the analyzed results of the worn surface examined by scanning electron microscopy (SEM), Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS).

High performance supercapacitor using N-doped graphene prepared via supercritical fluid processing with an oxime nitrogen source

International Nuclear Information System (INIS)

Balaji, S. Suresh; Elavarasan, A.; Sathish, M.

2016-01-01

Graphical abstract: N-doped graphene prepared via supercritical fluid processing with oxime nitrogen source (DMG) showed enhanced performance in electrochemical supercapacitor application. A maximum specific capacitance of 286 F g"−"1 at a current density of 0.5 A/g was achieved with a high specific capacity retention of 98% after 1000 cycles at 5 A/g. - Highlights: • N-functionalised graphene synthesized via supercritical fluid processing. • DMG, an oxime based nitrogen precursor. • Maximum specific capacitance of 286 F/g at 0.5 A/g in aqueous solution. • Pyridinic as well as quarternary nitrogen for enhanced capacitance. - Abstract: Heteroatom doped graphene has been proved for its promising applications in electrochemical energy storage systems. Here, nitrogen (N) doped graphene was prepared via two different techniques namely supercritical fluid assisted processing and hydrothermal heat treatment using dimethylglyoxime (DMG) as an oxime nitrogen precursor. The FT-IR and Raman spectra showed the N-containing functional group in the graphene. The XRD analysis revealed the complete reduction of graphene oxide during the supercritical fluid processing. The elemental analysis and X-ray photoelectron spectroscopy revealed the amount and nature of N-doping in the graphene, respectively. The surface morphology and physical nature of the samples were analyzed using scanning and transmission electron microscopic analysis. The electrochemical performance of prepared electrode materials was evaluated using cyclic voltammetry, galvanostatic charge-discharge analysis and electrochemical impedance spectroscopy. The N-doped graphene prepared via supercritical fluid assisted processing exhibit enhanced capacitive behaviour with a maximum specific capacitance of 286 F g"−"1 at a current density of 0.5 A/g. The cycling studies showed 98% specific capacity retention with 100% coulombic efficiency over 1000 cycles at 5 A/g. The enhanced specific capacitance of N

Determination of major aromatic constituents in vanilla using an on-line supercritical fluid extraction coupled with supercritical fluid chromatography.

Science.gov (United States)

Liang, Yanshan; Liu, Jiaqi; Zhong, Qisheng; Shen, Lingling; Yao, Jinting; Huang, Taohong; Zhou, Ting

2018-04-01

An on-line supercritical fluid extraction coupled with supercritical fluid chromatography method was developed for the determination of four major aromatic constituents in vanilla. The parameters of supercritical fluid extraction were systematically investigated using single factor optimization experiments and response surface methodology by a Box-Behnken design. The modifier ratio, split ratio, and the extraction temperature and pressure were the major parameters which have significant effects on the extraction. While the static extraction time, dynamic extraction time, and recycle time had little influence on the compounds with low polarity. Under the optimized conditions, the relative extraction efficiencies of all the constituents reached 89.0-95.1%. The limits of quantification were in the range of 1.123-4.747 μg. The limits of detection were in the range of 0.3368-1.424 μg. The recoveries of the four analytes were in the range of 76.1-88.9%. The relative standard deviations of intra- and interday precision ranged from 4.2 to 7.6%. Compared with other off-line methods, the present method obtained higher extraction yields for all four aromatic constituents. Finally, this method has been applied to the analysis of vanilla from different sources. On the basis of the results, the on-line supercritical fluid extraction-supercritical fluid chromatography method shows great promise in the analysis of aromatic constituents in natural products. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Oxidation Behavior of Mo-Si-B Alloys in Wet Air; TOPICAL

International Nuclear Information System (INIS)

M. Kramer; A. Thom; O. Degirmen; V. Behrani; M. Akinc

2002-01-01

Multiphase composite alloys based on the Mo-Si-B system are candidate materials for ultra-high temperature applications. In non load-bearing uses such as thermal barrier coatings or heat exchangers in fossil fuel burners, these materials may be ideally suited. The present work investigated the effect of water vapor on the oxidation behavior of Mo-Si-B phase assemblages. Three alloys were studied: Alloy 1= Mo(sub 5)Si(sub 3)B(sub x) (T1)- MoSi(sub 2)- MoB, Alloy 2= T1- Mo(sub 5)SiB(sub 2) (T2)- Mo(sub 3)Si, and Alloy 3= Mo- T2- Mo(sub 3)Si. Tests were conducted at 1000 and 1100C in controlled atmospheres of dry air and wet air nominally containing 18, 55, and 150 Torr H(sub 2)O. The initial mass loss of each alloy was approximately independent of the test temperature and moisture content of the atmosphere. The magnitude of these initial losses varied according to the Mo content of the alloys. All alloys formed a continuous, external silica scale that protected against further mass change after volatilization of the initially formed MoO(sub 3). All alloys experienced a small steady state mass change, but the calculated rates cannot be quantitatively compared due to statistical uncertainty in the individual mass measurements. Of particular interest is that Alloy 3, which contains a significant volume fraction of Mo metal, formed a protective scale. All alloys formed varying amounts of subscale Mo and MoO(sub 2). This implies that oxygen transport through the external silica scale has been significantly reduced. For all alloys, water vapor accelerated the growth of a multiphase interlayer at the silica scale/unoxidized alloy interface. This interlayer is likely composed of fine Mo and MoO(sub 2) that is dispersed within a thin silica matrix. Alloy 3 was particularly sensitive to water accelerated growth of this interlayer. At 1100 C, the scale thickness after 300 hours increased from about 20 mm in dry air to nearly 100 mm in wet air

Heat Transfer Phenomena of Supercritical Fluids

Energy Technology Data Exchange (ETDEWEB)

Krau, Carmen Isabella; Kuhn, Dietmar; Schulenberg, Thomas [Forschungszentrum Karlsruhe, Institute for Nuclear and Energy Technologies, 76021 Karlsruhe (Germany)

2008-07-01

In concepts for supercritical water cooled reactors, the reactor core is cooled and moderated by water at supercritical pressures. The significant temperature dependence of the fluid properties of water requires an exact knowledge of the heat transfer mechanism to avoid fuel pin damages. Near the pseudo-critical point a deterioration of heat transfer might happen. Processes, that take place in this case, are not fully understood and are due to be examined systematically. In this paper a general overview on the properties of supercritical water is given, experimental observations of different authors will be reviewed in order to identify heat transfer phenomena and onset of occurrence. The conceptional design of a test rig to investigate heat transfer in the boundary layer will be discussed. Both, water and carbon dioxide, may serve as operating fluids. The loop, including instrumentation and safety devices, is shown and suitable measuring methods are described. (authors)

Upgrading of bitumen using supercritical water

Energy Technology Data Exchange (ETDEWEB)

Kayukawa, T. [JGC Corp., Ibaraki (Japan)

2009-07-01

This presentation outlined the technical and economic aspects of thermal cracking by supercritical water. Supercritical water (SCW) is a commonly used method for upgrading heavy oil to produce pipeline-transportable oil from high-viscous bitumen. The process uses water and does not require hydrogen nor catalysts. Pre-heated bitumen and water enter a vertical reactor with flows of counter current at the supercritical point of water. The upgraded synthetic crude oil (SCO) and pitch are obtained from the top of the reactor when the bitumen is thermally cracked. Bench-scale studies have shown that Canadian oil sands bitumen can be converted to 80 volume per cent of SCO and 20 volume per cent of pitch. The SCO has satisfied Canadian pipeline specifications in terms of API gravity and kinetic viscosity. The kinetic viscosity of the pitch has also satisfied boiler fuel specifications. tabs., figs.

Updated heat transfer correlations for supercritical water-cooled reactor applications

International Nuclear Information System (INIS)

Mokry, S.J.; Pioro, I.L.; Farah, A.; King, K.

2011-01-01

In support of the development of SuperCritical Water-cooled Reactors (SCWRs), research is currently being conducted for heat-transfer at supercritical conditions. Currently, there are no experimental datasets for heat transfer from power reactor fuel bundles to the fuel coolant (Water) available in open literature. Therefore, for preliminary calculations, heat-transfer correlations obtained with bare tube data can be used as a conservative approach. A large set of experimental data, for supercritical water was analyzed and an updated heat-transfer correlation for forced-convective heat-transfer, in the normal heat transfer regime, was developed. This experimental dataset was obtained within conditions similar to those for proposed SCWR concepts. Thus, this new correlation can be used for preliminary heat-transfer calculations in SCWR fuel channels. It has demonstrated a good fit for the analyzed dataset. Experiments with SuperCritical Water (SCW) are very expensive. Therefore, a number of experiments are performed in modeling fluids, such as carbon dioxide and refrigerants. However, there is no common opinion if SC modeling fluids' correlations can be applied to SCW and vice versa. Therefore, a correlation for supercritical carbon dioxide heat transfer was developed as a less expensive alternative to using supercritical water. The conducted analysis also meets the objective of improving our fundamental knowledge of the transport processes and handling of supercritical fluids. These correlations can be used for supercritical water heat exchangers linked to indirect-cycle concepts and the cogeneration of hydrogen, for future comparisons with other independent datasets, with bundle data, for the verification of computer codes for SCWR core thermalhydraulics and for the verification of scaling parameters between water and modeling fluids. (author)

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.

Influence of Minor Alloying Elements on Selective Oxidation and Reactive Wetting of CMnSi TRIP Steel during Hot Dip Galvanizing

Science.gov (United States)

Cho, Lawrence; Kim, Myung Soo; Kim, Young Ha; De Cooman, Bruno C.

2014-09-01

The influence of the addition of minor alloying elements on the selective oxidation and the reactive wetting of CMnSi transformation-induced plasticity (TRIP) steels was studied by means of galvanizing simulator tests. Five TRIP steels containing small alloying additions of Cr, Ni, Ti, Cu, and Sn were investigated. After intercritical annealing (IA) at 1093 K (820 °C) in a N2 + 5 pct H2 gas atmosphere with a dew point of 213 K (-60 °C), two types of oxides were formed on the strip surface: Mn-rich xMnO·SiO2 ( x > 1.5) and Si-rich xMnO·SiO2 ( x galvanizing. The addition of a small amount of Sn is shown to significantly decrease the density of Zn-coating defects on CMnSi TRIP steels.

A finite-dimensional reduction method for slightly supercritical elliptic problems

Directory of Open Access Journals (Sweden)

Riccardo Molle

2004-01-01

Full Text Available We describe a finite-dimensional reduction method to find solutions for a class of slightly supercritical elliptic problems. A suitable truncation argument allows us to work in the usual Sobolev space even in the presence of supercritical nonlinearities: we modify the supercritical term in such a way to have subcritical approximating problems; for these problems, the finite-dimensional reduction can be obtained applying the methods already developed in the subcritical case; finally, we show that, if the truncation is realized at a sufficiently large level, then the solutions of the approximating problems, given by these methods, also solve the supercritical problems when the parameter is small enough.

Development of Nuclear Decontamination Technology Using Supercritical Fluid

Energy Technology Data Exchange (ETDEWEB)

Jung, Wonyoung; Park, Kwangheon; Park, Jihye; Lee, Donghee [Kyunghee Univ., Yongin (Korea, Republic of)

2014-05-15

Soil cleaning technologies that have been developed thus far increase treatment costs in contaminated soil recovery processes because they generate large amounts of secondary wastes. In this respect, this study is intended to develop soil decontamination methods using CO{sub 2}, which is a nontoxic, environmentally friendly substance, in order to fundamentally suppress the generation of secondary wastes from the decontamination process and to create high added values. In this study, to develop decontamination methods for uranium-contaminated soil using supercritical CO{sub 2}, a soil decontamination system using supercritical CO{sub 2} was constructed. In addition, the basic principle of supercritical CO{sub 2} decontamination using a TBP-HNO3 complex was explained. According to the results of the study, sea-sand samples having the same degree of contamination showed different results of decontamination according to the quantities of the TBP-HNO3 complex used as an extraction agent, which resulted in high extraction rates. Thus far, a most widely used method of extracting uranium has been the dissolving of uranium in acids. However, this method has the large adverse effect of generating strong acidic wastes that cannot be easily treated. On the other hand, supercritical CO{sub 2} requires critical conditions that are no more difficult to meet than those of other supercritical fluids, since its density can be changed from a very low state close to that of an ideal gas to a high state close to that of liquids. The critical gas conditions are a pressure of 71 bar and a temperature of 31 .deg. C, both of which are inexpensive to achieve. Moreover, CO{sub 2} is a solvent that is not harmful to the human body and few effects on environmental pollution. Therefore, nontoxic and environment friendly processes can be developed using supercritical CO{sub 2}. Supercritical CO{sub 2}'s advantages over prevailing methods suggest its potential for developing innovative

Development of Nuclear Decontamination Technology Using Supercritical Fluid

International Nuclear Information System (INIS)

Jung, Wonyoung; Park, Kwangheon; Park, Jihye; Lee, Donghee

2014-01-01

Soil cleaning technologies that have been developed thus far increase treatment costs in contaminated soil recovery processes because they generate large amounts of secondary wastes. In this respect, this study is intended to develop soil decontamination methods using CO 2 , which is a nontoxic, environmentally friendly substance, in order to fundamentally suppress the generation of secondary wastes from the decontamination process and to create high added values. In this study, to develop decontamination methods for uranium-contaminated soil using supercritical CO 2 , a soil decontamination system using supercritical CO 2 was constructed. In addition, the basic principle of supercritical CO 2 decontamination using a TBP-HNO3 complex was explained. According to the results of the study, sea-sand samples having the same degree of contamination showed different results of decontamination according to the quantities of the TBP-HNO3 complex used as an extraction agent, which resulted in high extraction rates. Thus far, a most widely used method of extracting uranium has been the dissolving of uranium in acids. However, this method has the large adverse effect of generating strong acidic wastes that cannot be easily treated. On the other hand, supercritical CO 2 requires critical conditions that are no more difficult to meet than those of other supercritical fluids, since its density can be changed from a very low state close to that of an ideal gas to a high state close to that of liquids. The critical gas conditions are a pressure of 71 bar and a temperature of 31 .deg. C, both of which are inexpensive to achieve. Moreover, CO 2 is a solvent that is not harmful to the human body and few effects on environmental pollution. Therefore, nontoxic and environment friendly processes can be developed using supercritical CO 2 . Supercritical CO 2 's advantages over prevailing methods suggest its potential for developing innovative decontamination methods, as demonstrated

Influence of Gas Atmosphere Dew Point on the Selective Oxidation and the Reactive Wetting During Hot Dip Galvanizing of CMnSi TRIP Steel

Science.gov (United States)

Cho, Lawrence; Lee, Seok Jae; Kim, Myung Soo; Kim, Young Ha; De Cooman, Bruno C.

2013-01-01

The selective oxidation and reactive wetting of intercritically annealed Si-bearing CMnSi transformation-induced plasticity steels were investigated by high-resolution transmission electron microscopy. In a N2 + 10 pct H2 gas atmosphere with a dew point (DP) ranging from 213 K to 278 K (-60 °C to 5 °C), a continuous layer of selective oxides was formed on the surface. Annealing in a higher DP gas atmosphere resulted in a thinner layer of external oxidation and a greater depth of internal oxidation. The hot dipping was carried out in a Zn bath containing 0.22 mass pct Al, and the bath temperature was 733 K (460 °C). Coarse and discontinuous Fe2Al5- x Zn x grains and Fe-Zn intermetallics (ζ and δ) were observed at the steel/coating interface after the hot dip galvanizing (HDG) of panels were annealed in a low DP atmosphere 213 K (-60 °C). The Fe-Zn intermetallics were formed both in areas where the Fe2Al5- x Zn x inhibition layer had not been formed and on top of non-stoichiometric Fe-Al-Zn crystals. Poor wetting was observed on panels annealed in a low DP atmosphere because of the formation of thick film-type oxides on the surface. After annealing in higher DP gas atmospheres, i.e., 263 K and 278 K (-10 °C and 5 °C), a continuous and fine-grained Fe2Al5- x Zn x layer was formed. No Fe-Zn intermetallics were formed. The small grain size of the inhibition layer was attributed to the nucleation of the Fe2Al5- x Zn x grains on small ferrite sub-surface grains and the presence of granular surface oxides. A high DP atmosphere can therefore significantly contribute to the decrease of Zn-coating defects on CMnSi TRIP steels processed in HDG lines.

Chemical deposition methods using supercritical fluid solutions

Science.gov (United States)

Sievers, Robert E.; Hansen, Brian N.

1990-01-01

A method for depositing a film of a desired material on a substrate comprises dissolving at least one reagent in a supercritical fluid comprising at least one solvent. Either the reagent is capable of reacting with or is a precursor of a compound capable of reacting with the solvent to form the desired product, or at least one additional reagent is included in the supercritical solution and is capable of reacting with or is a precursor of a compound capable of reacting with the first reagent or with a compound derived from the first reagent to form the desired material. The supercritical solution is expanded to produce a vapor or aerosol and a chemical reaction is induced in the vapor or aerosol so that a film of the desired material resulting from the chemical reaction is deposited on the substrate surface. In an alternate embodiment, the supercritical solution containing at least one reagent is expanded to produce a vapor or aerosol which is then mixed with a gas containing at least one additional reagent. A chemical reaction is induced in the resulting mixture so that a film of the desired material is deposited.

Optical wave microphone measurements of laser ablation of copper in supercritical carbon dioxide

Energy Technology Data Exchange (ETDEWEB)

Mitsugi, Fumiaki, E-mail: mitsugi@cs.kumamoto-u.ac.jp [Graduate School of Science and Technology, Kumamoto University, 2-39-1 Kurokami, Kumamoto 860-8555 (Japan); Ikegami, Tomoaki [Graduate School of Science and Technology, Kumamoto University, 2-39-1 Kurokami, Kumamoto 860-8555 (Japan); Nakamiya, Toshiyuki; Sonoda, Yoshito [Graduate School of Industrial Engineering, Tokai University, 9-1-1 Toroku, Kumamoto 862-8652 (Japan)

2013-11-29

Laser ablation plasma in a supercritical fluid has attracted much attention recently due to its usefulness in forming nanoparticles. Observation of the dynamic behavior of the supercritical fluid after laser irradiation of a solid is necessary for real-time monitoring and control of laser ablation. In this study, we utilized an optical wave microphone to monitor pulsed laser irradiation of a solid in a supercritical fluid. The optical wave microphone works based on Fraunhofer diffraction of phase modulation of light by changes in refractive index. We hereby report on our measurements for pulsed laser irradiation of a Cu target in supercritical carbon dioxide using an optical wave microphone. Photothermal acoustic waves which generated after single pulsed laser irradiation of a Cu target were detectable in supercritical carbon dioxide. The speed of sound around the critical point of supercritical carbon dioxide was clearly slower than that in gas. The optical wave microphone detected a signal during laser ablation of Cu in supercritical carbon dioxide that was caused by shockwave degeneration. - Highlights: • Photothermal acoustic wave in supercritical fluid was observed. • Sound speed around the critical point was slower than that in gas. • Optical wave microphone detected degeneration of a shockwave. • Ablation threshold of a solid in supercritical fluid can be estimated. • Generation of the second shockwave in supercritical phase was suggested.

Hydrolysis of Miscanthus for bioethanol production using dilute acid presoaking combined with wet explosion pre-treatment and enzymatic treatment

DEFF Research Database (Denmark)

Sørensen, Annette; Teller, Philip Johan; Hilstrøm, Troels

2008-01-01

xylose prior to wet explosion. The acid presoaking extracted 63.2% xylose and 5.2% glucose. Direct enzymatic hydrolysis of the presoaked biomass was found to give only low sugar yields of 24-26% glucose. Wet explosion is a pre-treatment method that combines wet-oxidation and steam explosion. The effect...... of wet explosion on non-presoaked and presoaked Miscanthus was investigated using both atmospheric air and hydrogen peroxide as the oxidizing agent. All wet explosion pre-treatments showed to have a disrupting effect on the lignocellulosic biomass, making the sugars accessible for enzymatic hydrolysis......Miscanthus is a high yielding bioenergy crop. In this study we used acid presoaking, wet explosion, and enzymatic hydrolysis to evaluate the combination of the different pre-treatment methods for bioethanol production with Miscanthus. Acid presoaking is primarily carried out in order to remove...

Environmentally benign destruction of waste energetic materials (EMs)

International Nuclear Information System (INIS)

Schneider, R. L.; Donahue, B. A.

1998-01-01

Studies by the U. S. Army Corps of Engineers during 1991-1997 involving various methods for the destruction of waste generated by pyrotechnic, explosive and propellant materials are described. The methods assessed and evaluated include controlled incineration (CI), wet air oxidation (WAO), and hydrothermal oxidation (HTO), using a U.S. Army triple-base propellant as the initial common standard for all destructor comparative testing. All three of these methods has special feed line restrictions requiring mechanical diminution and comminution of the energetic material which, for safety reasons, cannot be used with contaminated heterogeneous production wastes. Supercritical fluid extraction with carbon dioxide, alkaline hydrolysis, electrolysis and fluid cutting with very high pressure water jets and liquid nitrogen are alternate technologies that were evaluated as pre-treatment for production wastes. Wet air oxidation and electrochemical reduction studies were conducted using the U.S. Navy double propellant NOSIH-AA2, which contains a lead-based ballistic modifier. Wet air oxidation and hydrothermal oxidation studies were done using potassium dinitramide phase-stabilized nitrate as an oxidizer. All of these technologies are considered to be suitable for the environmentally benign destruction of pyrotechnic materials, including fireworks. 17 refs., 8 tabs., 4 figs

Experimental studies of applicability of the wet air oxidation for purification liquid radioactive waste

International Nuclear Information System (INIS)

Sergienko, V. I.; Dobrzansky, V. G.

2005-01-01

The scheme of handling with liquid radioactive waste (LRW) accepted to exploitation at atomic electric station (AWS) is often connected with evaporating technologies. In this case vat residues of evaporating systems with activity 10 5 -10 6 Bq/1 and containing to 200-300 g/1 of salts are delivered up to LRW storages for lasting keeping. This schema does not correlate to the modern safety standards of handling with LRW, therefore at present numerous works are being carried on including those using technology of accumulated vat residues processing. Some successful experiments on sorption purification of high-salt LRW from cesium radionuclides giving the principal contribution into the total activity of a certain LRW are known. Unfortunately, attempts of sorption purification of the vat residues from other long-lived radionuclides (mainly from 60 Co-radionuclide) were unsuccessful up to the present time. It is found with the fact that the vat residues contain a considerable amount of complexing agent producing stable complexes with transition metal radionuclides including those of 60 Co. Extreme oxidation of the vat residues for decomposition of radioactive organic complexes is one of the solutions of this problem. The works related to oxidation of LRW including the AES vat residues with ozone, hydrogen peroxide as well as photo catalytic and electrochemical oxidation are known, however, possibilities of wet air oxidation (WAO) for LRW processing are not studied till the present time. Condition for decomposition of cobalt complex compounds and necessary excess of oxidizing agent may be easily attained with WAO usage. The necessary experiments were carried out at the experimental plant with the great interface surface (oxygen-solutions) equal to 400m -1 and 3 mm probe bed thickness. The heating time of the reactor to the working temperature 250 .deg. C did not exceed 50 seconds. 20... 50-fold oxidizer excess was achieved by the initial oxygen pressure into the reactor

High Density Thermal Energy Storage with Supercritical Fluids

Science.gov (United States)

Ganapathi, Gani B.; Wirz, Richard

2012-01-01

A novel approach to storing thermal energy with supercritical fluids is being investigated, which if successful, promises to transform the way thermal energy is captured and utilized. The use of supercritical fluids allows cost-affordable high-density storage with a combination of latent heat and sensible heat in the two-phase as well as the supercritical state. This technology will enhance penetration of several thermal power generation applications and high temperature water for commercial use if the overall cost of the technology can be demonstrated to be lower than the current state-of-the-art molten salt using sodium nitrate and potassium nitrate eutectic mixtures.

Selective free radical reactions using supercritical carbon dioxide.

Science.gov (United States)

Cormier, Philip J; Clarke, Ryan M; McFadden, Ryan M L; Ghandi, Khashayar

2014-02-12

We report herein a means to modify the reactivity of alkenes, and particularly to modify their selectivity toward reactions with nonpolar reactants (e.g., nonpolar free radicals) in supercritical carbon dioxide near the critical point. Rate constants for free radical addition of the light hydrogen isotope muonium to ethylene, vinylidene fluoride, and vinylidene chloride in supercritical carbon dioxide are compared over a range of pressures and temperatures. Near carbon dioxide's critical point, the addition to ethylene exhibits critical speeding up, while the halogenated analogues display critical slowing. This suggests that supercritical carbon dioxide as a solvent may be used to tune alkene chemistry in near-critical conditions.

using Supercritical Fluid Extraction

African Journals Online (AJOL)

Methods: Supercritical CO2 extraction technology was adopted in this experiment to study the process of extraction of volatile oil from Polygonatum odoratum while gas chromatograph-mass spectrometer ..... Saponin rich fractions from.

Catalyst retention in continuous flow with supercritical carbon dioxide

NARCIS (Netherlands)

Stouten, S.C.; Noel, T.; Wang, Q.; Hessel, V.

2014-01-01

This review discusses the retention of organometallic catalysts in continuous flow processes utilizing supercritical carbon dioxide. Due to its innovative properties, supercritical carbon dioxide offers interesting possibilities for process intensification. As a result of safety and cost

Oxidation of hazardous waste in supercritical water: A comparison of modeling and experimental results for methanol destruction

International Nuclear Information System (INIS)

Butler, P.B.; Bergan, N.E.; Bramlette, T.T.; Pitz, W.J.; Westbrook, C.K.

1991-01-01

Recent experiments at Sandia National Laboratories conducted in conjunction with MODEC Corporation have demonstrated successful clean- up of contaminated water in a supercritical water reactor. These experiments targeted wastes of interest to Department of Energy production facilities. In this paper we present modeling and experimental results for a surrogate waste containing 98% water, 2% methanol, and parts per million of chlorinated hydrocarbons and laser dyes. Our initial modeling results consider only methanol and water. Experimental data are available for inlet and outlet conditions and axial temperature profiles along the outside reactor wall. The purpose of our model is to study the chemical and physical processes inside the reactor. We are particularly interested in the parameters that control the location of the reaction zone. The laboratory-scale reactor operates at 25 MPa., between 300 K and 900 K; it is modeled as a plug-flow reactor with a specified temperature profile. We use Chemkin Real-Gas to calculate mixture density, with the Peng-Robinson equation of state. The elementary reaction set for methanol oxidation and reactions of other C 1 and C 2 hydrocarbons is based on previous models for gas-phase kinetics. Results from our calculations show that the methanol is 99.9% destroyed at 1/3 the total reactor length. Although we were not able to measure composition of the fluid inside the experimental reactor, this prediction occurs near the location of the highest reactor temperature. This indicates that the chemical reaction is triggered by thermal effects, not kinetic rates. Results from ideal-gas calculations show nearly identical chemical profiles inside the reactor in dimensionless distance. However, reactor residence times are overpredicted by nearly 150% using an ideal-gas assumption. Our results indicate that this oxidation process can be successfully modeled using gas-phase chemical mechanisms. 23 refs., 8 figs

Industrial applications and current trends in supercritical fluid technologies

Directory of Open Access Journals (Sweden)

Gamse Thomas

2005-01-01

Full Text Available Supercritical fluids have a great potential for wide fields of processes Although CO2 is still one of the most used supercritical gases, for special purposes propane or even fluorinated-chlorinated fluids have also been tested. The specific characteristics of supercritical fluids behaviour were analyzed such as for example the solubilities of different components and the phase equilibria between the solute and solvent. The application at industrial scale (decaffeinating of tea and coffee, hop extraction or removal of pesticides from rice, activity in supercritical extraction producing total extract from the raw material or different fractions by using the fractionated separation of beverages (rum, cognac, whisky, wine, beer cider, of citrus oils and of lipids (fish oils, tall oil were also discussed. The main interest is still for the extraction of natural raw materials producing food ingredients, nutraceuticals and phytopharmaceuticals but also cleaning purposes were tested such as the decontamination of soils the removal of residual solvents from pharmaceutical products, the extraction of flame retardants from electronic waste or precision degreasing and cleaning of mechanical and electronic parts. An increasing interest obviously exists for impregnation purposes based on supercritical fluids behaviour, as well as for the dying of fibres and textiles. The production of fine particles in the micron and submicron range, mainly for pharmaceutical products is another important application of supercritical fluids. Completely new products can be produced which is not possible under normal conditions. Supercritical fluid technology has always had to compete with the widespread opinion that these processes are very expensive due to very high investment costs in comparison with classical low-pressure equipment. Thus the opinion is that these processes should be restricted to high-added value products. A cost estimation for different plant sizes and

The effect of supercritical isobutane regeneration on the nature of hydrocarbons deposited on a USY zeolite catalyst utilized for isobutane/butene alkylation

Energy Technology Data Exchange (ETDEWEB)

Daniel M. Ginosar; Lucia M. Petkovic

2004-11-01

The chemical nature of hydrocarbons remaining on an ultrastable Y-zeolite (USY) utilized for liquid phase isobutane/butene alkylation reaction at 333 K and 1.1x107 Pa before and after supercritical isobutane regeneration (SFR) at 453 K and 1.1x107 Pa are presented. Catalyst samples were deactivated to different levels by running the alkylation reaction for different times on stream (TOS) and regenerated under flowing supercritical isobutane for 60 min. Nitrogen physisorption, temperature-programmed oxidation (TPO), diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), and ultraviolet-visible (UV-Vis) spectroscopy measurements suggested that the SFR process was effective in recovering catalyst surface area and micropore volume and that most coke precursors were removed from samples regenerated after short TOS, when the level of activity for trimethylpentanes (TMP) production was high. Samples that were allowed to react for longer TOS contained unsaturated hydrocarbons that, instead of being extracted by the supercritical fluid, dehydrogenated during the SFR process to produce more condensed species.

Particle Formation by Supercritical Fluid Extraction and Expansion Process

Directory of Open Access Journals (Sweden)

Sujuan Pan

2013-01-01

Full Text Available Supercritical fluid extraction and expansion (SFEE patented technology combines the advantages of both supercritical fluid extraction (SFE and rapid expansion of supercritical solution (RESS with on-line coupling, which makes the nanoparticle formation feasible directly from matrix such as Chinese herbal medicine. Supercritical fluid extraction is a green separation technology, which has been developed for decades and widely applied in traditional Chinese medicines or natural active components. In this paper, a SFEE patented instrument was firstly built up and controlled by LABVIEW work stations. Stearic acid was used to verify the SFEE process at optimized condition; via adjusting the preexpansion pressure and temperature one can get different sizes of particles. Furthermore, stearic acid was purified during the SFEE process with HPLC-ELSD detecting device; purity of stearic acid increased by 19%, and the device can purify stearic acid.

Supercritical Water Reactor Cycle for Medium Power Applications

International Nuclear Information System (INIS)

BD Middleton; J Buongiorno

2007-01-01

Scoping studies for a power conversion system based on a direct-cycle supercritical water reactor have been conducted. The electric power range of interest is 5-30 MWe with a design point of 20 MWe. The overall design objective is to develop a system that has minimized physical size and performs satisfactorily over a broad range of operating conditions. The design constraints are as follows: Net cycle thermal efficiency (ge)20%; Steam turbine outlet quality (ge)90%; and Pumping power (le)2500 kW (at nominal conditions). Three basic cycle configurations were analyzed. Listed in order of increased plant complexity, they are: (1) Simple supercritical Rankine cycle; (2) All-supercritical Brayton cycle; and (3) Supercritical Rankine cycle with feedwater preheating. The sensitivity of these three configurations to various parameters, such as reactor exit temperature, reactor pressure, condenser pressure, etc., was assessed. The Thermoflex software package was used for this task. The results are as follows: (a) The simple supercritical Rankine cycle offers the greatest hardware simplification, but its high reactor temperature rise and reactor outlet temperature may pose serious problems from the viewpoint of thermal stresses, stability and materials in the core. (b) The all-supercritical Brayton cycle is not a contender, due to its poor thermal efficiency. (c) The supercritical Rankine cycle with feedwater preheating affords acceptable thermal efficiency with lower reactor temperature rise and outlet temperature. (d) The use of a moisture separator improves the performance of the supercritical Rankine cycle with feedwater preheating and allows for a further reduction of the reactor outlet temperature, thus it was selected for the next step. Preliminary engineering design of the supercritical Rankine cycle with feedwater preheating and moisture separation was performed. All major components including the turbine, feedwater heater, feedwater pump, condenser, condenser pump

Synergy in Lignin Upgrading by a Combination of Cu-Based Mixed Oxide and Ni-Phosphide Catalysts in Supercritical Ethanol.

Science.gov (United States)

Korányi, Tamás I; Huang, Xiaoming; Coumans, Alessandro E; Hensen, Emiel J M

2017-04-03

The depolymerization of lignin to bioaromatics usually requires a hydrodeoxygenation (HDO) step to lower the oxygen content. A mixed Cu-Mg-Al oxide (CuMgAlO x ) is an effective catalyst for the depolymerization of lignin in supercritical ethanol. We explored the use of Ni-based cocatalysts, i.e. Ni/SiO 2 , Ni 2 P/SiO 2 , and Ni/ASA (ASA = amorphous silica alumina), with the aim of combining lignin depolymerization and HDO in a single reaction step. While the silica-supported catalysts were themselves hardly active in lignin upgrading, Ni/ASA displayed comparable lignin monomer yield as CuMgAlO x . A drawback of using an acidic support is extensive dehydration of the ethanol solvent. Instead, combining CuMgAlO x with Ni/SiO 2 and especially Ni 2 P/SiO 2 proved to be effective in increasing the lignin monomer yield, while at the same time reducing the oxygen content of the products. With Ni 2 P/SiO 2 , the lignin monomer yield was 53 wt %, leading to nearly complete deoxygenation of the aromatic products.

Experimental study on the operating characteristics of an inner preheating transpiring wall reactor for supercritical water oxidation: Temperature profiles and product properties

International Nuclear Information System (INIS)

Zhang, Fengming; Xu, Chunyan; Zhang, Yong; Chen, Shouyan; Chen, Guifang; Ma, Chunyuan

2014-01-01

A new process to generate multiple thermal fluids by supercritical water oxidation (SCWO) was proposed to enhance oil recovery. An inner preheating transpiring wall reactor for SCWO was designed and tested to avoid plugging in the preheating section. Hot water (400–600 °C) was used as auxiliary heat source to preheat the feed to the reaction temperature. The effect of different operating parameters on the performance of the inner preheating transpiring wall reactor was investigated, and the optimized operating parameters were determined based on temperature profiles and product properties. The reaction temperature is close to 900 °C at an auxiliary heat source flow of 2.79 kg/h, and the auxiliary heat source flow is determined at 6–14 kg/h to avoid the overheating of the reactor. The useful reaction time is used to quantitatively describe the feed degradation efficiency. The outlet concentration of total organic carbon (TOC out ) and CO in the effluent gradually decreases with increasing useful reaction time. The useful reaction time needed for complete oxidation of the feed is 10.5 s for the reactor. - Highlights: • A new process to generate multiple thermal fluids by SCWO was proposed. • An inner preheating transpiring wall reactor for SCWO was designed and tested. • Hot water was used as auxiliary heat source to preheat the feed at room temperature. • Effect of operating parameters on the performance of the reactor was investigated. • The useful reaction time required for complete oxidation of the feed is 10.5 s

Kinetic models for supercritical CO2 extraction of oilseeds - a review

Directory of Open Access Journals (Sweden)

B. Nagy

2011-01-01

Full Text Available The supercritical fluid extraction of oilseeds is gaining increasing interest in commercial application for the last few decades, most particularly thanks to technical and environmental advantages of supercritical fluid extraction technology compared to current extraction methods with organic solvents. Furthermore, CO2 as a solvent is generally recognized as safe (GRAS. At present moment, supercritical fluid extractions on a commercial scale are limited to decaffeination, production of soluble hops extracts, sesame seed oil production and extraction of certain petroleum products. When considering industrial application, it is essential to test the applicability of the appropriate model for supercritical fluid extraction of oilseeds used for scale up of laboratory data to industrial design purposes. The aim of this paper is to review the most significant kinetic models reported in the literature for supercritical fluid extraction.

Supercritical fluid chromatography for lipid analysis in foodstuffs.

Science.gov (United States)

Donato, Paola; Inferrera, Veronica; Sciarrone, Danilo; Mondello, Luigi

2017-01-01

The task of lipid analysis has always challenged separation scientists, and new techniques in chromatography were often developed for the separation of lipids; however, no single technique or methodology is yet capable of affording a comprehensive screening of all lipid species and classes. This review acquaints the role of supercritical fluid chromatography within the field of lipid analysis, from the early developed capillary separations based on pure CO 2 , to the most recent techniques employing packed columns under subcritical conditions, including the niche multidimensional techniques using supercritical fluids in at least one of the separation dimensions. A short history of supercritical fluid chromatography will be introduced first, from its early popularity in the late 1980s, to the sudden fall and oblivion until the last decade, experiencing a regain of interest within the chromatographic community. Afterwards, the subject of lipid nomenclature and classification will be briefly dealt with, before discussing the main applications of supercritical fluid chromatography for food analysis, according to the specific class of lipids. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Calculation of partial molar volume of components in supercritical ammonia synthesis system

Institute of Scientific and Technical Information of China (English)

Cunwen WANG; Chuanbo YU; Wen CHEN; Weiguo WANG; Yuanxin WU; Junfeng ZHANG

2008-01-01

The partial molar volumes of components in supercritical ammonia synthesis system are calculated in detail by the calculation formula of partial molar volume derived from the R-K equation of state under different conditions. The objectives are to comprehend phase beha-vior of components and to provide the theoretic explana-tion and guidance for probing novel processes of ammonia synthesis under supercritical conditions. The conditions of calculation are H2/N2= 3, at a concentra-tion of NH3 in synthesis gas ranging from 2% to 15%, Concentration of medium in supercritical ammonia syn-thesis system ranging from 20% to 50%, temperature ran-ging from 243 K to 699 K and pressure ranging from 0.1 MPa to 187 MPa. The results show that the ammonia synthesis system can reach supercritical state by adding a suitable supercritical medium and then controlling the reaction conditions. It is helpful for the supercritical ammonia synthesis that medium reaches supercritical state under the conditions of the corresponding total pres-sure and components near the normal temperature or near the critical temperature of medium or in the range of tem-perature of industrialized ammonia synthesis.

Supercritical water decontamination of town gas soil

International Nuclear Information System (INIS)

Kocher, B.S.; Azzam, F.O.; Lee, S.

1994-01-01

Town gas sites represent a large environmental problem that exists in more than 2,000 sites across North America alone. The major contaminants in town gas sods are polycyclic aromatic hydrocarbons (PAHs). These are stable compounds that migrate deep into the soil and are traditionally very difficult to remove by conventional remediation processes. Supercritical fluids offer enhanced solvating properties along with reduced mass transfer resistances that make them ideal for removing compounds that are difficult or impossible to remove by conventional processes. Supercritical water is ideal for removing PAHs and other hydrocarbons from soil due to its high solvating power towards most hydrocarbon species. Supercritical water was investigated for its ability to remediate two different town gas sods containing from 3--20 wt% contamination. The sod was remediated in a 300-cc semi-continuous system to a more environmentally acceptable level

A wet-chemical approach to perovskite and fluorite-type nanoceramics: synthesis and processing

NARCIS (Netherlands)

Veldhuis, Sjoerd

2015-01-01

In thesis the low-temperature, wet-chemical approach to various functional inorganic oxide materials is described. The main focus of this research is to control the material’s synthesis from liquid precursor to metal oxide powder or thin film; while understanding its formation mechanism. In

Hydrogenation of diesel aromatic compounds in supercritical solvent environment

Directory of Open Access Journals (Sweden)

E.P. Martins

2000-09-01

Full Text Available Reactions under supercritical conditions have been employed in many processes. Furthermore, an increasing number of commercial reactions have been conducted under supercritical or near critical conditions. These reaction conditions offer several advantages when compared to conditions in conventional catalytic processes in liquid-phase, gas-liquid interface, or even some gas-phase reactions. Basically, a supercritical solvent can diminish the reactant’s transport resistance from the bulk region to the catalyst surface due to enhancement of liquid diffusivity values and better solubility than those in different phases. Another advantage is that supercritical solvents permit prompt and easy changes in intermolecular properties in order to modify reaction parameters, such as conversion or selectivity, or even proceed with the separation of reaction products. Diesel fractions from petroleum frequently have larger than desirable quantities of aromatic compounds. Diesel hydrogenation is intended to decrease these quantities, i.e., to increase the quantity of paraffin present in this petroleum fraction. In this work, the hydrogenation of tetralin was studied as a model reaction for the aromatic hydrogenation process. A conventional gas-liquid-solid catalytic process was compared with that of supercritical carbon dioxide substrate under similar conditions. Additionally, an equilibrium conversion diagram was calculated for this reaction in a wide range of temperature and reactant ratios, so as to optimize the operational conditions and improve the results of subsequent experiments. An increase in the rate of reaction at 493 K in supercritical fluid, as compared to that in the conventional process, was observed.

Supercritical fluid extraction of oregano (Origanum vulgare) essentials oils: anti-inflammatory properties based on cytokine response on THP-1 macrophages.

Science.gov (United States)

Ocaña-Fuentes, A; Arranz-Gutiérrez, E; Señorans, F J; Reglero, G

2010-06-01

Two fractions (S1 and S2) of an oregano (Origanum vulgare) extract obtained by supercritical fluid extraction have been used to test anti-inflammatory effects on activated human THP-1 cells. The main compounds present in the supercritical extract fractions of oregano were trans-sabinene hydrate, thymol and carvacrol. Fractions toxicity was assessed using the mitochondrial-respiration-dependent 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium (MTT) reduction method for several concentrations during 24 and 48 h of incubation. Concentrations higher than 30 microg/mL of both supercritical S1 and S2 oregano fractions caused a reduction in cell viability in a dose-dependent manner. Oxidized-LDLs (oxLDLs) activated THP-1 macrophages were used as cellular model of atherogenesis and the release/secretion of cytokines (TNT-alpha, IL-1beta, IL-6 and IL-10) and their respective mRNA expressions were quantified both in presence or absence of supercritical oregano extracts. The results showed a decrease in pro-inflammatory TNF-alpha, IL-1beta and IL-6 cytokines synthesis, as well as an increase in the production of anti-inflammatory cytokine IL-10. These results may suggest an anti-inflammatory effect of oregano extracts and their compounds in a cellular model of atherosclerosis. Copyright 2010 Elsevier Ltd. All rights reserved.

Supercritical solvent extraction of oil sand bitumen

Science.gov (United States)

Imanbayev, Ye. I.; Ongarbayev, Ye. K.; Tileuberdi, Ye.; Mansurov, Z. A.; Golovko, A. K.; Rudyk, S.

2017-08-01

The supercritical solvent extraction of bitumen from oil sand studied with organic solvents. The experiments were performed in autoclave reactor at temperature above 255 °C and pressure 29 atm with stirring for 6 h. The reaction resulted in the formation of coke products with mineral part of oil sands. The remaining products separated into SARA fractions. The properties of the obtained products were studied. The supercritical solvent extraction significantly upgraded extracted natural bitumen.

Mechanism of Bacillus subtilis spore inactivation by and resistance to supercritical CO2 plus peracetic acid.

Science.gov (United States)

Setlow, B; Korza, G; Blatt, K M S; Fey, J P; Setlow, P

2016-01-01

Determine how supercritical CO2 (scCO2 ) plus peracetic acid (PAA) inactivates Bacillus subtilis spores, factors important in spore resistance to scCO2 -PAA, and if spores inactivated by scCO2 -PAA are truly dead. Spores of wild-type B. subtilis and isogenic mutants lacking spore protective proteins were treated with scCO2 -PAA in liquid or dry at 35°C. Wild-type wet spores (aqueous suspension) were more susceptible than dry spores. Treated spores were examined for viability (and were truly dead), dipicolinic acid (DPA), mutations, permeability to nucleic acid stains, germination under different conditions, energy metabolism and outgrowth. ScCO2 -PAA-inactivated spores retained DPA, and survivors had no notable DNA damage. However, DPA was released from inactivated spores at a normally innocuous temperature (85°C), and colony formation from treated spores was salt sensitive. The inactivated spores germinated but did not outgrow, and these germinated spores had altered plasma membrane permeability and defective energy metabolism. Wet or dry coat-defective spores had increased scCO2 -PAA sensitivity, and dry spores but not wet spores lacking DNA protective proteins were more scCO2 -PAA sensitive. These findings suggest that scCO2 -PAA inactivates spores by damaging spores' inner membrane. The spore coat provided scCO2 -PAA resistance for both wet and dry spores. DNA protective proteins provided scCO2 -PAA resistance only for dry spores. These results provide information on mechanisms of spore inactivation of and resistance to scCO2 -PAA, an agent with increasing use in sterilization applications. © 2015 The Society for Applied Microbiology.

Channel type reactors with supercritical water coolant. Russian experience

International Nuclear Information System (INIS)

Kuznetsov, Y.N.; Gabaraev, B.A.

2003-01-01

Transition to coolant of supercritical parameters allows for principle engineering-andeconomic characteristics of light-water nuclear power reactors to be substantially enhanced. Russian experience in development of channel-type reactors with supercritical water coolant has demonstrated advantages and practical feasibility of such reactors. (author)

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.

Materials challenges for the supercritical water-cooled reactor (SCWR)

International Nuclear Information System (INIS)

Baindur, S.

2008-01-01

This paper discusses the materials requirements of the Supercritical Water-cooled Reactor (SCWR) which arise from its severe expected operating conditions: (i) Outlet Temperature (to 650 C); (ii) Pressure of 25 MPa for the coolant containment, (iii) Thermochemical stress in the presence of supercritical water, and (iv) Radiative damage (up to 150 dpa for the fast spectrum variant). These operating conditions are reviewed; the phenomenology of materials in the supercritical water environment that create the materials challenges is discussed; knowledge gaps are identified, and efforts to understand material behaviour under the operating conditions expected in the SCWR are described. (author)

Supercritical extraction of lycopene from tomato industrial wastes with ethane.

Science.gov (United States)

Nobre, Beatriz P; Gouveia, Luisa; Matos, Patricia G S; Cristino, Ana F; Palavra, António F; Mendes, Rui L

2012-07-11

Supercritical fluid extraction of all-E-lycopene from tomato industrial wastes (mixture of skins and seeds) was carried out in a semi-continuous flow apparatus using ethane as supercritical solvent. The effect of pressure, temperature, feed particle size, solvent superficial velocity and matrix initial composition was evaluated. Moreover, the yield of the extraction was compared with that obtained with other supercritical solvents (supercritical CO₂ and a near critical mixture of ethane and propane). The recovery of all-E-lycopene increased with pressure, decreased with the increase of the particle size in the initial stages of the extraction and was not practically affected by the solvent superficial velocity. The effect of the temperature was more complex. When the temperature increased from 40 to 60 °C the recovery of all-E-lycopene increased from 80 to 90%. However, for a further increase to 80 °C, the recovery remained almost the same, indicating that some E-Z isomerization could have occurred, as well as some degradation of lycopene. The recovery of all-E-lycopene was almost the same for feed samples with different all-E-lycopene content. Furthermore, when a batch with a higher all-E-lycopene content was used, supercritical ethane and a near critical mixture of ethane and propane showed to be better solvents than supercritical CO₂ leading to a faster extraction with a higher recovery of the carotenoid.

Photocatalytic and chemical oxidation of organic compounds in supercritical carbon dioxide. Progress report for FY97

International Nuclear Information System (INIS)

Blake, D.M.; Bryant, D.L.; Reinsch, V.

1997-01-01

'The background for the project is briefly reviewed and the work done during the nine months since funding was received is documented. Work began in January, 1997. A post doctoral fellow joined the team in April. The major activities completed this fiscal year were: staffing the project, design of the experimental system, procurement of components, assembly of the system. preparation of the Safe Operating Procedure and ES and H compliance, pressure testing, establishing data collection and storage methodology, and catalyst preparation. Objective The objective of the project is to develop new chemistry for the removal of organic contaminants from supercritical carbon dioxide. This has application in processes used for continuous cleaning and extraction of parts and waste materials. A secondary objective is to increase the fundamental understanding of photocatalytic chemistry. Cleaning and extraction using supercritical carbon dioxide (scCO 2 ) can be applied to the solution of a wide range of environmental and pollution prevention problems in the DOE complex. Work is being done that explores scCO 2 in applications ranging from cleaning contaminated soil to cleaning components constructed from plutonium. The rationale for use of scCO 2 are based on the benign nature, availability and low cost, attractive solvent properties, and energy efficient separation of the extracted solute from the solvent by moderate temperature or pressure changes. To date, R and D has focussed on the methods and applications of the extraction steps of the process. Little has been done that addresses methods to polish the scCO 2 for recycle in the cleaning or extraction operations. In many applications it will be desirable to reduce the level of contamination from that which would occur at steady state operation of a process. This proposal addresses chemistry to achieve that. This would be an alternative to removing a fraction of the contaminated scCO 2 for disposal and using makeup scCO 2

Photocatalytic and chemical oxidation of organic compounds in supercritical carbon dioxide. Progress report for FY97

Energy Technology Data Exchange (ETDEWEB)

Blake, D.M.; Bryant, D.L.; Reinsch, V.

1997-09-30

'The background for the project is briefly reviewed and the work done during the nine months since funding was received is documented. Work began in January, 1997. A post doctoral fellow joined the team in April. The major activities completed this fiscal year were: staffing the project, design of the experimental system, procurement of components, assembly of the system. preparation of the Safe Operating Procedure and ES and H compliance, pressure testing, establishing data collection and storage methodology, and catalyst preparation. Objective The objective of the project is to develop new chemistry for the removal of organic contaminants from supercritical carbon dioxide. This has application in processes used for continuous cleaning and extraction of parts and waste materials. A secondary objective is to increase the fundamental understanding of photocatalytic chemistry. Cleaning and extraction using supercritical carbon dioxide (scCO{sub 2}) can be applied to the solution of a wide range of environmental and pollution prevention problems in the DOE complex. Work is being done that explores scCO{sub 2} in applications ranging from cleaning contaminated soil to cleaning components constructed from plutonium. The rationale for use of scCO{sub 2} are based on the benign nature, availability and low cost, attractive solvent properties, and energy efficient separation of the extracted solute from the solvent by moderate temperature or pressure changes. To date, R and D has focussed on the methods and applications of the extraction steps of the process. Little has been done that addresses methods to polish the scCO{sub 2} for recycle in the cleaning or extraction operations. In many applications it will be desirable to reduce the level of contamination from that which would occur at steady state operation of a process. This proposal addresses chemistry to achieve that. This would be an alternative to removing a fraction of the contaminated scCO{sub 2} for

Design of experimental system for supercritical CO2 fracturing under confining pressure conditions

Science.gov (United States)

Wang, H.; Lu, Q.; Li, X.; Yang, B.; Zheng, Y.; Shi, L.; Shi, X.

2018-03-01

Supercritical CO2 has the characteristics of low viscosity, high diffusion and zero surface tension, and it is considered as a new fluid for non-polluting and non-aqueous fracturing which can be used for shale gas development. Fracturing refers to a method of utilizing the high-pressure fluid to generate fractures in the rock formation so as to improve the oil and gas flow conditions and increase the oil and gas production. In this article, a new type of experimental system for supercritical CO2 fracturing under confining pressure conditions is designed, which is based on characteristics of supercritical CO2, shale reservoir and down-hole environment. The experimental system consists of three sub-systems, including supercritical CO2 generation system, supercritical CO2 fracturing system and data analysis system. It can be used to simulate supercritical CO2 fracturing under geo-stress conditions, thus to study the rock initiation pressure, the formation of the rock fractures, fractured surface morphology and so on. The experimental system has successfully carried out a series of supercritical CO2 fracturing experiments. The experimental results confirm the feasibility of the experimental system and the high efficiency of supercritical CO2 in fracturing tight rocks.

Research on the Development of the Supercritical CO{sub 2} Dual Brayton Cycle

Energy Technology Data Exchange (ETDEWEB)

Baik, Young-Jin; Na, Sun Ik; Cho, Junhyun; Shin, Hyung-Ki; Lee, Gilbong [Korea Institute of Energy Research (KIER), Daejeon (Korea, Republic of)

2016-10-15

Because of the growing interest in supercritical carbon dioxide power cycle technology owing to its potential enhancement in compactness and efficiency, supercritical carbon dioxide cycles have been studied in the fields of nuclear power, concentrated solar power (CSP), and fossil fuel power generation. This study introduces the current status of the research project on the supercritical carbon dioxide power cycle by Korea Institute of Energy Research (KIER). During the first phase of the project, the un-recuperated supercritical Brayton cycle test loop was built and tested. In phase two, researchers are designing and building a supercritical carbon dioxide dual Brayton cycle, which utilizes two turbines and two recuperators. Under the simulation condition considered in this study, it was confirmed that the design parameter has an optimal value for maximizing the net power in the supercritical carbon dioxide dual cycle.

Charting the Landscape of Supercritical String Theory

International Nuclear Information System (INIS)

Hellerman, Simeon; Swanson, Ian

2007-01-01

Special solutions of string theory in supercritical dimensions can interpolate in time between theories with different numbers of spacetime dimensions and different amounts of world sheet supersymmetry. These solutions connect supercritical string theories to the more familiar string duality web in ten dimensions and provide a precise link between supersymmetric and purely bosonic string theories. Dimension quenching and c duality appear to be natural concepts in string theory, giving rise to large networks of interconnected theories

Feasibility analysis of the modified ATHLET code for supercritical water cooled systems

Energy Technology Data Exchange (ETDEWEB)

Zhou Chong, E-mail: ch.zhou@sjtu.edu.cn [School of Nuclear Science and Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240 (China); Institute of Fusion and Reactor Technology, Karlsruhe Institute of Technology, Vincenz-Priessnitz-Str. 3, 76131 Karlsruhe (Germany); Yang Yanhua [School of Nuclear Science and Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240 (China); Cheng Xu [Institute of Fusion and Reactor Technology, Karlsruhe Institute of Technology, Vincenz-Priessnitz-Str. 3, 76131 Karlsruhe (Germany)

2012-09-15

Highlights: Black-Right-Pointing-Pointer Modification of system code ATHLET for supercritical water application. Black-Right-Pointing-Pointer Development and assessment of a heat transfer package for supercritical water. Black-Right-Pointing-Pointer Validation of the modified code at supercritical pressures with the theoretical point-hydraulics model and the SASC code. Black-Right-Pointing-Pointer Application of the modified code to LOCA analysis of a supercritical water cooled in-pile fuel qualification test loop. - Abstract: Since the existing thermal-hydraulic computer codes for light water reactors are not applicable to supercritical water cooled reactors (SCWRs) owing to the limitation of physical models and numerical treatments, the development of a reliable thermal-hydraulic computer code is very important to design analysis and safety assessment of SCWRs. Based on earlier modification of ATHLET for SCWR, a general interface is implemented to the code, which serves as the platform for information exchange between ATHLET and the external independent physical modules. A heat transfer package containing five correlations for supercritical water is connected to the ATHLET code through the interface. The correlations are assessed with experimental data. To verify the modified ATHLET code, the Edwards-O'Brian blow-down test is simulated. As first validation at supercritical pressures, a simplified supercritical water cooled loop is modeled and its stability behavior is analyzed. Results are compared with that of the theoretical model and SASC code in the reference and show good agreement. To evaluate its feasibility, the modified ATHLET code is applied to a supercritical water cooled in-pile fuel qualification test loop. Loss of coolant accidents (LOCAs) due to break of coolant supply lines are calculated for the loop. Sensitivity analysis of some safety system parameters is performed to get further knowledge about their influence on the function of the

Materials identification and surveillance project item evaluation: Items, impure plutonium oxide (ATL27960) and pure plutonium oxide (PEOR3258)

International Nuclear Information System (INIS)

Allen, T.; Appert, Q.; Davis, C.

1997-03-01

In this report, Los Alamos scientists characterize properties relevant to storage of an impure plutonium oxide (74 mass % plutonium) in accordance with the Department of Energy (DOE) standard DOE-STD-3013-96. This oxide is of interest because it is the first impure plutonium oxide sample to be evaluated and it is similar to other materials that must be stored. Methods used to characterize the oxide at certain points during calcination include surface-area analyses, mass loss-on-ignition (LOI) measurements, elemental analysis, moisture-adsorption measurements, and quantitative supercritical-CO 2 extraction of adsorbed water. Significant decreases in the LOI and surface area occurred as the oxide was calcined at progressively increasing temperatures. Studies indicate that supercritical-CO 2 extraction is an effective method for removing adsorbed water from oxides. We extracted the water from powdered oxides (high-purity ZrO 2 , pure PuO 2 , and impure plutonium oxide) using CO 2 at 3000 psi pressure and 75 degrees C, and we quantitatively determined it by using gravimetric and dew-point procedures. The effectiveness of the extraction method is demonstrated by good agreement between the amounts of water extracted from pure zirconium and plutonium dioxides and the mass changes obtained from LOI analyses. However, the amount of moisture (0.025 mass %) extracted from the impure plutonium oxide after it had been calcined at 950 degrees C and stored for a period of months is much less than the LOI value (0.97 mass %). These results imply that the impure plutonium oxide is free of adsorbed water after calcination at 950 degrees C, even though the sample does not satisfy the LOI requirement of <0.50 mass % for storage

Comparative Batch and Column Evaluation of Thermal and Wet ...

African Journals Online (AJOL)

The efficiency of regenerated spent commercial activated carbon for synthetic dye removal was studied using thermal and wet oxidative regeneration methods. Two types of experiments were carried out, batch adsorption experiments and continous flow (fixed bed) column experiment to study the mechanism of dye removal ...

Specifics of forced-convective heat transfer in supercritical carbon dioxide

Energy Technology Data Exchange (ETDEWEB)

Saltanov, A.E.; Mann, B.D.; Harvel, C.G.; Pioro, D.I., E-mail: Eugene.saltanov@hotmail.com [University of Ontario Institute of Technology, Oshawa, ON (Canada)

2015-07-01

The appropriate description of heat-transfer to coolants at supercritical state is one of the main challenges in development of supercritical-fluids applications for the Generation-IV reactors. In this paper the basis for comparison of relatively recent experimental data on supercritical carbon dioxide (CO{sub 2}) obtained at facilities of the Korea Atomic Energy Research Institute (KAERI) and Chalk River Laboratories (CRL) of Atomic Energy of Canada Limited (AECL) is discussed, and a preliminary heat-transfer correlation for joint CRL and KAERI datasets is presented. (author)

H2-O2 supercritical combustion modeling using a CFD code

Directory of Open Access Journals (Sweden)

Benarous Abdallah

2009-01-01

Full Text Available The characteristics of propellant injection, mixing, and combustion have a profound effect on liquid rocket engine performance. The necessity of raising rocket engines performance requires a combustion chamber operation often in a supercritical regime. A supercritical combustion model based on a one-phase multi-components approach is developed and tested on a non-premixed H2-O2 flame configuration. A two equations turbulence model is used for describing the jet dynamics where a limited Pope correction is added to account for the oxidant spreading rate. Transport properties of the mixture are calculated using extended high pressure forms of the mixing rules. An equilibrium chemistry scheme is adopted in this combustion case, with both algebraic and stochastic expressions for the chemistry/turbulence coupling. The model was incorporated into a computational fluid dynamics commercial code (Fluent 6.2.16. The validity of the present model was investigated by comparing predictions of temperature, species mass fractions, recirculation zones and visible flame length to the experimental data measured on the Mascotte test rig. The results were confronted also with advanced code simulations. It appears that the agreement between the results was fairly good in the chamber regions situated downstream the near injection zone.

Radio-frequency magnetron sputtering and wet thermal oxidation of ZnO thin film

International Nuclear Information System (INIS)

Liu, H. F.; Chua, S. J.; Hu, G. X.; Gong, H.; Xiang, N.

2007-01-01

The authors studied the growth and wet thermal oxidation (WTO) of ZnO thin films using a radio-frequency magnetron sputtering technique. X-ray diffraction reveals a preferred orientation of [1010]ZnO(0002)//[1120]Al 2 O 3 (0002) coexisted with a small amount of ZnO (1011) and ZnO (1013) crystals on the Al 2 O 3 (0001) substrate. The ZnO (1011) and ZnO (1013) crystals, as well as the in-plane preferred orientation, are absent from the growth of ZnO on the GaAs(001) substrate. WTO at 550 deg. C improves the crystalline and the photoluminescence more significantly than annealing in air, N 2 and O 2 ambient; it also tends to convert the crystal from ZnO (1011) and ZnO (1013) to ZnO (0002). The evolution of the photoluminescence upon WTO and annealing reveals that the green and orange emissions, centered at 520 and 650 nm, are likely originated from oxygen vacancies and oxygen interstitials, respectively; while the 420 nm emission, which is very sensitive to the postgrowth thermal processing regardless of the substrate and the ambient gas, is likely originated from the surface-state related defects

Selective chelation-supercritical fluid extraction of metal ions from waste materials

International Nuclear Information System (INIS)

Wai, C.N.; Laintz, K.E.; Yonker, C.R.

1993-01-01

The removal of toxic organics, metals, and radioisotopes from solids or liquids is a major concern in the treatment of industrial and nuclear wastes. For this reason, developing methods for selective separation of toxic metals and radioactive materials from solutions of complex matrix is an important problem in environmental research. Recent developments indicate supercritical fluids are good solvents for organic compounds. Many gases become supercritical fluids under moderate temperatures and pressures. For example, the critical temperature and pressure of carbon dioxide are 31 degrees C and 73 atm, respectively. The high diffusivity, low viscosity, and T-P dependence of solvent strength are some attractive properties of supercritical fluid extraction (SFE). Since CO 2 offers the additional benefits of stability and non-toxicity, the SFE technique avoids generation of organic liquid waste and exposure of personnel to toxic solvents. While direct extraction of metal ions by supercritical fluids is highly inefficient, these ions when complexed with organic ligands become quite soluble in supercritical fluids. Specific ligands can be used to achieve selective extraction of metal ions in this process. After SFE, the fluid phase can be depressurized for precipitation of the metal chelates and recycled. The ligand can also be regenerated for repeated use. The success of this selective chelation-supercritical fluid extraction (SC-SFE) process depends on a number of factors including the efficiencies of the selective chelating agents, solubilities of metal chelates in supercritical fluids, rate of extraction, ease of regeneration of the ligands, etc. In this report, the authors present recent results on the studies of the solubilities of metal chelates in supercritical CO 2 , experimental ions from aqueous solution, and the development of selective chelating agents (ionizable crown ethers) for the extraction of lanthanides and actinides

Chemical recycling of carbon fibers reinforced epoxy resin composites in oxygen in supercritical water

International Nuclear Information System (INIS)

Bai, Yongping; Wang, Zhi; Feng, Liqun

2010-01-01

The carbon fibers in carbon fibers reinforced epoxy resin composites were recovered in oxygen in supercritical water at 30 ± 1 MPa and 440 ± 10 o C. The microstructure of the recovered carbon fibers was observed using scanning electron microscopy (SEM) and atom force microscopy (AFM). The results revealed that the clean carbon fibers were recovered and had higher tensile strength relative to the virgin carbon fibers when the decomposition rate was above 85 wt.%, although the recovered carbon fibers have clean surface, the epoxy resin on the surface of the recovered carbon fibers was readily observed. As the decomposition rate increased to above 96 wt.%, no epoxy resin was observed on the surface of the carbon fibers and the oxidation of the recovered carbon fibers was readily measured by X-ray photoelectron spectroscopy (XPS) analysis. The carbon fibers were ideally recovered and have original strength when the decomposition rates were between 94 and 97 wt.%. This study clearly showed the oxygen in supercritical water is a promising way for recycling the carbon fibers in carbon fibers reinforced resin composites.

Supercritical fluid extraction: spectroscopic study of interactions comparison to solvent extraction

Energy Technology Data Exchange (ETDEWEB)

Rustenholtz Farawila, A

2005-06-15

Supercritical fluid carbon dioxide (SF-CO{sub 2}) was chosen to study Supercritical Fluid Extraction (SFE) of cesium and uranium. At first, crown ethers were considered as chelating agents for the SFE of cesium. The role of water and its interaction with crown ethers were especially studied using Fourier-Transform Infra-Red (FT-IR) spectroscopy in SF-CO{sub 2}. A sandwich configuration between two crown ethers and a water molecule was observed in the SF-CO{sub 2} phase for the first time. The equilibrium between the single and the bridge configurations was defined. The enthalpy of the hydrogen bond formation was also calculated. These results were then compared to the one in different mixtures of chloroform and carbon tetra-chloride using Nuclear Magnetic Resonance (NMR). To conclude this first part and in order to understand the whole picture of the recovery of cesium, I studied the role of water in the equilibrium between the cesium and the di-cyclo-hexano18-crown-6.In a second part, the supercritical fluid extraction of uranium was studied in SF-CO{sub 2}. For this purpose, different complexes of Tributyl Phosphate (TBP), nitric acid and water were used as chelating and oxidizing agents. I first used FT-IR to study the TBP-water interaction in SF-CO{sub 2}. These results were then compared to the one obtained with NMR in chloroform. NMR spectroscopy was also used to understand the TBP-nitric acid-water interaction first alone and then in chloroform. To conclude my research work, I succeeded to improve the efficiency of uranium extraction and stripping into water for a pilot-plant where enriched uranium is extracted from incinerated waste coming from nuclear fuel fabrication. TBP-nitric acid complexes were used in SF-CO{sub 2} for the extraction of uranium from ash. (author)

Supercritical fluid extraction: spectroscopic study of interactions comparison to solvent extraction

International Nuclear Information System (INIS)

Rustenholtz Farawila, A.

2005-06-01

Supercritical fluid carbon dioxide (SF-CO 2 ) was chosen to study Supercritical Fluid Extraction (SFE) of cesium and uranium. At first, crown ethers were considered as chelating agents for the SFE of cesium. The role of water and its interaction with crown ethers were especially studied using Fourier-Transform Infra-Red (FT-IR) spectroscopy in SF-CO 2 . A sandwich configuration between two crown ethers and a water molecule was observed in the SF-CO 2 phase for the first time. The equilibrium between the single and the bridge configurations was defined. The enthalpy of the hydrogen bond formation was also calculated. These results were then compared to the one in different mixtures of chloroform and carbon tetra-chloride using Nuclear Magnetic Resonance (NMR). To conclude this first part and in order to understand the whole picture of the recovery of cesium, I studied the role of water in the equilibrium between the cesium and the di-cyclo-hexano18-crown-6.In a second part, the supercritical fluid extraction of uranium was studied in SF-CO 2 . For this purpose, different complexes of Tributyl Phosphate (TBP), nitric acid and water were used as chelating and oxidizing agents. I first used FT-IR to study the TBP-water interaction in SF-CO 2 . These results were then compared to the one obtained with NMR in chloroform. NMR spectroscopy was also used to understand the TBP-nitric acid-water interaction first alone and then in chloroform. To conclude my research work, I succeeded to improve the efficiency of uranium extraction and stripping into water for a pilot-plant where enriched uranium is extracted from incinerated waste coming from nuclear fuel fabrication. TBP-nitric acid complexes were used in SF-CO 2 for the extraction of uranium from ash. (author)

Laboratory experiments for understanding mechanical properties of fractured granite under supercritical conditions

Science.gov (United States)

Kitamura, M.; Takahashi, M.; Takagi, K.; Hirano, N.; Tsuchiya, N.

2017-12-01

To extract geothermal energy effectively and safely from magma and/or adjacent hot rock, we need to tackle many issues which require new technology development, such as a technique to control a risk from induced-earthquakes. On a development of induced-earthquake mitigation technology, it is required to understand roles of factors on occurrences of the induced-earthquake (e.g., strength, crack density, and fluid-rock reaction) and their intercorrelations (e.g., Asanuma et al., 2012). Our purpose of this series of experiments is to clarify a relationship between the rock strength and the crack density under supercritical conditions. We conducted triaxial deformation test on intact granite rock strength under high-temperature (250 - 750°C), high-pressure (104 MPa) condition at a constant load velocity (0.1 μm/sec) using a gas-rig at AIST. We used Oshima granite, which has initially Young's modulus increased with decreasing the temperature from 32.3 GPa at 750°C to 57.4 GPa at 250°C. At 400 °C, the stress drop accelerated the deformation with 98 times faster velocity than that at load-point. In contrast, at 650°C and 750°C, the velocity during stress drop kept the same order of the load-point velocity. Therefore, the deformation mechanism may start to be changed from brittle to ductile when the temperature exceeds 650°C. Highly dense cracked granite specimens were formed by a rapid decompression test (RDT) using an autoclave settled at Tohoku University (Hirano et al., 2016JpGU), caused by a reduction of fluid pressure within 1-2 sec from vapor/supercritical state (10 - 48 MPa, 550 °C) to ambient pressure. The specimens after RDT show numerous microcracks on X-ray CT images. The RDT imposed the porosity increasing towards 3.75 % and Vp and Vs decreasing towards 1.37±0.52 km/s and 0.97±0.25 km/s. The Poisson's ratio shows the negative values in dry and 0.5 in wet. In the meeting, we will present results of triaxial deformation test on such cracked granites

Nitrate conversion and supercritical fluid extraction of UO2-CeO2 solid solution prepared by an electrolytic reduction-coprecipitation method

International Nuclear Information System (INIS)

Zhu, L.Y.; Duan, W.H.; Wen, M.F.; Xu, J.M.; Zhu, Y.J.

2014-01-01

A low-waste technology for the reprocessing of spent nuclear fuel (SNF) has been developed recently, which involves the conversion of actinide and lanthanide oxides with liquid N 2 O 4 into their nitrates followed by supercritical fluid extraction of the nitrates. The possibility of the reprocessing of SNF from high-temperature gas-cooled reactors (HTGRs) with nitrate conversion and supercritical fluid extraction is a current area of research in China. Here, a UO 2 -CeO 2 solid solution was prepared as a surrogate for a UO 2 -PuO 2 solid solution, and the recovery of U and Ce from the UO 2 -CeO 2 solid solution with liquid N 2 O 4 and supercritical CO 2 containing tri-n-butyl phosphate (TBP) was investigated. The UO 2 -CeO 2 solid solution prepared by electrolytic reduction-coprecipitation method had square plate microstructures. The solid solution after heat treatment was completely converted into nitrates with liquid N 2 O 4 . The XRD pattern of the nitrates was similar to that of UO 2 (NO 3 ) 2 . 3H 2 O. After 120 min of online extraction at 25 MPa and 50 , 99.98% of the U and 98.74% of the Ce were recovered from the nitrates with supercritical CO 2 containing TBP. The results suggest a promising potential technology for the reprocessing of SNF from HTGRs. (orig.)

Continuous production of biodiesel under supercritical methyl acetate conditions: Experimental investigation and kinetic model.

Science.gov (United States)

Farobie, Obie; Matsumura, Yukihiko

2017-10-01

In this study, biodiesel production by using supercritical methyl acetate in a continuous flow reactor was investigated for the first time. The aim of this study was to elucidate the reaction kinetics of biodiesel production by using supercritical methyl. Experiments were conducted at various reaction temperatures (300-400°C), residence times (5-30min), oil-to-methyl acetate molar ratio of 1:40, and a fixed pressure of 20MPa. Reaction kinetics of biodiesel production with supercritical methyl acetate was determined. Finally, biodiesel yield obtained from this method was compared to that obtained with supercritical methanol, ethanol, and MTBE (methyl tertiary-butyl ether). The results showed that biodiesel yield with supercritical methyl acetate increased with temperature and time. The developed kinetic model was found to fit the experimental data well. The reactivity of supercritical methyl acetate was the lowest, followed by that of supercritical MTBE, ethanol, and methanol, under the same conditions. Copyright © 2017. Published by Elsevier Ltd.

Precipitation of fluticasone propionate microparticles using supercritical antisolvent

Directory of Open Access Journals (Sweden)

A Vatanara

2009-03-01

Full Text Available ABSTRACT Background: The ability of supercritical fluids (SCFs, such as carbon dioxide, to dissolve and expand or extract organic solvents and as result lower their solvation power, makes it possible the use of SCFs for the precipitation of solids from organic solutions. The process could be the injection of a solution of the substrate in an organic solvent into a vessel which is swept by a supercritical fluid. The aim of this study was to ascertain the feasibility of supercritical processing to prepare different particulate forms of fluticasone propionate (FP, and to evaluate the influence of different liquid solvents and precipitation temperatures on the morphology, size and crystal habit of particles. Method: The solution of FP in organic solvents, was precipitated by supercritical carbon dioxide (SCCO2 at two pressure and temperature levels. Effects of process parameters on the physicochemical characteristics of harvested microparticles were evaluated. Results: Particle formation was observed only at the lower selected pressure, whilst at the higher pressure, no precipitation of particles was occurred due to dissolution of FP in supercritical antisolvent. The micrographs of the produced particles showed different morphologies for FP obtained from different conditions. The results of thermal analysis of the resulted particles showed that changes in the processing conditions didn't influence thermal behavior of the precipitated particles. Evaluation of the effect of temperature on the size distribution of particles showed that increase in the temperature from 40 oC to 50 oC, resulted in reduction of the mean particle size from about 30 µm to about 12 μm. ‍Conclusion: From the results of this study it may be concluded that, processing of FP by supercritical antisolvent could be an approach for production of diverse forms of the drug and drastic changes in the physical characteristics of microparticles could be achieved by changing the

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.

Thermal performance and efficiency of supercritical nuclear reactors

International Nuclear Information System (INIS)

Romney Duffey; Tracy Zhou; Hussam Khartabil

2009-01-01

The paper reviews the major advances and innovative aspects of the thermal performance of recent concepts for super-critical water-cooled nuclear reactors (SCWR). The concepts are based on the extensive experience in the thermal power industry with super and ultra-supercritical boilers and turbines. The challenges and goals of increased efficiency, reduced cost, enhanced safety and co-generation have been pursued over the last ten years, and have resulted both in viable concepts and a vibrant defined R and D effort. The supercritical concept has wide acceptance among industry, as it reflects standard engineering practices and current thermal plant technology that is being already deployed. The SCWR concept represents a continuous development of water-cooled reactor technology, which utilizes the best and latest advances made in the thermal power industry. (author)

Wet etching rates of InGaZnO for the fabrication of transparent thin-film transistors on plastic substrates

International Nuclear Information System (INIS)

Lee, Chi-Yuan; Chang, Chienliu; Shih, Wen-Pin; Dai, Ching-Liang

2010-01-01

The wet etch process for amorphous indium gallium zinc oxide (a-IGZO or a-InGaZnO) by using various etchants is reported. The etch rates of a-IGZO, compared to another indium-based oxides including indium gallium oxide (IGO), indium zinc oxide (IZO), and indium tin oxide (ITO), are measured by using acetic acid, citric acid, hydrochloric acid, perchloric acid, and aqua ammonia as etchants, respectively. In our experimental results, the etch rate of the transparent oxide semiconductor (TOS) films by using acid solutions ranked accordingly from high to low are IZO, IGZO, IGO and ITO. Comparatively, the etch rate of the TOS films by using alkaline ammonia solution ranked from high to low are IGZO, IZO, IGO and ITO, in that order. Using the proposed wet etching process with high etch selectivity, bottom-gate-type thin-film transistors (TFTs) based on a-IGZO channels and Y 2 O 3 gate-insulators were fabricated by radio-frequency sputtering on plastic substrates. The wet etch processed TFT with 30 μm gate length and 120 μm gate width exhibits a saturation mobility of 46.25 cm 2 V -1 s -1 , a threshold voltage of 1.3 V, a drain current on-off ratio > 10 6 , and subthreshold gate voltage swing of 0.29 V decade -1 . The performance of the TFTs ensures the applicability of the wet etching process for IGZO to electronic devices on organic polymer substrates.

Wet treatment of low-quality coal; Tratamiento de Carbones de Baja Calidad

Energy Technology Data Exchange (ETDEWEB)

NONE

1998-12-31

This project was aimed at the theoretical investigation of the wet oxidation destruction process of low-quality coal under occurrence of oxygen, which could permit the use of slack with a high ratio of inert materials with the above-mentioned technology. This first stage of the project is posed as the theoretical stage in which the proposed patterns are examined and then the pattern which is considered the most profitable one of all the patterns examined up to now is selected. Then the computer simulation was carried out using the process simulator ASPEN PLUS which is used in order to simulate all the stages of the life-cycle of a treatment plant. Afterwards the kinetic equation for the oxidation process of low-quality coal was examined. It can be deduced from the theoretical studies carried out that the technology of wet oxidation can be applied to the treatment of slacks. At a second stage of the project this technology will be examined at an experimental level. (Author)

Thermodynamic analysis and numerical modeling of supercritical injection

OpenAIRE

Banuti, Daniel

2015-01-01

Although liquid propellant rocket engines are operational and have been studied for decades, cryogenic injection at supercritical pressures is still considered essentially not understood. This thesis intends to approach this problem in three steps: by developing a numerical model for real gas thermodynamics, by extending the present thermodynamic view of supercritical injection, and finally by applying these methods to the analysis of injection. A new numerical real gas thermodynamics mode...

Supercritical fluid chromatography-A Hybrid of GC and LC

Directory of Open Access Journals (Sweden)

Neha Sethi

2010-01-01

Full Text Available High performance specifications and unique functionality of chromatographic techniques is a demand of pharmaceutical industry and research. This leads to the origin of Supercritical Fluid Chromatography (SFC. It is a rapidly expanding analytical technique. The main feature that differentiates SFC from other chromatographic techniques is the replacement of either the liquid or gas mobile phase with a supercritical fluid mobile phase. It is considered a hybrid of GC and LC technique. High diffusion coefficient and low viscosity of supercritical fluids is responsible for high speed analysis, high efficiency and high sensitivity. Low mobile-phase flow rate, density programming and compatability with GC and LC detectors make SFC a versatile chromatographic technique in analytical re-search and development. It has a unique characteristic of analyzing thermo labile or non-volatile substances. This review highlights the role of supercritical fluid chromatography in the separation of polymers, thermally labile pesticides, fatty acids, metal chelates and organometallic compounds, chiral and achiral molecules, identification and analysis of polar samples, explosives, drugs of abuse and application of SFC in forensic science (fingerprint-ing.

Monitoring of corrosion rates of Fe-Cu alloys under wet/dry condition in weakly alkaline environments

International Nuclear Information System (INIS)

Kim, Je Kyoung; Nishikata, Atsushi; Tsuru, Tooru

2002-01-01

When the steel, containing scrap elements like copper, is used as reinforcing steel bars for concrete, the steel is exposed to alkaline environments. in this study, AC impedance technique has been applied to the monitoring of corrosion rates of iron and several Fe-Cu (0.4, 10wt%) alloys in a wet-dry cycle condition. The wet-dry cycle was conducted by exposure to alternate conditions of 1 hour-immersion in a simulated pH10 concrete solution (Ca(OH) 2 ) containing 0.01M NaCl and 3 hour-drying at 298K and 50%RH. The corrosion rate of the iron is greatly accelerated by the wet-dry cycles. Because the active FeOOH species, which are produced by the oxidation of Fe(II, III)oxide in air during drying, act as very strong oxidants to the corrosion in the wet condition. As the drying progresses, iron shows a large increase in the corrosion rate and a small shift of the corrosion potential to the positive values. This can be explained by acceleration of oxygen transport through the thin electrolyte layer In contrast to iron, the Fe-Cu alloys show low corrosion rates and the high corrosion potentials in whole cycles

Molecular simulation of CO chemisorption on Co(0001) in presence of supercritical fluid solvent: A potential of mean force study

Energy Technology Data Exchange (ETDEWEB)

Asiaee, Alireza; Benjamin, Kenneth M., E-mail: kenneth.benjamin@sdsmt.edu [Department of Chemical and Biological Engineering, South Dakota School of Mines and Technology, 501 E. Saint Joseph St., Rapid City, South Dakota 57701 (United States)

2016-08-28

For several decades, heterogeneous catalytic processes have been improved through utilizing supercritical fluids (SCFs) as solvents. While numerous experimental studies have been established across a range of chemistries, such as oxidation, pyrolysis, amination, and Fischer-Tropsch synthesis, still there is little fundamental, molecular-level information regarding the role of the SCF on elementary heterogeneous catalytic steps. In this study, the influence of hexane solvent on the adsorption of carbon monoxide on Co(0001), as the first step in the reaction mechanism of many processes involving syngas conversion, is probed. Simulations are performed at various bulk hexane densities, ranging from ideal gas conditions (no SCF hexane) to various near- and super-critical hexane densities. For this purpose, both density functional theory and molecular dynamics simulations are employed to determine the adsorption energy and free energy change during CO chemisorption. Potential of mean force calculations, utilizing umbrella sampling and the weighted histogram analysis method, provide the first commentary on SCF solvent effects on the energetic aspects of the chemisorption process. Simulation results indicate an enhanced stability of CO adsorption on the catalyst surface in the presence of supercritical hexane within the reduced pressure range of 1.0–1.5 at a constant temperature of 523 K. Furthermore, it is shown that the maximum stability of CO in the adsorbed state as a function of supercritical hexane density at 523 K nearly coincides with the maximum isothermal compressibility of bulk hexane at this temperature.

Use of supercritical carbon dioxide extraction

Energy Technology Data Exchange (ETDEWEB)

Taniguchi, Masayuki (Niigata Univ., Faculty of Engineering, Niigata, (Japan))

1989-09-25

Supercritical fluid extraction is a novel diffusion and separation technique which exploits simultaneously the increase of vapor pressure and the difference of chemical affinities of fluids near the critical point. A solvent which is used as the supercritical fluid has the following features: the critical point exists in the position of relatively ease of handling, the solvent is applicable to the extraction of a physiological active substance of thermal instability. Carbon dioxide as the solvent is non-flammable, non-corrosive, non-toxic, cheap, and readily available of high purity. The results of studies on the use of supercritical carbon dioxide (SC-CO{sub 2}) as a solvent for natural products in the fermentation and food industries, were collected. SC-CO{sub 2} extraction are used in many fields, examples for the application are as follows: removal of organic solvents from antibiotics; extraction of vegetable oils contained in wheat germ oil, high quality mustard seeds, rice bran and so on; brewing of sake using rice and rice-koji; use as a non-aqueous medium for the synthesis of precursors of the Aspartame; and use in sterilization. 66 refs., 17 figs., 21 tabs.

Production of FAME by palm oil transesterification via supercritical methanol technology

International Nuclear Information System (INIS)

Tan, Kok Tat; Lee, Keat Teong; Mohamed, Abdul Rahman

2009-01-01

The present study employed non-catalytic supercritical methanol technology to produce biodiesel from palm oil. The research was carried out in a batch-type tube reactor and heated beyond supercritical temperature and pressure of methanol, which are at 239 o C and 8.1 MPa respectively. The effects of temperature, reaction time and molar ratio of methanol to palm oil on the yield of fatty acid methyl esters (FAME) or biodiesel were investigated. The results obtained showed that non-catalytic supercritical methanol technology only required a mere 20 min reaction time to produce more than 70% yield of FAME. Compared to conventional catalytic methods, which required at least 1 h reaction time to obtain similar yield, supercritical methanol technology has been shown to be superior in terms of time and energy consumption. Apart from the shorter reaction time, it was found that separation and purification of the products were simpler since no catalyst is involved in the process. Hence, formation of side products such as soap in catalytic reactions does not occur in the supercritical methanol method.

Supercritical fluid carbon dioxide extraction of actinides

International Nuclear Information System (INIS)

Rao, Ankita; Tomar, B.S.

2016-01-01

Supercritical fluid extraction (SFE) is a process akin to liquid-liquid or solvent extraction where a Supercritical fluid (SCF) is contacted with a solid/ liquid matrix for the purpose of separating the component of interest from the original matrix. Carbon dioxide is a preferred choice as supercritical fluid (SCF) owing to its moderate critical parameter (P c = 7.38 MPa and T c = 304.1K) coupled with radiation and chemical stability, non toxic nature and low cost. Despite widespread applications for extraction of organic compounds and associated advantages especially liquid waste minimization, the SFE of metal ions was left unexplored for quite some time, as direct metal ion extraction is inefficient due charge neutralization requirement and weak solute-solvent interaction. Neutral SCF soluble metal-ligand complexation is imperative and SFE of actinides was reported only in 1994. Several studies have been carried out on SFE of uranium, thorium and plutonium from nitric acid medium employing different sets of ligands (organophosphorus, diketones, amides). Especially attractive is the possibility of direct dissolution and extraction of actinides employing ligand-acid adducts (like TBP.HNO 3 adduct) from solid matrices of different stages of nuclear fuel cycle viz. ores, spent nuclear fuels and radioactive wastes. Also, partitioning of actinides from fission products has been explored in spent nuclear fuel. These studies on supercritical fluid extraction of actinides indicate a more efficient and environmentally sustainable technology. (author)

Mass transfer of SCWO processes: Molecular diffusion and mass transfer coefficients of inorganic nitrate species in sub- and supercritical water

Energy Technology Data Exchange (ETDEWEB)

Goemans, M.G.E.; Gloyna, E.F. [Univ. of Texas, Austin, TX (United States). Dept. of Civil Engineering; Buelow, S.J. [Los Alamos National Lab., NM (United States)

1996-04-01

Molecular diffusion coefficients of lithium-, sodium-, potassium-, cesium-, calcium-, and strontium nitrate in subcritical water were determined by analysis of Taylor dispersion profiles. Pressures ranged from 300 to 500 bar at temperatures ranging from 25{degrees}C to 300{degrees}C. The reported diffusion values were determined at infinite dilution. Molecular diffusion coefficients were 10 to 20 times faster in near-critical subcritical water than in water at ambient temperature and pressure (ATP). These findings implied that the diffusion rates were more liquid like than they were gas like, hence experimental results were correlated with diffusion models for liquids. The subcritical diffusion data presented in this work, and supercritical diffusion results published elsewhere were correlated with hydrodynamic diffusion equations. Both the Wilke-Chang correlation and the Stokes-Einstein equation yielded predictions within 10% of the experimental results if the structure of the diffusing species could be estimated. The effect of the increased diffusion rates on mass transfer rates in supercritical water oxidation applications was quantified, with emphasis on heterogeneous oxidation processes. This study and results published elsewhere showed that diffusion limited conditions are much more likely to be encountered in SCWO processes than commonly acknowledged.

Wetting front instability in an initially wet unsaturated fracture

International Nuclear Information System (INIS)

Nicholl, M.J.; Glass, R.J.; Nguyen, H.A.

1992-01-01

Experimental results exploring gravity-driven wetting front instability in a pre-wetted, rough-walled analog fracture are presented. Initial conditions considered include a uniform moisture field wetted to field capacity of the analog fracture and the structured moisture field created by unstable infiltration into an initially dry fracture. As in previous studies performed under dry initial conditions, instability was found to result both at the cessation of stable infiltration and at flux lower than the fracture capacity under gravitational driving force. Individual fingers were faster, narrower, longer, and more numerous than observed under dry initial conditions. Wetting fronts were found to follow existing wetted structure, providing a mechanism for rapid recharge and transport

Wetting front instability in an initially wet unsaturated fracture

International Nuclear Information System (INIS)

Nicholl, M.J.; Glass, R.J.; Nguyen, H.A.

1993-01-01

Experimental results exploring gravity-driven wetting from instability in a pre-wetted, rough-walled analog fractures such as those at Yucca Mountain are presented. Initial conditions considered include a uniform moisture field wetted to field capacity of the analog fracture and the structured moisture field created by unstable infiltration into an initially dry fracture. As in previous studies performed under dry initial conditions, instability was found to result both at the cessation of stable infiltration and at flux lower than the fracture capacity under gravitational driving force. Individual fingers were faster, narrower, longer, and more numerous than observed under dry initial conditions. Wetting fronts were found to follow existing wetted structure, providing a mechanism for rapid recharge and transport

Use and practice of achiral and chiral supercritical fluid chromatography in pharmaceutical analysis and purification.

Science.gov (United States)

Lemasson, Elise; Bertin, Sophie; West, Caroline

2016-01-01

The interest of pharmaceutical companies for complementary high-performance chromatographic tools to assess a product's purity or enhance this purity is on the rise. The high-throughput capability and economic benefits of supercritical fluid chromatography, but also the "green" aspect of CO2 as the principal solvent, render supercritical fluid chromatography very attractive for a wide range of pharmaceutical applications. The recent reintroduction of new robust instruments dedicated to supercritical fluid chromatography and the progress in stationary phase technology have also greatly benefited supercritical fluid chromatography. Additionally, it was shown several times that supercritical fluid chromatography could be orthogonal to reversed-phase high-performance liquid chromatography and could efficiently compete with it. Supercritical fluid chromatography is an adequate tool for small molecules of pharmaceutical interest: synthetic intermediates, active pharmaceutical ingredients, impurities, or degradation products. In this review, we first discuss about general chromatographic conditions for supercritical fluid chromatography analysis to better suit compounds of pharmaceutical interest. We also discuss about the use of achiral and chiral supercritical fluid chromatography for analytical purposes and the recent applications in these areas. The use of preparative supercritical fluid chromatography by pharmaceutical companies is also covered. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

PREFACE: Dynamics of wetting Dynamics of wetting

Science.gov (United States)

Grest, Gary S.; Oshanin, Gleb; Webb, Edmund B., III

2009-11-01

Capillary phenomena associated with fluids wetting other condensed matter phases have drawn great scientific interest for hundreds of years; consider the recent bicentennial celebration of Thomas Young's paper on equilibrium contact angles, describing the geometric shape assumed near a three phase contact line in terms of the relevant surface energies of the constituent phases [1]. Indeed, nearly a century has passed since the seminal papers of Lucas and Washburn, describing dynamics of capillary imbibition [2, 3]. While it is generally appreciated that dynamics of fluid wetting processes are determined by the degree to which a system is out of capillary equilibrium, myriad complications exist that challenge the fundamental understanding of dynamic capillary phenomena. The topic has gathered much interest from recent Nobel laureate Pierre-Gilles de Gennes, who provided a seminal review of relevant dissipation mechanisms for fluid droplets spreading on solid surfaces [4] Although much about the dynamics of wetting has been revealed, much remains to be learned and intrinsic technological and fundamental interest in the topic drives continuing high levels of research activity. This is enabled partly by improved experimental capabilities for resolving wetting processes at increasingly finer temporal, spatial, and chemical resolution. Additionally, dynamic wetting research advances via higher fidelity computational modeling capabilities, which drive more highly refined theory development. The significance of this topic both fundamentally and technologically has resulted in a number of reviews of research activity in wetting dynamics. One recent example addresses the evaluation of existing wetting dynamics theories from an experimentalist's perspective [5]. A Current Opinion issue was recently dedicated to high temperature capillarity, including dynamics of high temperature spreading [6]. New educational tools have recently emerged for providing instruction in wetting

Effect of thermal treatment on the corrosion resistance of Type 316L stainless steel exposed in supercritical water

Energy Technology Data Exchange (ETDEWEB)

Jiao, Y. [Department of Materials Science & Engineering, McMaster University, Hamilton, ON (Canada); Zheng, W. [CanmetMATERIALS, Natural Resources Canada, Hamilton, ON (Canada); Guzonas, D.A. [Canadian Nuclear Laboratories Chalk River Laboratories, ON (Canada); Cook, W.G. [Department of Chemical Engineering, University of New Brunswick, Fredericton, NB (Canada); Kish, J.R., E-mail: kishjr@mcmaster.ca [Department of Materials Science & Engineering, McMaster University, Hamilton, ON (Canada)

2015-09-15

There are still unknown aspects about the growth mechanism of oxide scales formed on candidate stainless steel fuel cladding materials during exposure in supercritical water (SCW) under the conditions relevant to the Canadian supercritical water-cooled reactor (SCWR). The tendency for intermetallic precipitates to form within the grains and on grain boundaries during prolonged exposure at high temperatures represents an unknown factor to corrosion resistance, since they tend to bind alloyed Cr. The objective of this study was to better understand the extent to which intermetallic precipitates affects the mode and extent of corrosion in SCW. Type 316L stainless steel, used as a model Fe–Cr–Ni–Mo alloy, was exposed to 25 MPa SCW at 550 °C for 500 h in a static autoclave for this purpose. Mechanically-abraded samples were tested in the mill-annealed (MA) and a thermally-treated (TT) condition. The thermal treatment was conducted at 815 °C for 1000 h to precipitate the carbide (M{sub 23}C{sub 6}), chi (χ), laves (η) and sigma (σ) phases. It was found that although relatively large intermetallic precipitates formed at the scale/alloy interface locally affected the oxide scale formation, their discontinuous formation did not affect the short-term overall apparent corrosion resistance.

Effect of thermal treatment on the corrosion resistance of Type 316L stainless steel exposed in supercritical water

Science.gov (United States)

Jiao, Y.; Zheng, W.; Guzonas, D. A.; Cook, W. G.; Kish, J. R.

2015-09-01

There are still unknown aspects about the growth mechanism of oxide scales formed on candidate stainless steel fuel cladding materials during exposure in supercritical water (SCW) under the conditions relevant to the Canadian supercritical water-cooled reactor (SCWR). The tendency for intermetallic precipitates to form within the grains and on grain boundaries during prolonged exposure at high temperatures represents an unknown factor to corrosion resistance, since they tend to bind alloyed Cr. The objective of this study was to better understand the extent to which intermetallic precipitates affects the mode and extent of corrosion in SCW. Type 316L stainless steel, used as a model Fe-Cr-Ni-Mo alloy, was exposed to 25 MPa SCW at 550 °C for 500 h in a static autoclave for this purpose. Mechanically-abraded samples were tested in the mill-annealed (MA) and a thermally-treated (TT) condition. The thermal treatment was conducted at 815 °C for 1000 h to precipitate the carbide (M23C6), chi (χ), laves (η) and sigma (σ) phases. It was found that although relatively large intermetallic precipitates formed at the scale/alloy interface locally affected the oxide scale formation, their discontinuous formation did not affect the short-term overall apparent corrosion resistance.

Reaction kinetics of cellulose hydrolysis in subcritical and supercritical water

Science.gov (United States)

Olanrewaju, Kazeem Bode

The uncertainties in the continuous supply of fossil fuels from the crisis-ridden oil-rich region of the world is fast shifting focus on the need to utilize cellulosic biomass and develop more efficient technologies for its conversion to fuels and chemicals. One such technology is the rapid degradation of cellulose in supercritical water without the need for an enzyme or inorganic catalyst such as acid. This project focused on the study of reaction kinetics of cellulose hydrolysis in subcritical and supercritical water. Cellulose reactions at hydrothermal conditions can proceed via the homogeneous route involving dissolution and hydrolysis or the heterogeneous path of surface hydrolysis. The work is divided into three main parts. First, the detailed kinetic analysis of cellulose reactions in micro- and tubular reactors was conducted. Reaction kinetics models were applied, and kinetics parameters at both subcritical and supercritical conditions were evaluated. The second major task was the evaluation of yields of water soluble hydrolysates obtained from the hydrolysis of cellulose and starch in hydrothermal reactors. Lastly, changes in molecular weight distribution due to hydrothermolytic degradation of cellulose were investigated. These changes were also simulated based on different modes of scission, and the pattern generated from simulation was compared with the distribution pattern from experiments. For a better understanding of the reaction kinetics of cellulose in subcritical and supercritical water, a series of reactions was conducted in the microreactor. Hydrolysis of cellulose was performed at subcritical temperatures ranging from 270 to 340 °C (tau = 0.40--0.88 s). For the dissolution of cellulose, the reaction was conducted at supercritical temperatures ranging from 375 to 395 °C (tau = 0.27--0.44 s). The operating pressure for the reactions at both subcritical and supercritical conditions was 5000 psig. The results show that the rate-limiting step in

Geological model of supercritical geothermal reservoir related to subduction system

Science.gov (United States)

Tsuchiya, Noriyoshi

2017-04-01

Following the Great East Japan Earthquake and the accident at the Fukushima Daiichi Nuclear power station on 3.11 (11th March) 2011, geothermal energy came to be considered one of the most promising sources of renewable energy for the future in Japan. The temperatures of geothermal fields operating in Japan range from 200 to 300 °C (average 250 °C), and the depths range from 1000 to 2000 m (average 1500 m). In conventional geothermal reservoirs, the mechanical behavior of the rocks is presumed to be brittle, and convection of the hydrothermal fluid through existing network is the main method of circulation in the reservoir. In order to minimize induced seismicity, a rock mass that is "beyond brittle" is one possible candidate, because the rock mechanics of "beyond brittle" material is one of plastic deformation rather than brittle failure. Supercritical geothermal resources could be evaluated in terms of present volcanic activities, thermal structure, dimension of hydrothermal circulation, properties of fracture system, depth of heat source, depth of brittle factures zone, dimension of geothermal reservoir. On the basis of the GIS, potential of supercritical geothermal resources could be characterized into the following four categories. 1. Promising: surface manifestation d shallow high temperature, 2 Probability: high geothermal gradient, 3 Possibility: Aseismic zone which indicates an existence of melt, 4 Potential : low velocity zone which indicates magma input. Base on geophysical data for geothermal reservoirs, we have propose adequate tectonic model of development of the supercritical geothermal reservoirs. To understand the geological model of a supercritical geothermal reservoir, granite-porphyry system, which had been formed in subduction zone, was investigated as a natural analog of the supercritical geothermal energy system. Quartz veins, hydrothermal breccia veins, and glassy veins are observed in a granitic body. The glassy veins formed at 500-550 �

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%.

Solubility of 1:1 Alkali Nitrates and Chlorides in Near-Critical and Supercritical Water : 1 Alkali Nitrates and Chlorides in Near-Critical and Supercritical Water

NARCIS (Netherlands)

Leusbrock, Ingo; Metz, Sybrand J.; Rexwinkel, Glenn; Versteeg, Geert F.

2009-01-01

To increase the available data oil systems containing supercritical water and inorganic compounds, all experimental setup was designed to investigate the solubilities of inorganic compounds Ill supercritical water, In this work, three alkali chloride salts (LiCl, NaCl, KCl) and three alkali nitrate

The effect of low-concentration inorganic materials on the behaviour of supercritical water

Energy Technology Data Exchange (ETDEWEB)

Imre, A.R., E-mail: imre@aeki.kfki.h [KFKI Atomic Energy Research Institute, POB 49, Budapest (Hungary); Hazi, G.; Horvath, A.; Maraczy, Cs. [KFKI Atomic Energy Research Institute, POB 49, Budapest (Hungary); Mazur, V.; Artemenko, S. [Odessa State Academy of Refrigeration, 1/3 Dvoryanslaya Str., 65026, Odessa (Ukraine)

2011-01-15

Research highlights: Small amount of inorganic materials (like corrosion products) can be dissolved in the supercritical water. Pseudo-critical temperature and other properties will be changed. Thermal and hydraulic behaviours of the SCW with small amount of contaminants differ in great extent from the behaviour of pure SCW. - Abstract: Supercritical water is a promising working fluid in the new Generation IV nuclear power plants. Due to the presence of the pseudo-critical line, the thermo-hydraulics (thermal and flow properties) and the physical chemistry of the supercritical water differ significantly from the pressurized hot water used in pressurized water reactors. In this study we would like to analyse the effect of small amount of inorganic material on the thermo-hydraulics of the supercritical water cooled nuclear reactors and other, non-nuclear supercritical water loops.

Effects of Supercritical CO 2 Conditioning on Cross-Linked Polyimide Membranes

KAUST Repository

Kratochvil, Adam M.; Koros, William J.

2010-01-01

The effects of supercritical CO2 (scCO2) conditioning on high-performance cross-linked polyimide membranes is examined through gas permeation and sorption experiments. Under supercritical conditions, the cross-linked polymers do not exhibit a

Effects of wet-ROA on shallow interface traps of n-type 4H-SiC MOS capacitors

International Nuclear Information System (INIS)

Zhu Qiaozhi; Wang Dejun

2014-01-01

The effects of wet re-oxidation annealing (wet-ROA) on the shallow interface traps of n-type 4H-SiC metal—oxide—semiconductor (MOS) capacitors were investigated by Gray—Brown method and angle-dependent X-ray photoelectron spectroscopy technique. The results present the energy distribution of the density of interface traps (D it ) from 0 to 0.2 eV below SiC conduction band edge (E C ) of the sample with wet-ROA for the first time, and indicate that wet-ROA could reduce the D it in this energy range by more than 60%. The reduction in D it is attributed to the reaction between the introduced oxygen and the SiO x C y species, which results in C release and SiO x C y transformation into higher oxidation states, thus reducing the SiO x C y content and the SiO x C y interface transition region thickness. (semiconductor devices)

[Wet work].

Science.gov (United States)

Kieć-Swierczyńska, Marta; Chomiczewska, Dorota; Krecisz, Beata

2010-01-01

Wet work is one of the most important risk factors of occupational skin diseases. Exposure of hands to the wet environment for more than 2 hours daily, wearing moisture-proof protective gloves for a corresponding period of time or necessity to wash hands frequently lead to the disruption of epidermal stratum corneum, damage to skin barrier function and induction of irritant contact dermatitis. It may also promote penetration of allergens into the skin and increase the risk of sensitization to occupational allergens. Exposure to wet work plays a significant role in occupations, such as hairdressers and barbers, nurses and other health care workers, cleaning staff, food handlers and metalworkers. It is more common among women because many occupations involving wet work are female-dominated. The incidence of wet-work-induced occupational skin diseases can be reduced by taking appropriate preventive measures. These include identification of high-risk groups, education of workers, organization of work enabling to minimize the exposure to wet work, use of personal protective equipment and skin care after work.

Effect of Composition and Mass Ratio on the Catalytic Wet Air Oxidation Catalyst Cu–Fe–La/FSC

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