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Sample records for methanol reformate gas

  1. Methanol partial oxidation reformer

    DOEpatents

    Ahmed, S.; Kumar, R.; Krumpelt, M.

    1999-08-17

    A partial oxidation reformer is described comprising a longitudinally extending chamber having a methanol, water and an air inlet and an outlet. An igniter mechanism is near the inlets for igniting a mixture of methanol and air, while a partial oxidation catalyst in the chamber is spaced from the inlets and converts methanol and oxygen to carbon dioxide and hydrogen. Controlling the oxygen to methanol mole ratio provides continuous slightly exothermic partial oxidation reactions of methanol and air producing hydrogen gas. The liquid is preferably injected in droplets having diameters less than 100 micrometers. The reformer is useful in a propulsion system for a vehicle which supplies a hydrogen-containing gas to the negative electrode of a fuel cell. 7 figs.

  2. Methanol partial oxidation reformer

    DOEpatents

    Ahmed, Shabbir; Kumar, Romesh; Krumpelt, Michael

    1999-01-01

    A partial oxidation reformer comprising a longitudinally extending chamber having a methanol, water and an air inlet and an outlet. An igniter mechanism is near the inlets for igniting a mixture of methanol and air, while a partial oxidation catalyst in the chamber is spaced from the inlets and converts methanol and oxygen to carbon dioxide and hydrogen. Controlling the oxygen to methanol mole ratio provides continuous slightly exothermic partial oxidation reactions of methanol and air producing hydrogen gas. The liquid is preferably injected in droplets having diameters less than 100 micrometers. The reformer is useful in a propulsion system for a vehicle which supplies a hydrogen-containing gas to the negative electrode of a fuel cell.

  3. Methanol partial oxidation reformer

    DOEpatents

    Ahmed, Shabbir; Kumar, Romesh; Krumpelt, Michael

    2001-01-01

    A partial oxidation reformer comprising a longitudinally extending chamber having a methanol, water and an air inlet and an outlet. An igniter mechanism is near the inlets for igniting a mixture of methanol and air, while a partial oxidation catalyst in the chamber is spaced from the inlets and converts methanol and oxygen to carbon dioxide and hydrogen. Controlling the oxygen to methanol mole ratio provides continuous slightly exothermic partial oxidation reactions of methanol and air producing hydrogen gas. The liquid is preferably injected in droplets having diameters less than 100 micrometers. The reformer is useful in a propulsion system for a vehicle which supplies a hydrogen-containing gas to the negative electrode of a fuel cell.

  4. Methanol partial oxidation reformer

    DOEpatents

    Ahmed, S.; Kumar, R.; Krumpelt, M.

    1999-08-24

    A partial oxidation reformer is described comprising a longitudinally extending chamber having a methanol, water and an air inlet and an outlet. An igniter mechanism is near the inlets for igniting a mixture of methanol and air, while a partial oxidation catalyst in the chamber is spaced from the inlets and converts methanol and oxygen to carbon dioxide and hydrogen. Controlling the oxygen to methanol mole ratio provides continuous slightly exothermic partial oxidation reactions of methanol and air producing hydrogen gas. The liquid is preferably injected in droplets having diameters less than 100 micrometers. The reformer is useful in a propulsion system for a vehicle which supplies a hydrogen-containing gas to the negative electrode of a fuel cell. 7 figs.

  5. Development of a selective oxidation CO removal reactor for methanol reformate gas

    SciTech Connect

    Okada, Shunji; Takatani, Yoshiaki; Terada, Seijo; Ohtani, Shinichi

    1996-12-31

    This report forms part of a joint study on a PEFC propulsion system for surface ships, summarized in a presentation to this Seminar, entitled {open_quotes}Study on a Polymer Electrolyte Fuel Cell (PEFC) Propulsion System for Surface Ships{close_quotes}, and which envisages application to a 1,500 DWT cargo vessel. The aspect treated here concerns laboratory-scale tests aimed at reducing by selective oxidation to a level below 10 ppm the carbon monoxide (CO) contained to a concentration of around 1% in reformate gas.

  6. Method of steam reforming methanol to hydrogen

    DOEpatents

    Beshty, Bahjat S.

    1990-01-01

    The production of hydrogen by the catalyzed steam reforming of methanol is accomplished using a reformer of greatly reduced size and cost wherein a mixture of water and methanol is superheated to the gaseous state at temperatures of about 800.degree. to about 1,100.degree. F. and then fed to a reformer in direct contact with the catalyst bed contained therein, whereby the heat for the endothermic steam reforming reaction is derived directly from the superheated steam/methanol mixture.

  7. Methanol Steam Reforming for Hydrogen Production

    SciTech Connect

    Palo, Daniel R.; Dagle, Robert A.; Holladay, Jamie D.

    2007-09-11

    Review article covering developments in methanol steam reforming in the context of PEM fuel cell power systems. Subjects covered include methanol background, use, and production, comparison to other fuels, power system considerations, militrary requirements, competing technologies, catalyst development, and reactor and system development and demonstration.

  8. Methanol Steam Reformer on a Silicon Wafer

    SciTech Connect

    Park, H; Malen, J; Piggott, T; Morse, J; Sopchak, D; Greif, R; Grigoropoulos, C; Havstad, M; Upadhye, R

    2004-04-15

    A study of the reforming rates, heat transfer and flow through a methanol reforming catalytic microreactor fabricated on a silicon wafer are presented. Comparison of computed and measured conversion efficiencies are shown to be favorable. Concepts for insulating the reactor while maintaining small overall size and starting operation from ambient temperature are analyzed.

  9. Single Step Bi-reforming and Oxidative Bi-reforming of Methane (Natural Gas) with Steam and Carbon Dioxide to Metgas (CO-2H2) for Methanol Synthesis: Self-Sufficient Effective and Exclusive Oxygenation of Methane to Methanol with Oxygen.

    PubMed

    Olah, George A; Goeppert, Alain; Czaun, Miklos; Mathew, Thomas; May, Robert B; Prakash, G K Surya

    2015-07-15

    Catalysts based on suitable metal oxide supports, such as NiO/MgO and CoO/MgO, were shown to be active for single step bi-reforming, the combined steam and dry reforming of methane or natural gas with H2O and CO2 exclusively to metgas (CO-2H2) for efficient methanol synthesis. Reactions were carried out in a tubular flow reactor under pressures up to 42 bar at 830-910 °C. Using a CH4 to steam to CO2 ratio of ∼3:2:1 in the gas feed, the H2/CO ratio of 2:1 was achieved, which is desired for subsequent methanol synthesis. The needed 2/1 steam/CO2 feed ratio together with the reaction heat for the endothermic bi-reforming can be conveniently obtained by the complete combustion of a quarter part of the overall used methane (natural gas) with oxygen of the air (oxidative bi-reforming). Complete combustion of a part of methane followed by bi-reforming leads to the production of metgas (H2/CO in 2:1 mol ratio) for self-sufficient exclusive methanol synthesis. The long sought after but elusive efficient and selective oxygenation of methane to methanol is thus achieved in an effective and economic way without any oxidation byproduct formation according to CH4 + 1/2O2 → CH3OH. PMID:26086090

  10. Methanol steam reforming in a fuel cell drive system

    NASA Astrophysics Data System (ADS)

    Wiese, W.; Emonts, B.; Peters, R.

    Within the framework of the Joule III project a compact methanol reformer (CMR) with a specific weight of 2 kg/kW (lower heating value of H 2) was developed. This CMR contains a methanol and water vaporizer, a steam reformer, a heat carrier circuit and a catalytic burner unit. A laboratory fixed-bed reactor consisting of four tubes which could be filled with different amounts of catalyst was used to investigate the catalyst performance and the ageing behaviour. A hydrogen yield of 10 m N3/(h l Cat) can be achieved at 280°C. In this case, the methanol conversion rate is 95% and the dry product gas contains 0.9% CO. A linear decrease of the catalyst activity was observed which can be described by a loss of active catalyst mass of 5.5 mg/h. The catalyst was operated for more than 1000 h without having exhibited activity losses that made a catalyst change necessary. Besides, the stationary behaviour of the reforming reactor, the dynamic behaviour was studied. The time needed for start-up procedures has to be improved for reformers of a next generation. Moreover, the hydrogen production during reformer load changes will be discussed. Simulations of the power train in driving cycles show the different states of a reformer during dynamic operation.

  11. Methanol reformers for fuel cell powered vehicles: Some design considerations

    SciTech Connect

    Kumar, R.; Ahmed, S.; Krumpelt, M.; Myles, K.M.

    1990-01-01

    Fuel cells are being developed for use in automotive propulsion systems as alternatives for the internal combustion engine in buses, vans, passenger cars. The two most important operational requirements for a stand-alone fuel cell power system for a vehicle are the ability to start up quickly and the ability to supply the necessary power on demand for the dynamically fluctuating load. Methanol is a likely fuel for use in fuel cells for transportation applications. It is a commodity chemical that is manufactured from coal, natural gas, and other feedstocks. For use in a fuel cell, however, the methanol must first be converted (reformed) to a hydrogen-rich gas mixture. The desired features for a methanol reformer include rapid start-up, good dynamic response, high fuel conversion, small size and weight, simple construction and operation, and low cost. In this paper the present the design considerations that are important for developing such a reformer, namely: (1) a small catalyst bed for quick starting, small size, and low weight; (2) multiple catalysts for optimum operation of the dissociation and reforming reactions; (3) reforming by direct heat transfer partial oxidation for rapid response to fluctuating loads; and (4) thermal independence from the rest of the fuel cell system. 10 refs., 1 fig.

  12. Methanol simplifies gas processing

    SciTech Connect

    Minkkinen, A.; Jonchere, J.P.

    1997-12-31

    Recent development of a simple single solvent technology goes far to meet the complete gas processing needs. The use of methanol, as practiced in the IPFEXOL process, where it is used not only as a hydrate inhibitor and antifreeze agent but as an acid gas extraction solvent makes the complete gas processing scheme simple and probably the most cost effective as well. This paper presents several gas processing applications where water, hydrocarbon liquids and acid gases are removed from natural wellhead production gases. Water and hydrocarbon liquids removal is achieved to the extent necessary to make a pipeline transportable gas or meet downstream cryogenic processing demands. These are illustrated with recent applications of the IFPEX-1 process successfully operating today in North America and the Far East. A recent North Sea offshore project is highlighted showing the particular advantages in offshore applications. For the removal of water and hydrocarbon liquids together with a substantial quantity of not only CO{sub 2} but H{sub 2}S, the most complete methanol use scheme is presented. This is illustrated with the development of an advanced version of the IFPEX-2 process containing some innovative but simple equipment concepts which yields high pressure dry acid gases for reinjection or a high quality acid gas destined to Claus type sulfur recovery.

  13. Materials experience in methanol reforming units

    SciTech Connect

    Baumert, K.L.; Hoffman, J.J.

    1997-09-01

    Metallurgical evaluations were performed on samples of Type 310 and aluminized 304 SS after long-term, high temperature exposure in methanol reforming service. The secondary phases were identified and the effectiveness of aluminizing at inhibiting metal dusting was examined. Secondary phases adversely affect the materials service life and repairability. Aluminizing effectively inhibits metal dusting for at least 13--14 years. Metal dusting is most severe in crevices on bare metal.

  14. Application of Flexible Micro Temperature Sensor in Oxidative Steam Reforming by a Methanol Micro Reformer

    PubMed Central

    Lee, Chi-Yuan; Lee, Shuo-Jen; Shen, Chia-Chieh; Yeh, Chuin-Tih; Chang, Chi-Chung; Lo, Yi-Man

    2011-01-01

    Advances in fuel cell applications reflect the ability of reformers to produce hydrogen. This work presents a flexible micro temperature sensor that is fabricated based on micro-electro-mechanical systems (MEMS) technology and integrated into a flat micro methanol reformer to observe the conditions inside that reformer. The micro temperature sensor has higher accuracy and sensitivity than a conventionally adopted thermocouple. Despite various micro temperature sensor applications, integrated micro reformers are still relatively new. This work proposes a novel method for integrating micro methanol reformers and micro temperature sensors, subsequently increasing the methanol conversion rate and the hydrogen production rate by varying the fuel supply rate and the water/methanol ratio. Importantly, the proposed micro temperature sensor adequately controls the interior temperature during oxidative steam reforming of methanol (OSRM), with the relevant parameters optimized as well. PMID:22319407

  15. Hydrogen from methanol for fuel cells in mobile systems: development of a compact reformer

    NASA Astrophysics Data System (ADS)

    Höhlein, B.; Boe, M.; Bøgild-Hansen, J.; Bröckerhoff, P.; Colsman, G.; Emonts, B.; Menzer, R.; Riedel, E.

    On-board generation of hydrogen from methanol with a reformer in connection with the use of a proton-exchange membrane fuel cell (PEMFC) is an attractive option for a passenger car drive. Special considerations are required to obtain low weight and volume. Furthermore, the PEMFC of today cannot tolerate more than 10 ppm of carbon monoxide in the fuel. Therefore a gas conditioning step is needed after the methanol reformer. Our main research activities focus on the conceptual design of a drive system for a passenger car with methanol reformer and PEMFC: engineering studies with regard to different aspects of this design including reformer, catalytic burner, gas conditioning, balances of the fuel cycles and basic design of a compact methanol reformer. The work described here was carried out within the framework of a JOULE II project of the European Union (1993-1995). Extensive experimental studies have been carried out at the Forschungszentrum Jülich GmbH (KFA) in Germany and at Haldor Topsøe A/S in Denmark.

  16. Reformers for the production of hydrogen from methanol and alternative fuels for fuel cell powered vehicles

    SciTech Connect

    Kumar, R.; Ahmed, S.; Krumpelt, M.; Myles, K.M.

    1992-08-01

    The objective of this study was (i) to assess the present state of technology of reformers that convert methanol (or other alternative fuels) to a hydrogen-rich gas mixture for use in a fuel cell, and (ii) to identify the R&D needs for developing reformers for transportation applications. Steam reforming and partial oxidation are the two basic types of fuel reforming processes. The former is endothermic while the latter is exothermic. Reformers are therefore typically designed as heat exchange systems, and the variety of designs used includes shell-and-tube, packed bed, annular, plate, and cyclic bed types. Catalysts used include noble metals and oxides of Cu, Zn, Cr, Al, Ni, and La. For transportation applications a reformer must be compact, lightweight, and rugged. It must also be capable of rapid start-up and good dynamic performance responsive to fluctuating loads. A partial oxidation reformer is likely to be better than a steam reformer based on these considerations, although its fuel conversion efficiency is expected to be lower than that of a steam reformer. A steam reformer better lends itself to thermal integration with the fuel cell system; however, the thermal independence of the reformer from the fuel cell stack is likely to yield much better dynamic performance of the reformer and the fuel cell propulsion power system. For both steam reforming and partial oxidation reforming, research is needed to develop compact, fast start-up, and dynamically responsive reformers. For transportation applications, steam reformers are likely to prove best for fuel cell/battery hybrid power systems, and partial oxidation reformers are likely to be the choice for stand-alone fuel cell power systems.

  17. Reformers for the production of hydrogen from methanol and alternative fuels for fuel cell powered vehicles

    SciTech Connect

    Kumar, R.; Ahmed, S.; Krumpelt, M.; Myles, K.M.

    1992-08-01

    The objective of this study was (i) to assess the present state of technology of reformers that convert methanol (or other alternative fuels) to a hydrogen-rich gas mixture for use in a fuel cell, and (ii) to identify the R D needs for developing reformers for transportation applications. Steam reforming and partial oxidation are the two basic types of fuel reforming processes. The former is endothermic while the latter is exothermic. Reformers are therefore typically designed as heat exchange systems, and the variety of designs used includes shell-and-tube, packed bed, annular, plate, and cyclic bed types. Catalysts used include noble metals and oxides of Cu, Zn, Cr, Al, Ni, and La. For transportation applications a reformer must be compact, lightweight, and rugged. It must also be capable of rapid start-up and good dynamic performance responsive to fluctuating loads. A partial oxidation reformer is likely to be better than a steam reformer based on these considerations, although its fuel conversion efficiency is expected to be lower than that of a steam reformer. A steam reformer better lends itself to thermal integration with the fuel cell system; however, the thermal independence of the reformer from the fuel cell stack is likely to yield much better dynamic performance of the reformer and the fuel cell propulsion power system. For both steam reforming and partial oxidation reforming, research is needed to develop compact, fast start-up, and dynamically responsive reformers. For transportation applications, steam reformers are likely to prove best for fuel cell/battery hybrid power systems, and partial oxidation reformers are likely to be the choice for stand-alone fuel cell power systems.

  18. Compact methanol reformer test for fuel-cell powered light-duty vehicles

    NASA Astrophysics Data System (ADS)

    Emonts, B.; Bøgild Hansen, J.; Lœgsgaard Jørgensen, S.; Höhlein, B.; Peters, R.

    On-board production of hydrogen from methanol based on a steam reformer in connection with the use of low-temperature fuel-cells (PEMFC) is an attractive option as energy conversion unit for light-duty vehicles. A steam reforming process at higher pressures with an external burner offers advantages in comparison to a steam reformer with integrated partial oxidation in terms of total efficiency for electricity production. The main aim of a common project carried out by the Forschungszentrum Jülich (FZJ), Haldor Topsøe A/S (HTAS) and Siemens AG is to design, to construct and to test a steam reformer reactor concept (HTAS) with external catalytic burner (FZJ) as heat source as well as catalysts for heterogeneously catalyzed hydrogen production (HTAS), concepts for gas treatment (HTAS, FZJ) and a low-temperature fuel cell (Siemens). Based on the experimental results obtained so far concerning methanol reformers, catalytic burners and gas conditioning units, our report describes the total system, a test unit and preliminary test results related to a hydrogen production capacity of 50 kW (LHV) and dynamic operating conditions. This hydrogen production system is aimed at reducing the specific weight (<2 kg/kWth or 4 kg/kWel) combined with high efficiency for net electricity generation from methanol (about 50%) and low specific emissions. The application of Pd-membranes as gas cleaning unit fulfill the requirements with high hydrogen permeability and low cost of the noble metal.

  19. Kinetics, simulation and optimization of methanol steam reformer for fuel cell applications

    NASA Astrophysics Data System (ADS)

    Choi, Yongtaek; Stenger, Harvey G.

    To evaluate reaction rates for making hydrogen from methanol, kinetic studies of methanol decomposition, methanol steam reforming, the water gas shift reaction, and CO selective oxidation have been performed. These reactions were studied in a microreactor testing unit using a commercial Cu-ZnO/Al 2O 3 catalyst for the first three reactions and Pt-Fe/γ-alumina catalyst for the last reaction. The activity tests were performed between 120 and 325 °C at atmospheric pressure with a range of feed rates and compositions. For methanol decomposition, a simplified reaction network of five elementary reactions was proposed and parameters for all five rate expressions were obtained using non-linear least squares optimization, numerical integration of a one-dimensional PFR model, and extensive experimental data. Similar numerical analysis was carried out to obtain the rate expressions for methanol steam reaction, the water gas shift reaction, and CO selective oxidation. Combining the three reactors with several heat exchange options, an integrated methanol reformer system was designed and simulated using MATLAB. Using this simulation, the product distribution, the effects of reactor volume and temperature, and the options of water and air injection rates were studied. Also, a series of optimization tests were conducted to give maximum hydrogen yield and/or maximum economic profit.

  20. Characterization of ZrO 2-promoted Cu/ZnO/nano-Al 2O 3 methanol steam reforming catalysts

    NASA Astrophysics Data System (ADS)

    Jones, Samuel D.; Neal, Luke M.; Everett, Michael L.; Hoflund, Gar B.; Hagelin-Weaver, Helena E.

    2010-10-01

    Three Cu/ZnO/ZrO 2/Al 2O 3 methanol reforming catalysts were investigated using X-ray photoelectron spectroscopy (XPS). The catalysts which contained ZrO 2 from a monoclinic nanoparticle ZrO 2 precursor exhibit both a higher activity toward the methanol steam reforming reaction and a lower CO production rate compared to catalysts composed of an XRD-amorphous ZrO 2 produced by impregnation using a Zr(NO 3) 2 precursor. The presence of a monoclinic phase appears to result in an increased charge transfer between the Zr and Cu species, as evidenced by a relatively electron-rich ZrO 2 phase and a partially oxidized Cu species on reduced catalysts. This electron deficient Cu species is more reactive toward the methanol reforming reaction and partially suppresses CO formation through the reverse water gas shift or methanol decomposition reactions.

  1. Evaluation of dissociated and steam-reformed methanol as automotive engine fuels

    NASA Technical Reports Server (NTRS)

    Lalk, T. R.; Mccall, D. M.; Mccanlies, J. M.

    1984-01-01

    Dissociated and steam reformed methanol were evaluated as automotive engine fuels. Advantages and disadvantages in using methanol in the reformed rather than liquid state were discussed. Engine dynamometer tests were conducted with a four cylinder, 2.3 liter, spark ignition automotive engine to determine performance and emission characteristics operating on simulated dissociated and steam reformed methanol (2H2 + CO and 3H2 + CO2 respectively), and liquid methanol. Results are presented for engine performance and emissions as functions of equivalence ratio, at various throttle settings and engine speeds. Operation on dissociated and steam reformed methanol was characterized by flashback (violent propagation of a flame into the intake manifold) which limited operation to lower power output than was obtainable using liquid methanol. It was concluded that: an automobile could not be operated solely on dissociated or steam reformed methanol over the entire required power range - a supplementary fuel system or power source would be necessary to attain higher powers; the use of reformed mechanol, compared to liquid methanol, may result in a small improvement in thermal efficiency in the low power range; dissociated methanol is a better fuel than steam reformed methanol for use in a spark ignition engine; and use of dissociated or steam reformed methanol may result in lower exhaust emissions compared to liquid methanol.

  2. Hydrogen production from the steam reforming of Dinethyl Ether and Methanol

    SciTech Connect

    Semelsberger, T. A.; Borup, R. L.

    2004-01-01

    This study investigates dimethyl ether (DME) steam reforming for the generation of hydrogen rich fuel cell feeds for fuel cell applications. Methanol has long been considered as a fuel for the generation of hydrogen rich fuel cell feeds due to its high energy density, low reforming temperature, and zero impurity content. However, it has not been accepted as the fuel of choice due its current limited availability, toxicity and corrosiveness. While methanol steam reforming for the generation of hydrogen rich fuel cell feeds has been extensively studied, the steam reforming of DME, CH{sub 3}OCH{sub 3} + 3H{sub 2}O = 2CO{sub 2} + 6H{sub 2}, has had limited research effort. DME is the simplest ether (CH{sub 3}OCH{sub 3}) and is a gas at ambient conditions. DME has physical properties similar to those of LPG fuels (i.e. propane and butane), resulting in similar storage and handling considerations. DME is currently used as an aerosol propellant and has been considercd as a diesel substitute due to the reduced NOx, SOx and particulate emissions. DME is also being considered as a substitute for LPG fuels, which is used extensively in Asia as a fuel for heating and cooking, and naptha, which is used for power generation. The potential advantages of both methanol and DME include low reforming temperature, decreased fuel proccssor startup energy, environmentally benign, visible flame, high heating value, and ease of storage and transportation. In addition, DME has the added advantages of low toxicity and being non-corrosive. Consequently, DME may be an ideal candidate for the generation of hydrogen rich fuel cell feeds for both automotive and portable power applications. The steam reforming of DME has been demonstrated to occur through a pair of reactions in series, where the first reaction is DME hydration followed by MeOH steam reforming to produce a hydrogen rich stream.

  3. Hydrogen generation for fuel-cell power systems by high-pressure catalytic methanol-steam reforming

    SciTech Connect

    Peppley, B.A.; Amphlett, J.C.; Kearns, L.M.; Mann, R.F.; Roberge, P.R.

    1997-12-31

    Results of kinetic studies of methanol-steam reforming on a commercial low-temperature shift catalyst, BASF K3-110, are reported. A comprehensive Langmuir-Hinshelwood kinetic model of methanol-steam reforming on Cu/ZnO/Al{sub 2}O{sub 3} catalyst was used to simulate a methanol-steam reformer operating at pressures up to 45 bar. At constant temperature and steam-to-methanol ratio, increasing the pressure results in an increase in the initial rate of the reaction and a corresponding improvement in reformer performance. This is partially offset as the equilibrium conversion decreases with increasing pressure. The rate of reaction is highest at low conversion. The result is that there is a large heat demand near the entrance of the catalyst bed which causes a strong endothermic effect and a corresponding temperature minimum. In the worst case, this temperature minimum can be below the dewpoint temperature of the operating fluid causing a loss in reformer performance due to condensation in the pores of the catalyst. The situation is exacerbated by the potential for thermal damage to other regions of the catalyst bed if the heating temperature is increased to overcome the endothermic effect. Catalyst deactivation at elevated pressures was also studied in an 80 hour experiment at 260 C. Increasing the operating pressure did not accelerate the rate of deactivation for the typical gas compositions encountered during normal reformer operation. No catalyst fouling was observed for experimental pressures as high as 40 bar at steam-to-methanol ratios greater than unity even though the tendency for carbon formation increases with pressure. Catalyst selectivity improved at lower conversion due to kinetic effects. The equilibrium CO concentration, however, does not vary significantly with pressure because of the stoichiometry of the water-gas shift reaction.

  4. A passively-fed methanol steam reformer heated with two-stage bi-fueled catalytic combustor

    NASA Astrophysics Data System (ADS)

    Lo, Kai-Fan; Wong, Shwin-Chung

    2012-09-01

    This paper presents further progress on our simple novel passively-fed methanol steam reformer. The present study focuses on the development of a catalytic combustor workable with both hydrogen and methanol fuels. The aim is to reutilize the exhaust hydrogen from a fuel cell under stable operation but burn methanol during the start-up. On a copper plate, the catalytic combustor in a u-turn channel is integrally machined under a two-turn serpentine-channel reformer. To resolve the highly different fuel reactivities, a suitably diluted catalyst formula demonstrates uniform temperature distributions burning with either liquid methanol or an H2/CO2 mixture simulating the exhaust gas from a fuel cell. In a two-stage process, it first takes 25 min to reach 270 °C by burning methanol. After the fuel is switched to the H2/CO2 mixture, another 20 min is needed to attain an optimal steady state which yields a high methanol conversion of 95% and acceptably low CO fraction of 1.04% at a reaction temperature of 278 °C. The H2 and CO2 concentrations are 75.1% and 23.6%.

  5. Controller design and experiment for autothermal reforming of methanol in miniature reactor.

    PubMed

    Lu, Jiangang; Zhuang, Hong; Yang, Qinmin; Wang, Xuefei; Zheng, Jianfeng; Chen, Jinshui; Sun, Youxian

    2014-09-01

    In this paper, a miniature methanol fuel processor and its controller design is introduced for onboard hydrogen production. The hydrogen is generated via autothermal reforming of methanol. The control scheme consists of a hydrogen flow rate controller and a reforming temperature controller. To deal with uncertain system dynamics and external disturbance, an adaptive sliding mode control algorithm is adopted as the hydrogen flow rate controller for regulating hydrogen flow rate by manipulating methanol flow rate. Additionally, a high-gain observer is implemented to estimate the unmeasurable system state. The stability of closed-loop system is guaranteed by standard Lyapunov analysis. Furthermore, a variable ratio control law is employed as the reforming temperature controller to achieve steady reforming temperature by adjusting the reforming air flow rate. Finally, the effectiveness of the entire system is testified by experimental means. PMID:24398056

  6. Rapid catalytic processes in reforming of methane and successive synthesis of methanol and its derivatives

    NASA Astrophysics Data System (ADS)

    Inui, Tomoyuki

    1997-11-01

    In order to obtain high quality fuels and basic raw materials for petrochemical industries, novel catalysts which enable the realization of new synthetic routes have been investigated. First, a highly active Rh-modified Ni-based composite catalyst, NiCe 2O 3PtRh, supported on a ceramic fiber in a plate shape was developed, which reformed methane into the syngas having an appropriate ratio of H2/CO. Furthermore, more combustible ethane or propane was added into the reaction gas and its catalytic combustion was allowed to occur on the same catalyst. The combustion heat compensated the reforming heat resulting in an extraordinarily high space-time yield of hydrogen, as high as 10,000 mol/1·h, even under the condition of a very short contact time, 5 ms, and a very low furnace temperature at around 400°C. Next, a highly active catalyst for methanol synthesis from CO 2-rich or CO-rich syngases was developed. A Cu-based CuZnCrAlGa mixed oxide catalyst was prepared by the uniform gelation method and it was mixed with Pd supported on χ-alumina. The composite catalyst exhibited a much higher activity than the conventional catalyst prepared by the precipitation method and a space-time yield of methanol of 1,300 and 6,730 g/l·h was amounted, respectively, from CO 2-rich and CO-rich syngases under 80 atm and at 270°C. Finally, the products obtained as mentioned above were introduced into the reactor, which was connected in series and the methanol was totally converted into hydrocarbons. In the case of a HGa-silicate catalyst, gasoline was obtained at as high a value as 1,860 g/l·h in space-time yield, and in the case of SAPO-34, ethylene and propylene were obtained with an equivalent selectivity.

  7. A MEMS-based reformed methanol fuel cell for portable power

    NASA Astrophysics Data System (ADS)

    Morse, J. D.; Upadhye, R. S.; Graff, R. T.; Spadaccini, C.; Park, H. G.; Hart, E. K.

    2007-09-01

    A reformed methanol fuel cell system is described. The use of a microfluidic fuel processor enables component scaling and integration sufficient to achieve power sources in the 2 10 W regime that are competitive in size and energy density in comparison to alternative power sources. While carbon monoxide tolerance of proton conducting membranes has typically limited the performance of reformed methanol fuel cells, phosphoric-acid-doped polybenzimidazole (PBI) membranes have been tested that exhibit no degradation for carbon monoxide >2% mole fraction. Further benefits of the PBI membrane include operating temperature of 150 200 °C, and no need for water to assist protonic conduction. As a result, a chemically and thermally robust fuel cell power source is realized. Results of methanol steam reforming and catalytic combustor heating elements formed in a silicon MEMS platform, and PBI membrane performance with reformate fuel feed will be discussed.

  8. HYDROGEN PRODUCTION FOR FUEL CELLS VIA REFORMING COAL-DERIVED METHANOL

    SciTech Connect

    Paul A. Erickson

    2006-04-01

    Hydrogen can be produced from many feedstocks including coal. The objectives of this project are to establish and prove a hydrogen production pathway from coal-derived methanol for fuel cell applications. This progress report is the tenth report submitted to the DOE reporting on the status and progress made during the course of the project. This report covers the time period of January 1-March 31, 2006. This quarter saw progress in six areas. These areas are: (1) The effect of catalyst dimension on steam reforming, (2) Transient characteristics of autothermal reforming, (3) Rich and lean autothermal reformation startup, (4) Autothermal reformation degradation with coal derived methanol, (5) Reformate purification system, and (6) Fuel cell system integration. All of the projects are proceeding on or slightly ahead of schedule.

  9. Activation of catalysts for synthesizing methanol from synthesis gas

    DOEpatents

    Blum, David B.; Gelbein, Abraham P.

    1985-01-01

    A method for activating a methanol synthesis catalyst is disclosed. In this method, the catalyst is slurried in an inert liquid and is activated by a reducing gas stream. The activation step occurs in-situ. That is, it is conducted in the same reactor as is the subsequent step of synthesizing methanol from a methanol gas stream catalyzed by the activated catalyst still dispersed in a slurry.

  10. The Effects of PdZn Crystallite Size on Methanol Steam Reforming

    SciTech Connect

    Dagle, Robert A.; Chin, Ya-Huei; Wang, Yong

    2007-11-30

    Exceptional activity and selectivity of Pd/ZnO catalysts for methanol steam reforming have been attributed to the formation of PdZn alloy. In this paper, we evaluated the crystallite size effects of PdZn alloy on methanol steam reforming. An organic preparation method was used to avoid the complexity from the alteration of ZnO morphology typically associated with the conventional aqueous preparation method. Both Pd loading and reduction temperature (>350ºC) were used to vary the crystallite size of PdZn alloy. Experimental activity studies and transmission electron microscope (TEM) characterizations indicated that formation of large sized PdZn crystallites exhibit high reactivity and low CO selectivity during methanol steam reforming.

  11. In situ XPS study of methanol reforming on PdGa near-surface intermetallic phases

    PubMed Central

    Rameshan, Christoph; Stadlmayr, Werner; Penner, Simon; Lorenz, Harald; Mayr, Lukas; Hävecker, Michael; Blume, Raoul; Rocha, Tulio; Teschner, Detre; Knop-Gericke, Axel; Schlögl, Robert; Zemlyanov, Dmitry; Memmel, Norbert; Klötzer, Bernhard

    2012-01-01

    In situ X-ray photoelectron spectroscopy and low-energy ion scattering were used to study the preparation, (thermo)chemical and catalytic properties of 1:1 PdGa intermetallic near-surface phases. Deposition of several multilayers of Ga metal and subsequent annealing to 503–523 K led to the formation of a multi-layered 1:1 PdGa near-surface state without desorption of excess Ga to the gas phase. In general, the composition of the PdGa model system is much more variable than that of its PdZn counterpart, which results in gradual changes of the near-surface composition with increasing annealing or reaction temperature. In contrast to near-surface PdZn, in methanol steam reforming, no temperature region with pronounced CO2 selectivity was observed, which is due to the inability of purely intermetallic PdGa to efficiently activate water. This allows to pinpoint the water-activating role of the intermetallic/support interface and/or of the oxide support in the related supported PdxGa/Ga2O3 systems, which exhibit high CO2 selectivity in a broad temperature range. In contrast, corresponding experiments starting on the purely bimetallic model surface in oxidative methanol reforming yielded high CO2 selectivity already at low temperatures (∼460 K), which is due to efficient O2 activation on PdGa. In situ detected partial and reversible oxidative Ga segregation on intermetallic PdGa is associated with total oxidation of intermediate C1 oxygenates to CO2. PMID:22875996

  12. Non-syngas direct steam reforming of methanol to hydrogen and carbon dioxide at low temperature.

    PubMed

    Yu, Kai Man Kerry; Tong, Weiyi; West, Adam; Cheung, Kevin; Li, Tong; Smith, George; Guo, Yanglong; Tsang, Shik Chi Edman

    2012-01-01

    A non-syngas direct steam reforming route is investigated for the conversion of methanol to hydrogen and carbon dioxide over a CuZnGaO(x) catalyst at 150-200 °C. This route is in marked contrast with the conventional complex route involving steam reformation to syngas (CO/H2) at high temperature, followed by water gas shift and CO cleanup stages for hydrogen production. Here we report that high quality hydrogen and carbon dioxide can be produced in a single-step reaction over the catalyst, with no detectable CO (below detection limit of 1 ppm). This can be used to supply proton exchange membrane fuel cells for mobile applications without invoking any CO shift and cleanup stages. The working catalyst contains, on average, 3-4 nm copper particles, alongside extremely small size of copper clusters stabilized on a defective ZnGa2O4 spinel oxide surface, providing hydrogen productivity of 393.6 ml g(-1)-cat h(-1) at 150 °C. PMID:23187630

  13. Performance evaluation of a proof-of-concept 70 W internal reforming methanol fuel cell system

    NASA Astrophysics Data System (ADS)

    Avgouropoulos, G.; Schlicker, S.; Schelhaas, K.-P.; Papavasiliou, J.; Papadimitriou, K. D.; Theodorakopoulou, E.; Gourdoupi, N.; Machocki, A.; Ioannides, T.; Kallitsis, J. K.; Kolb, G.; Neophytides, S.

    2016-03-01

    A proof-of-concept 70 W Internal Reforming Methanol Fuel Cell (IRMFC) stack including Balance-of-Plant (BoP) was designed, assembled and tested. Advent TPS® high-temperature, polymer electrolyte membrane electrode assemblies were employed for fuel cell operation at 200 °C. In order to avoid phosphoric acid poisoning of the reformer, the anode electrocatalyst of each cell was indirectly adjoined, via a separation plate, to a highly active CuMnAlOx catalyst coated onto copper foam, which served as methanol reforming layer. The reformer was in-situ converting the methanol/steam feed to the required hydrogen (internal reforming concept) at 200 °C, which was readily oxidized at the anode electrodes. The operation of the IRMFC was supported through a number of BoP components consisting of a start-up subsystem (air blower, evaporator and monolithic burner), a combined afterburner/evaporator device, methanol/water supply and data acquisition units (reactants/products analysis, temperature control, flow control, system load/output control). Depending on the composition of the liquid MeOH/H2O feed streams, current densities up to 0.18 A cm-2 and power output up to 70 W could be obtained with remarkable repeatability. Specific targets for improvement of the efficiency were identified.

  14. Bi-reforming of methane from any source with steam and carbon dioxide exclusively to metgas (CO-2H2) for methanol and hydrocarbon synthesis.

    PubMed

    Olah, George A; Goeppert, Alain; Czaun, Miklos; Prakash, G K Surya

    2013-01-16

    A catalyst based on nickel oxide on magnesium oxide (NiO/MgO) thermally activated under hydrogen is effective for the bi-reforming with steam and CO(2) (combined steam and dry reforming) of methane as well as natural gas in a tubular flow reactor at elevated pressures (5-30 atm) and temperatures (800-950 °C). By adjusting the CO(2)-to-steam ratio in the gas feed, the H(2)/CO ratio in the produced syn-gas could be easily adjusted in a single step to the desired value of 2 for methanol and hydrocarbon synthesis. PMID:23256664

  15. Autothermal Reforming of Natural Gas to Synthesis Gas

    SciTech Connect

    Steven F. Rice; David P. Mann

    2007-04-13

    This Project Final Report serves to document the project structure and technical results achieved during the 3-year project titled Advanced Autothermal Reformer for US Dept of Energy Office of Industrial Technology. The project was initiated in December 2001 and was completed March 2005. It was a joint effort between Sandia National Laboratories (Livermore, CA), Kellogg Brown & Root LLC (KBR) (Houston, TX) and Süd-Chemie (Louisville, KY). The purpose of the project was to develop an experimental capability that could be used to examine the propensity for soot production in an Autothermal Reformer (ATR) during the production of hydrogen-carbon monoxide synthesis gas intended for Gas-to-Liquids (GTL) applications including ammonia, methanol, and higher hydrocarbons. The project consisted of an initial phase that was focused on developing a laboratory-scale ATR capable of reproducing conditions very similar to a plant scale unit. Due to budget constraints this effort was stopped at the advanced design stages, yielding a careful and detailed design for such a system including ATR vessel design, design of ancillary feed and let down units as well as a PI&D for laboratory installation. The experimental effort was then focused on a series of measurements to evaluate rich, high-pressure burner behavior at pressures as high as 500 psi. The soot formation measurements were based on laser attenuation at a view port downstream of the burner. The results of these experiments and accompanying calculations show that soot formation is primarily dependent on oxidation stoichiometry. However, steam to carbon ratio was found to impact soot production as well as burner stability. The data also showed that raising the operating pressure while holding mass flow rates constant results in considerable soot formation at desirable feed ratios. Elementary reaction modeling designed to illuminate the role of CO2 in the burner feed showed that the conditions in the burner allow for the direct

  16. Renewable Electricity Generation via Solar-Powered Methanol Reforming: Hybrid Proton Exchange Membrane Fuel Cell Systems Based on Novel Non-Concentrating, Intermediate-Temperature Solar Collectors

    NASA Astrophysics Data System (ADS)

    Real, Daniel J.

    Tremendous research efforts have been conducted studying the capturing and conversion of solar energy. Solar thermal power systems offer a compelling opportunity for renewable energy utilization with high efficiencies and excellent cost-effectiveness. The goal of this work was to design a non-concentrating collector capable of reaching temperatures above 250 °C, use this collector to power methanol steam reforming, and operate a proton exchange membrane (PEM) fuel cell using the generated hydrogen. The study presents the construction and characterization of a non-concentrating, intermediate-temperature, fin-in-tube evacuated solar collector, made of copper and capable of reaching stagnation temperatures of 268.5 °C at 1000 W/m2 irradiance. The collector was used to power methanol steam reforming, including the initial heating and vaporization of liquid reactants and the final heating of the gaseous reactants. A preferential oxidation (PROX) catalyst was used to remove CO from simulated reformate gas, and this product gas was used to operate a PEM fuel cell. The results show 1) that the outlet temperature is not limited by heat transfer from the absorber coating to the heat transfer fluid, but by the amount of solar energy absorbed. This implicates a constant heat flux description of the heat transfer process and allows for the usage of materials with lower thermal conductivity than copper. 2) It is possible to operate a PEM fuel cell from reformate gas if a PROX catalyst is used to remove CO from the gas. 3) The performance of the fuel cell is only slightly decreased (~4%) by CO2 dilution present in the reformate and PROX gas. These results provide a foundation for the first renewable electricity generation via solar-powered methanol reforming through a hybrid PEM fuel cell system based on novel non-concentrating, intermediate-temperature solar collectors.

  17. HYDROGEN PRODUCTION FOR FUEL CELLS VIA REFORMING COAL-DERIVED METHANOL

    SciTech Connect

    Paul A. Erickson

    2006-01-01

    Hydrogen can be produced from many feedstocks including coal. The objectives of this project are to establish and prove a hydrogen production pathway from coal-derived methanol for fuel cell applications. This progress report is the ninth report submitted to the DOE reporting on the status and progress made during the course of the project. This report covers the time period of October 1, 2005-December 31, 2005. This quarter saw progress in four areas. These areas are: (1) reformate purification, (2) heat transfer enhancement, (3) autothermal reforming coal-derived methanol degradation test; and (4) model development for fuel cell system integration. The project is on schedule and is now shifting towards the design of an integrated PEM fuel cell system capable of using the coal-derived product. This system includes a membrane clean up unit and a commercially available PEM fuel cell.

  18. An introduction of CO₂ conversion by dry reforming with methane and new route of low-temperature methanol synthesis.

    PubMed

    Shi, Lei; Yang, Guohui; Tao, Kai; Yoneyama, Yoshiharu; Tan, Yisheng; Tsubaki, Noritatsu

    2013-08-20

    Carbon dioxide is one of the highest contributors to the greenhouse effect, as well as a cheap and nontoxic building block for single carbon source chemistry. As such, CO₂ conversion is one of most important research areas in energy and environment sciences, as well as in catalysis technology. For chemical conversion of CO₂, natural gas (mainly CH₄) is a promising counterpart molecule to the CO₂-related reaction, due to its high availability and low price. More importantly, being able to convert CH₄ to useful fuels and molecules is advantageous, because it is also a kind of "greenhouse effect" gas, and can be an energy alternative to petroleum oil. In this Account, we discuss our development of efficient catalysts with precisely designed nanostructure for CO₂ reforming of CH₄ to produce syngas (mixture of CO and H₂), which can then be converted to many chemicals and energy products. This new production flow can establish a GTL (gas-to-liquid) industry, being currently pushed by the shale gas revolution. From the viewpoint of GTL industry, developing a catalyst for CO₂ reforming of CH₄ is a challenge, because they need a very high production rate to make the huge GTL methane reformer as small as possible. In addition, since both CO₂ and CH₄ give off carbon deposits that deactivate non-precious metallic catalysts very quickly, the total design of catalyst support and supported metallic nanoparticles is necessary. We present a simple but useful method to prepare bimodal catalyst support, where small pores are formed inside large ones during the self-organization of nanoparticles from solution. Large pores enhance the mass transfer rate, while small pores provide large surface areas to disperse active metallic nanoparticles. More importantly, building materials for small pores can also be used as promoters or cocatalysts to further enhance the total activity and stability. Produced syngas from methane reforming is generally catalytically

  19. Methanol steam reforming in microreactor with constructal tree-shaped network

    NASA Astrophysics Data System (ADS)

    Chen, Yongping; Zhang, Chengbin; Wu, Rui; Shi, Mingheng

    2011-08-01

    The construcal tree-shaped network is introduced into the design of a methanol steam microreactor in the context of optimization of the flow configuration. A three-dimensional model for methanol steam reaction in this designed microreactor is developed and numerically analyzed. The methanol conversion, CO concentration in the product and the total pressure drop of the gases in the microreactor with constructal tree-shaped network are evaluated and compared with those in the serpentine reactor. It is found that the reaction of methanol steam reforming is enhanced in the constructal tree-shaped microreactor, since the tree-shaped reactor configuration, which acts an optimizer for the reactant distribution, provides a reaction space with larger surface-to-volume ratio and the reduction of reactant velocities in the branches. Compared with the serpentine microreactor, the constructal reactor possesses a higher methanol conversion rate accompanied with a higher CO concentration. The conversion rate of the constructal microreactor is more than 10% over that of serpentine reactor. More particularly, the reduction of flow distance makes the constructal microreactor still possess almost the same pressure drop as the corresponding serpentine reactor, despite that the bifurcations induce extra local pressure loss, and the reduction of channel size in branches also causes pressure losses.

  20. Hynol -- An economic process for methanol production from biomass and natural gas with reduced CO{sub 2} emission

    SciTech Connect

    Steinberg, M.; Dong, Yuanji

    1993-10-01

    The Hynol process is proposed to meet the demand for an economical process for methanol production with reduced CO{sub 2} emission. This new process consists of three reaction steps: (a) hydrogasification of biomass, (b) steam reforming of the produced gas with additional natural gas feedstock, and (c) methanol synthesis of the hydrogen and carbon monoxide produced during the previous two steps. The H{sub 2}-rich gas remaining after methanol synthesis is recycled to gasify the biomass in an energy neutral reactor so that there is no need for an expensive oxygen plant as required by commercial steam gasifiers. Recycling gas allows the methanol synthesis reactor to perform at a relatively lower pressure than conventional while the plant still maintains high methanol yield. Energy recovery designed into the process minimizes heat loss and increases the process thermal efficiency. If the Hynol methanol is used as an alternative and more efficient automotive fuel, an overall 41% reduction in CO{sub 2} emission can be achieved compared to the use of conventional gasoline fuel. A preliminary economic estimate shows that the total capital investment for a Hynol plant is 40% lower than that for a conventional biomass gasification plant. The methanol production cost is $0.43/gal for a 1085 million gal/yr Hynol plant which is competitive with current U.S. methanol and equivalent gasoline prices. Process flowsheet and simulation data using biomass and natural gas as cofeedstocks are presented. The Hynol process can convert any condensed carbonaceous material, especially municipal solid waste (MSW), to produce methanol.

  1. Hynol: An economic process for methanol production from biomass and natural gas with reduced CO2 emission

    NASA Astrophysics Data System (ADS)

    Steinberg, M.; Dong, Yuanji

    1993-10-01

    The Hynol process is proposed to meet the demand for an economical process for methanol production with reduced CO2 emission. This new process consists of three reaction steps: (1) hydrogasification of biomass, (2) steam reforming of the produced gas with additional natural gas feedstock, and (3) methanol synthesis of the hydrogen and carbon monoxide produced during the previous two steps. The H2-rich gas remaining after methanol synthesis is recycled to gasify the biomass in an energy neutral reactor so that there is no need for an expensive oxygen plant as required by commercial steam gasifiers. Recycling gas allows the methanol synthesis reactor to perform at a relatively lower pressure than conventional while the plant still maintains high methanol yield. Energy recovery designed into the process minimizes heat loss and increases the process thermal efficiency. If the Hynol methanol is used as an alternative and more efficient automotive fuel, an overall 41% reduction in CO2 emission can be achieved compared to the use of conventional gasoline fuel. A preliminary economic estimate shows that the total capital investment for a Hynol plant is 40% lower than that for a conventional biomass gasification plant. The methanol production cost is $0.43/gal for a 1085 million gal/yr Hynol plant which is competitive with current U.S. methanol and equivalent gasoline prices. Process flowsheet and simulation data using biomass and natural gas as cofeedstocks are presented. The Hynol process can convert any condensed carbonaceous material, especially municipal solid waste (MSW), to produce methanol.

  2. A non-syn-gas catalytic route to methanol production.

    PubMed

    Wu, Cheng-Tar; Yu, Kai Man Kerry; Liao, Fenglin; Young, Neil; Nellist, Peter; Dent, Andrew; Kroner, Anna; Tsang, Shik Chi Edman

    2012-01-01

    Methanol is an important platform molecule for chemical synthesis and its high energy density also renders it a good candidate as a cleaner transportation fuel. At present, methanol is manufactured from natural gas via the indirect syn-gas route. Here we show that ethylene glycol, a versatile chemical derived from biomass or fossil fuels, can be directly converted to methanol in hydrogen with high selectivity over a Pd/Fe(2)O(3) co-precipitated catalyst. This opens up a possibility for diversification in natural resources for energy-starved countries. The working catalyst contains extremely small 'PdFe' clusters and metal adatoms on defective iron oxide to give the required metal-support interaction for the novel synthesis. PMID:22968696

  3. Bio-methanol from Bio-oil Reforming Syngas Using Dual-reactor

    NASA Astrophysics Data System (ADS)

    Ye, Tong-qi; Yan, Shi-zhi; Xu, Yong; Qiu, Song-bai; Liu, Yong; Li, Quan-xin

    2011-08-01

    A dual-reactor, assembled with the on-line syngas conditioning and methanol synthesis, was successfully applied for high efficient conversion of rich CO2 bio-oil derived syngas to bio-methanol. In the forepart catalyst bed reactor, the catalytic conversion can effectively adjust the rich-CO2 crude bio-syngas into the CO-containing bio-syngas using the CuZnAlZr catalyst. After the on-line syngas conditioning at 450 °C, the CO2/CO ratio in the bio-syngas significantly decreased from 6.3 to 1.2. In the rearward catalyst bed reactor, the conversion of the conditioned bio-syngas to bio-methanol shows the maximum yield about 1.21 kg/(kgcatal·h) MeOH with a methanol selectivity of 97.9% at 260 °C and 5.05 MPa using conventional CuZnAl catalyst, which is close to the level typically obtained in the conventional methanol synthesis process using natural gas. The influences of temperature, pressure and space velocity on the bio-methanol synthesis were also investigated in detail.

  4. CO(2)-selective methanol steam reforming on In-doped Pd studied by in situ X-ray photoelectron spectroscopy.

    PubMed

    Rameshan, Christoph; Lorenz, Harald; Mayr, Lukas; Penner, Simon; Zemlyanov, Dmitry; Arrigo, Rosa; Haevecker, Michael; Blume, Raoul; Knop-Gericke, Axel; Schlögl, Robert; Klötzer, Bernhard

    2012-11-01

    In situ X-ray photoelectron spectroscopy (in situ XPS) was used to study the structural and catalytic properties of Pd-In near-surface intermetallic phases in correlation with previously studied PdZn and PdGa.Room temperature deposition of ∼4 monolayer equivalents (MLEs) of In metal on Pd foil and subsequent annealing to 453 K in vacuum yields a ∼1:1 Pd/In near-surface multilayer intermetallic phase. This Pd(1)In(1) phase exhibits a similar "Cu-like" electronic structure and indium depth distribution as its methanol steam reforming (MSR)-selective multilayer Pd(1)Zn(1) counterpart.Catalytic characterization of the multilayer Pd(1)In(1) phase in MSR yielded a CO(2)-selectivity of almost 100% between 493 and 550 K. In contrast to previously studied In(2)O(3)-supported PdIn nanoparticles and pure In(2)O(3), intermediate formaldehyde is only partially converted to CO(2) using this Pd(1)In(1) phase. Strongly correlated with PdZn, on an In-diluted PdIn intermetallic phase with "Pd-like" electronic structure, prepared by thermal annealing at 623 K, methanol steam reforming is suppressed and enhanced CO formation via full methanol dehydrogenation is observed.To achieve CO(2)-TOF values on the isolated Pd(1)In(1) intermetallic phase as high as on supported PdIn/In(2)O(3), at least 593 K reaction temperature is required. A bimetal-oxide synergism, with both bimetallic and oxide synergistically contributing to the observed catalytic activity and selectivity, manifests itself by accelerated formaldehyde-to-CO(2) conversion at markedly lowered temperatures as compared to separate oxide and bimetal. Combination of suppression of full methanol dehydrogenation to CO on Pd(1)In(1) inhibited inverse water-gas-shift reaction on In(2)O(3) and fast water activation/conversion of formaldehyde is the key to the low-temperature activity and high CO(2)-selectivity of the supported catalyst. PMID:23226689

  5. CO2-selective methanol steam reforming on In-doped Pd studied by in situ X-ray photoelectron spectroscopy

    PubMed Central

    Rameshan, Christoph; Lorenz, Harald; Mayr, Lukas; Penner, Simon; Zemlyanov, Dmitry; Arrigo, Rosa; Haevecker, Michael; Blume, Raoul; Knop-Gericke, Axel; Schlögl, Robert; Klötzer, Bernhard

    2012-01-01

    In situ X-ray photoelectron spectroscopy (in situ XPS) was used to study the structural and catalytic properties of Pd–In near-surface intermetallic phases in correlation with previously studied PdZn and PdGa. Room temperature deposition of ∼4 monolayer equivalents (MLEs) of In metal on Pd foil and subsequent annealing to 453 K in vacuum yields a ∼1:1 Pd/In near-surface multilayer intermetallic phase. This Pd1In1 phase exhibits a similar “Cu-like” electronic structure and indium depth distribution as its methanol steam reforming (MSR)-selective multilayer Pd1Zn1 counterpart. Catalytic characterization of the multilayer Pd1In1 phase in MSR yielded a CO2-selectivity of almost 100% between 493 and 550 K. In contrast to previously studied In2O3-supported PdIn nanoparticles and pure In2O3, intermediate formaldehyde is only partially converted to CO2 using this Pd1In1 phase. Strongly correlated with PdZn, on an In-diluted PdIn intermetallic phase with “Pd-like” electronic structure, prepared by thermal annealing at 623 K, methanol steam reforming is suppressed and enhanced CO formation via full methanol dehydrogenation is observed. To achieve CO2-TOF values on the isolated Pd1In1 intermetallic phase as high as on supported PdIn/In2O3, at least 593 K reaction temperature is required. A bimetal-oxide synergism, with both bimetallic and oxide synergistically contributing to the observed catalytic activity and selectivity, manifests itself by accelerated formaldehyde-to-CO2 conversion at markedly lowered temperatures as compared to separate oxide and bimetal. Combination of suppression of full methanol dehydrogenation to CO on Pd1In1 inhibited inverse water–gas-shift reaction on In2O3 and fast water activation/conversion of formaldehyde is the key to the low-temperature activity and high CO2-selectivity of the supported catalyst. PMID:23226689

  6. Steam reforming of methanol over a Cu/ZnO/Al 2O 3 catalyst: a kinetic analysis and strategies for suppression of CO formation

    NASA Astrophysics Data System (ADS)

    Agrell, Johan; Birgersson, Henrik; Boutonnet, Magali

    Steam reforming of methanol (CH 3OH+H 2O→CO 2+3H 2) was studied over a commercial Cu/ZnO/Al 2O 3 catalyst for production of hydrogen onboard proton exchange membrane (PEM) fuel cell vehicles. A simple power-law rate expression was fitted to experimental data in order to predict the rates of CO 2 and H 2 formation under various reaction conditions. The apparent activation energy ( Ea) was estimated to be 100.9 kJ mol -1, in good agreement with values reported in the literature. Appreciable amounts of CO by-product were formed in the reforming process at low contact times and high methanol conversions. Being a catalyst poison that deactivates the electrocatalyst at the fuel cell anode at concentrations exceeding a few ppm, special attention was paid to the pathways for CO formation and strategies for its suppression. It was found that increasing the steam-methanol ratio effectively decreases CO formation. Likewise, addition of oxygen or air to the steam-methanol mixture minimises the production of CO. By shortening the contact time and lowering the maximum temperature in the reactor, CO production can be further decreased by suppressing the reverse water-gas shift reaction.

  7. Where does methanol lose hydrogen to trigger steam reforming? A revisit of methanol dehydrogenation on the PdZn alloy model obtained from kinetic Monte Carlo simulations.

    PubMed

    Cheng, Feng; Chen, Zhao-Xu

    2016-02-01

    Pd/ZnO is a promising catalyst studied for methanol steam reforming (MSR) and the 1 : 1 PdZn alloy is demonstrated to be the active component. It is believed that MSR starts from methanol dehydrogenation to methoxy. Previous studies of methanol dehydrogenation on the ideal PdZn(111) surface show that methanol adsorbs weakly on the PdZn(111) surface and it is hard for methanol to transform into methoxy because of the high dehydrogenation barrier, indicating that the catalyst model is not appropriate for investigating the first step of MSR. Using the model derived from our recent kinetic Monte Carlo simulations, we examined the process CH3OH → CH3O → CH2O → CHO → CO. Compared with the ideal model, methanol adsorbs much more strongly and the barrier from CH3OH → CH3O is much lower on the kMC model. On the other hand, the C-H bond breaking of CH3O, CH2O and CHO becomes harder. We show that co-adsorbed water is important for refreshing the active sites. The present study shows that the first MSR step most likely takes place on three-fold hollow sites formed by Zn atoms, and the inhomogeneity of the PdZn alloy may exert significant influences on reactions. PMID:26771029

  8. Cu-Al spinel oxide as an efficient catalyst for methanol steam reforming.

    PubMed

    Xi, Hongjuan; Hou, Xiaoning; Liu, Yajie; Qing, Shaojun; Gao, Zhixian

    2014-10-27

    Cu-Al spinel oxide, which contains a small portion of the CuO phase, has been successfully used in methanol steam reforming (MSR) without prereduction. The omission of prereduction not only avoids the copper sintering prior to the catalytic reaction, but also slows down the copper-sintering rate in MSR. During this process, the CuO phase can initiate MSR at a lower temperature, and CuAl2O4 releases active copper gradually. The catalyst CA2.5-900, calcined at 900 °C with n(Al)/n(Cu) = 2.5, has a higher CuAl2O4 content, higher BET surface area, and smaller CuAl2O4 crystal size. Its activity first increases and then decreases during MSR. Furthermore, both fresh and regenerated CA2.5-900 showed better catalytic performance than the commercial Cu-Zn-Al catalyst. PMID:25213737

  9. HYDROGEN PRODUCTION FOR FUEL CELLS VIA REFORMING COAL-DERIVED METHANOL

    SciTech Connect

    Paul A. Erickson

    2004-04-01

    Hydrogen can be produced from many feed stocks including coal. The objectives of this project are to establish and prove a hydrogen production pathway from coal-derived methanol for fuel cell applications. This progress report is the first such report that will be submitted to the DOE reporting on the status and progress made during the course of the project. This report covers the time period of October 1--December 31, 2003. This quarter saw progress in three areas. These areas are: (1) Evaluations of coal based methanol and the fuel cell grade baseline fuel, (2) Design and set up of the autothermal reactor, as well as (3) Set up and data collection of baseline performance using the steam reformer. All of the projects are proceeding on schedule. During this quarter one conference paper was written that will be presented at the ASME Power 2004 conference in March 2004, which outlines the research direction and basis for looking at the coal to hydrogen pathway.

  10. Steam reforming of methanol over copper loaded anodized aluminum oxide (AAO) prepared through electrodeposition

    NASA Astrophysics Data System (ADS)

    Linga Reddy, E.; Karuppiah, J.; Lee, Hyun Chan; Kim, Dong Hyun

    2014-12-01

    In order to study the steam reforming of methanol (SRM) to produce hydrogen for fuel cells, porous γ-alumina support is developed on Al substrate using anodic oxidation process and copper catalyst particles are deposited homogeneously over anodic aluminum oxide (AAO) surface by electrodeposition method. We investigated the effect of electrodeposition time and hot water treatment (HWT) on the activity of catalysts for SRM reaction in the temperature range between 160 and 360 °C. The experimental results indicate that the SRM activity, CO2 and dimethyl ether (DME) selectivity's over Cu catalysts increased as the electrodeposition time increased from 30 to 120 s, further increment in deposition time of Cu have no significant effect on it. The rates of SRM conversion are found to be higher for the catalysts made from the supports obtained after HWT, which may be due to the enhancement in the surface area of AAO support. It is found that the SRM activity and CO2 selectivity strongly depended upon the free exposed copper sites available for methanol adsorption and reaction, and DME in products is mainly observed in the reaction temperature range between 300 and 350 °C and it is higher for the catalysts with low Cu content.

  11. Methanol

    Integrated Risk Information System (IRIS)

    Methanol ; CASRN 67 - 56 - 1 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic Effects )

  12. Activity and stability enhancement of copper-alumina catalysts using cerium and zinc promoters for the selective production of hydrogen via steam reforming of methanol

    NASA Astrophysics Data System (ADS)

    Patel, Sanjay; Pant, K. K.

    The catalytic activity and hydrogen selectivity of cerium and zinc promoted copper-alumina catalysts have been investigated for the selective production of hydrogen via steam reforming of methanol (SRM). The SRM was carried out in a fixed bed tubular reactor at atmospheric pressure over a temperature range 200-300 °C. The major reaction products were hydrogen and carbon dioxide with traces of carbon monoxide. Catalysts of varying compositions were prepared by the wet impregnation method and characterized by atomic absorption spectroscopy (AAS), BET surface area, pore volume, pore size, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and thermogravimetry analysis (TGA). Results revealed that the methanol conversion, hydrogen selectivity and carbon monoxide formation varied with the type of promoter and content of copper in the catalyst. Cerium promoted Cu-Zn-Ce-Al-oxide catalysts improved the activity and hydrogen selectivity greatly and also kept the CO formation very low. Using cerium the SRM could be carried out at lower temperature with high methanol conversion, results in suppression of methanol decomposition and reverse water gas shift reactions eventually end-up with the low carbon monoxide and hydrogen rich product stream. Cerium also stabilizes the copper-alumina catalysts effectively that was confirmed by deactivation studies in which cerium promoted Cu-Zn-Ce-Al-oxide catalysts gave the consistent performance for a long run-time compared to catalysts containing only zinc promoter. The optimum operating conditions for SRM have been investigated by detailed study of effects of reaction temperature, contact time and steam to methanol molar ratio on methanol conversion, hydrogen selectivity and CO formation. Reaction pathway has been proposed for the SRM based on results obtained.

  13. Methanol production with elemental phosphorus byproduct gas: technical and economic feasibility

    SciTech Connect

    Lyke, S.E.; Moore, R.H.

    1981-01-01

    The technical and economic feasibility of using a typical, elemental, phosphorus byproduct gas stream in methanol production is assessed. The purpose of the study is to explore the potential of a substitute for natural gas. The first part of the study establishes economic tradeoffs between several alternative methods of supplying the hydrogen which is needed in the methanol synthesis process to react with CO from the off gas. The preferred alternative is the Battelle Process, which uses natural gas in combination with the off gas in an economically sized methanol plant. The second part of the study presents a preliminary basic design of a plant to (1) clean and compress the off gas, (2) return recovered phosphorus to the phosphorus plant, and (3) produce methanol by the Battelle Process. Use of elemental phosphorus byproduct gas in methanol production appears to be technically feasible. The Battelle Process shows a definite but relatively small economic advantage over conventional methanol manufacture based on natural gas alone. The process would be economically feasible only where natural gas supply and methanol market conditions at a phosphorus plant are not significantly less favorable than at competing methanol plants. If off-gas streams from two or more phosphorus plants could be combined, production of methanol using only offgas might also be economically feasible. The North American methanol market, however, does not seem likely to require another new methanol project until after 1990. The off-gas cleanup, compression, and phosphorus-recovery system could be used to produce a CO-rich stream that could be economically attractive for production of several other chemicals besides methanol.

  14. Twenty kW fuel cell units of compact design. Part 5: Hydrogen production by steam reforming of methanol

    NASA Astrophysics Data System (ADS)

    Grave, B.

    1980-09-01

    To assess its potential use in alkaline fuel cells, The production of hydrogen by steam reforming of methanol was studied analytically and experimentally. The reformer, the converter, and the purification system of a prototype installation were designed and the optimal operation parameters derived and experimentally confirmed. For comparison, hydrogen production by ammonia cracking was also studied. An estimate of the manufacturing costs for a fuel cell aggregate of 20 kW indicates economical operation only to be possible at very high duty cycles. As a result the project was terminated.

  15. Thermodynamic equilibrium composition analysis of methanol autothermal reforming for proton exchanger membrane fuel cell based on FLUENT Software

    NASA Astrophysics Data System (ADS)

    Wang, Sheng; Wang, Shudong

    Methanol autothermal reforming was thermodynamically analyzed using FLUENT software. The calculation methodology using this software is simple and convenient, and its validity was confirmed by comparing the obtained data with previous studies. As a function of the effects of temperature, pressure, molar steam-to-carbon ratio (S/C), and molar oxygen-to-carbon ratio (O/C) on the objective products, favorable operational parameters were evaluated, under which H 2 yield maximizes, the CO molar fraction minimizes and carbon deposition can be eliminated. The equilibrium constants of the possible reactions involved in oxidative methanol steam reforming, coupled with the reaction mechanism for the entire investigated temperature range, were elucidated and discussed. On the basis of the concluded possible mechanisms, three areas are inferred. In each individual area, H 2 or CO yield reached a maximum, or solid C was efficiently suppressed. Therein, a favorable operational range is proposed to assure the most optimized product yield.

  16. Methanol steam reforming promoted by molten salt-modified platinum on alumina catalysts.

    PubMed

    Kusche, Matthias; Agel, Friederike; Ní Bhriain, Nollaig; Kaftan, Andre; Laurin, Mathias; Libuda, Jörg; Wasserscheid, Peter

    2014-09-01

    We herein describe a straight forward procedure to increase the performance of platinum-on-alumina catalysts in methanol steam reforming by applying an alkali hydroxide coating according to the "solid catalyst with ionic liquid layer" (SCILL) approach. We demonstrate by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and temperature-programmed desorption (TPD) studies that potassium doping plays an important role in the catalyst activation. Moreover, the hygroscopic nature and the basicity of the salt modification contribute to the considerable enhancement in catalytic performance. During reaction, a partly liquid film of alkali hydroxides/carbonates forms on the catalyst/alumina surface, thus significantly enhancing the availability of water at the catalytically active sites. Too high catalyst pore fillings with salt introduce a considerable mass transfer barrier into the system as indicated by kinetic studies. Thus, the optimum interplay between beneficial catalyst modification and detrimental mass transfer effects had to be identified and was found on the applied platinum-on-alumina catalyst at KOH loadings around 7.5 mass%. PMID:25124120

  17. Durable Cu composite catalyst for hydrogen production by high temperature methanol steam reforming

    NASA Astrophysics Data System (ADS)

    Matsumura, Yasuyuki

    2014-12-01

    Durable catalysts are necessitated for the high temperature methanol steam reforming in compact hydrogen processors. The high durability at 400 °C can be obtained with a composite Cu catalyst where a small amount of Cu-ZnO-ZrO2-Y2O3-In2O3 is coprecipitated on a zirconia support. The lifetime of the composite catalyst containing 3 wt.% Cu is estimated to be as long as 53 × 102 h at 400 °C to produce the full conversion at a contact time of 250 g h m-3. The deactivation rate empirically relates to the cube of the activity. The gradual deactivation is caused by the gradual reduction of the Cu surface amount and also by the reduction of the surface activity which is believed to decrease with an increase in the Cu particle size. The interaction between the thin layer of the coprecipitate and the support surface probably suppresses the aggregation of the coprecipitate leading to Cu sintering.

  18. Methanol Steam Reforming Promoted by Molten Salt-Modified Platinum on Alumina Catalysts

    PubMed Central

    Kusche, Matthias; Agel, Friederike; Ní Bhriain, Nollaig; Kaftan, Andre; Laurin, Mathias; Libuda, Jörg; Wasserscheid, Peter

    2014-01-01

    We herein describe a straight forward procedure to increase the performance of platinum-on-alumina catalysts in methanol steam reforming by applying an alkali hydroxide coating according to the “solid catalyst with ionic liquid layer” (SCILL) approach. We demonstrate by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and temperature-programmed desorption (TPD) studies that potassium doping plays an important role in the catalyst activation. Moreover, the hygroscopic nature and the basicity of the salt modification contribute to the considerable enhancement in catalytic performance. During reaction, a partly liquid film of alkali hydroxides/carbonates forms on the catalyst/alumina surface, thus significantly enhancing the availability of water at the catalytically active sites. Too high catalyst pore fillings with salt introduce a considerable mass transfer barrier into the system as indicated by kinetic studies. Thus, the optimum interplay between beneficial catalyst modification and detrimental mass transfer effects had to be identified and was found on the applied platinum-on-alumina catalyst at KOH loadings around 7.5 mass %. PMID:25124120

  19. Self-sufficient and exclusive oxygenation of methane and its source materials with oxygen to methanol via metgas using oxidative bi-reforming.

    PubMed

    Olah, George A; Prakash, G K Surya; Goeppert, Alain; Czaun, Miklos; Mathew, Thomas

    2013-07-10

    A combination of complete methane combustion with oxygen of the air coupled with bi-reforming leads to the production of metgas (H2/CO in 2:1 mole ratio) for exclusive methanol synthesis. The newly developed oxidative bi-reforming allows direct oxygenation of methane to methanol in an overall economic and energetically efficient process, leaving very little, if any, carbon footprint or byproducts. PMID:23795911

  20. Polymer electrolyte membrane fuel cell grade hydrogen production by methanol steam reforming: A comparative multiple reactor modeling study

    NASA Astrophysics Data System (ADS)

    Katiyar, Nisha; Kumar, Shashi; Kumar, Surendra

    2013-12-01

    Analysis of a fuel processor based on methanol steam reforming has been carried out to produce fuel cell grade H2. Six reactor configurations namely FBR1 (fixed bed reactor), MR1 (H2 selective membrane reactor with one reaction tube), MR2 (H2 selective membrane reactor with two reaction tubes), FBR2 (FBR1 + preferential CO oxidation (PROX) reactor), MR3 (MR1 + PROX), and MR4 (MR2 + PROX) are evaluated by simulation to identify the suitable processing scheme. The yield of H2 is significantly affected by H2 selective membrane, residence time, temperature, and pressure conditions at complete methanol conversion. The enhancement in residence time in MR2 by using two identical reaction tubes provides H2 yield of 2.96 with 91.25 mol% recovery at steam/methanol ratio of 1.5, pressure of 2 bar and 560 K temperature. The exit retentate gases from MR2 are further treated in PROX reactor of MR4 to reduce CO concentration to 4.1 ppm to ensure the safe discharge to the environment. The risk of carbon deposition on reforming catalyst is highly reduced in MR4, and MR4 reactor configuration generates 7.4 NL min-1 of CO free H2 from 0.12 mol min-1 of methanol which can provide 470 W PEMFC feedstock requirement. Hence, process scheme in MR4 provides a compact and innovative fuel cell grade H2 generating unit.

  1. Preferential oxidation of methanol and carbon monoxide for gas cleanup during methanol fuel processing

    SciTech Connect

    Birdsell, S.A.; Vanderborgh, N.E.; Inbody, M.A.

    1993-07-01

    Methanol fuel processing generates hydrogen for low-temperature, PEM fuel cell systems now being considered for transportation and other applications. Although liquid methanol fuel is convenient for this application, existing fuel processing techniques generate contaminants that degrade fuel cell performance. Through mathematical models and laboratory experiments chemical processing is described that removes CO and other contaminants from the anode feed stream.

  2. METHANOL MEASUREMENT IN AUTO EXHAUST USING A GAS-FILTER CORRELATION SPECTROMETER

    EPA Science Inventory

    Spectroscopic methods offer an alternative to wet chemical methods for analysis of methanol emissions from automobiles. The gas filter correlation infrared optical analysis approach appears very promising. The report describes the gas correlation optical system constructed to ana...

  3. Autothermal reforming of natural gas to synthesis gas:reference: KBR paper #2031.

    SciTech Connect

    Mann, David; Rice, Steven, D.

    2007-04-01

    This Project Final Report serves to document the project structure and technical results achieved during the 3-year project titled Advanced Autothermal Reformer for US Dept of Energy Office of Industrial Technology. The project was initiated in December 2001 and was completed March 2005. It was a joint effort between Sandia National Laboratories (Livermore, CA), Kellogg Brown & Root LLC (KBR) (Houston, TX) and Sued-Chemie (Louisville, KY). The purpose of the project was to develop an experimental capability that could be used to examine the propensity for soot production in an Autothermal Reformer (ATR) during the production of hydrogen-carbon monoxide synthesis gas intended for Gas-to-Liquids (GTL) applications including ammonia, methanol, and higher hydrocarbons. The project consisted of an initial phase that was focused on developing a laboratory-scale ATR capable of reproducing conditions very similar to a plant scale unit. Due to budget constraints this effort was stopped at the advanced design stages, yielding a careful and detailed design for such a system including ATR vessel design, design of ancillary feed and let down units as well as a PI&D for laboratory installation. The experimental effort was then focused on a series of measurements to evaluate rich, high-pressure burner behavior at pressures as high as 500 psi. The soot formation measurements were based on laser attenuation at a view port downstream of the burner. The results of these experiments and accompanying calculations show that soot formation is primarily dependent on oxidation stoichiometry. However, steam to carbon ratio was found to impact soot production as well as burner stability. The data also showed that raising the operating pressure while holding mass flow rates constant results in considerable soot formation at desirable feed ratios. Elementary reaction modeling designed to illuminate the role of CO{sub 2} in the burner feed showed that the conditions in the burner allow for the

  4. Test and evaluation of methanol in a gas turbine system. Final report

    SciTech Connect

    Weir, A. Jr.; vonKleinSmid, W.H.; Danko, E.A.

    1981-02-01

    A test was conducted to compare the operational and emission characteristics of two Turbo Power and Marine Systems, Inc. (TPM) gas turbines, one operating on distillate fuel (Jet A) and the other operating on methanol. The test, which included 523 h of methanol burn time, was conducted at Southern California Edison Company's (SCE) Ellwood Energy Support Facility in Goleta, California. The facility consisted of two gas turbines combined with an electric generator in a TP-4 Twin Pac configuration. Normally, distilled water is injected into the combustion chambers of each turbine to reduce oxides of nitrogen emissions. During the major portion of the program, no water was injected into the methanol fueled turbine. Periodically during the program, performance and emission tests as well as physical inspections of the hot section of each turbine were conducted. Emission and performance tests were also conducted on natural gas. One series of tests was conducted with distilled water injected into the combustion chamber during methanol operations. Oxides of nitrogen emissions on the methanol-fueled turbine, without water injection, were approximately 80% of the emissions of the distillate fueled turbine with water injection. There was a significant reduction in particulate emissions during methanol operation. An additional reduction in oxides of nitrogen emission was obtained during operations of the methanol-fueled turbine with water injection. No significant problems occurred during the test that could be attributed to firing methanol. The hot end inspections indicated cleaner components within the methanol fueled turbine.

  5. Federal Onshore Oil and Gas Leasing Reform Act of 1987

    SciTech Connect

    Not Available

    1988-01-01

    This book was designed for persons who lease federal lands for oil and gas development and who require an understanding of both the current and historic laws relating to leasing. The manual from this workshop is useful as a reference tool for attorneys, landsmen, and others who require information on the original Mineral Leasing Act of 1920 and all subsequent amendments, including the Federal Onshore Oil and Gas Leasing Reform Act of 1987 and selected legislative history. Included in this manual is a lengthy discussion of the Oil and Gas Leasing Reform Act, along with a reference section containing full text of: Mineral Leasing Act of February 25, 1920, with all amendments including the Federal Onshore Oil and Gas Leasing Reform Act of 1987, comprehensively footnoted with subject notations and comments; Senate Report 100-188: Committee Report on Leasing Reform Act; House Report 100-495: Joint Explanatory Statement on Leasing Reform Act; Testimony of the Independent Petroleum Association of Mountain States to House Interior Subcommittee on Mining and Natural Resources.

  6. 40 CFR 86.120-94 - Gas meter or flow instrumentation calibration; particulate, methanol and formaldehyde measurement.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... calibration; particulate, methanol and formaldehyde measurement. 86.120-94 Section 86.120-94 Protection of... Procedures § 86.120-94 Gas meter or flow instrumentation calibration; particulate, methanol and formaldehyde measurement. (a) Sampling for particulate, methanol and formaldehyde emissions requires the use of gas...

  7. 40 CFR 86.120-94 - Gas meter or flow instrumentation calibration; particulate, methanol and formaldehyde measurement.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... calibration; particulate, methanol and formaldehyde measurement. 86.120-94 Section 86.120-94 Protection of... Procedures § 86.120-94 Gas meter or flow instrumentation calibration; particulate, methanol and formaldehyde measurement. (a) Sampling for particulate, methanol and formaldehyde emissions requires the use of gas...

  8. Water and methanol in low-mass protostellar outflows: gas-phase synthesis, ice sputtering and destruction

    NASA Astrophysics Data System (ADS)

    Suutarinen, A. N.; Kristensen, L. E.; Mottram, J. C.; Fraser, H. J.; van Dishoeck, E. F.

    2014-05-01

    Water in outflows from protostars originates either as a result of gas-phase synthesis from atomic oxygen at T ≳ 200 K, or from sputtered ice mantles containing water ice. We aim to quantify the contribution of the two mechanisms that lead to water in outflows, by comparing observations of gas-phase water to methanol (a grain surface product) towards three low-mass protostars in NGC 1333. In doing so, we also quantify the amount of methanol destroyed in outflows. To do this, we make use of James Clerk Maxwell Telescope and Herschel-Heterodyne Instrument for the Far-Infrared data of H2O, CH3OH and CO emission lines and compare them to RADEX non-local thermodynamic equilibrium excitation simulations. We find up to one order of magnitude decrease in the column density ratio of CH3OH over H2O as the velocity increases in the line wings up to ˜15 km s-1. An independent decrease in X(CH3OH) with respect to CO of up to one order of magnitude is also found in these objects. We conclude that gas-phase formation of H2O must be active at high velocities (above 10 km s-1 relative to the source velocity) to re-form the water destroyed during sputtering. In addition, the transition from sputtered water at low velocities to form water at high velocities must be gradual. We place an upper limit of two orders of magnitude on the destruction of methanol by sputtering effects.

  9. METHANOL PRODUCTION FROM BIOMASS AND NATURAL GAS AS TRANSPORTATION FUEL

    EPA Science Inventory

    Two processes are examined for production of methanol. They are assessed against the essential requirements of a future alternative fuel for road transport: that it (i) is producible in amounts comparable to the 19 EJ of motor fuel annually consumed in the U.S., (ii) minimizes em...

  10. Improvement in methanol production by regulating the composition of synthetic gas mixture and raw biogas.

    PubMed

    Patel, Sanjay K S; Mardina, Primata; Kim, Dongwook; Kim, Sang-Yong; Kalia, Vipin C; Kim, In-Won; Lee, Jung-Kul

    2016-10-01

    Raw biogas can be an alternative feedstock to pure methane (CH4) for methanol production. In this investigation, we evaluated the methanol production potential of Methylosinus sporium from raw biogas originated from an anaerobic digester. Furthermore, the roles of different gases in methanol production were investigated using synthetic gas mixtures of CH4, carbon dioxide (CO2), and hydrogen (H2). Maximum methanol production was 5.13, 4.35, 6.28, 7.16, 0.38, and 0.36mM from raw biogas, CH4:CO2, CH4:H2, CH4:CO2:H2, CO2, and CO2:H2, respectively. Supplementation of H2 into raw biogas increased methanol production up to 3.5-fold. Additionally, covalent immobilization of M. sporium on chitosan resulted in higher methanol production from raw biogas. This study provides a suitable approach to improve methanol production using low cost raw biogas as a feed containing high concentrations of H2S (0.13%). To our knowledge, this is the first report on methanol production from raw biogas, using immobilized cells of methanotrophs. PMID:27371792

  11. Using Rare Gas Permeation to Probe Methanol Diffusion near the Glass Transition Temperature

    NASA Astrophysics Data System (ADS)

    Matthiesen, Jesper; Smith, R. Scott; Kay, Bruce D.

    2009-12-01

    The permeation of rare-gas atoms through deeply supercooled metastable liquid methanol films is used to probe the diffusivity. The technique allows for measurement of supercooled liquid mobility at temperatures near the glass transition. The temperature dependence of the diffusivity is well described by a Vogel-Fulcher-Tamman equation. These new measurements and the temperature dependent kinetic parameters obtained from their analysis provide clear evidence that methanol is a fragile liquid near the glass transition.

  12. Using rare gas permeation to probe methanol diffusion near the glass transition temperature.

    PubMed

    Matthiesen, Jesper; Smith, R Scott; Kay, Bruce D

    2009-12-11

    The permeation of rare-gas atoms through deeply supercooled metastable liquid methanol films is used to probe the diffusivity. The technique allows for measurement of supercooled liquid mobility at temperatures near the glass transition. The temperature dependence of the diffusivity is well described by a Vogel-Fulcher-Tamman equation. These new measurements and the temperature dependent kinetic parameters obtained from their analysis provide clear evidence that methanol is a fragile liquid near the glass transition. PMID:20366212

  13. A self-reductive mesoporous CuO(x)/Fe/silicate nanocomposite as a highly active and stable catalyst for methanol reforming.

    PubMed

    Li, Chien-Cheng; Chen, Yan-Wun; Lin, Ran-Jin; Chang, Ching-Chun; Chen, Kuei-Hsien; Lin, Hong-Ping; Chen, Li-Chyong

    2011-09-01

    A simple and convenient one-pot synthetic route to directly prepare a self-reductive mesoporous copper-iron-silicate (CuO(x)-Fe-silicate)-based catalyst has been developed. The resultant catalyst is highly active and stable in methanol reforming without needing a pre-reduction procedure. PMID:21773606

  14. 40 CFR 86.1320-90 - Gas meter or flow instrumentation calibration; particulate, methanol, and formaldehyde measurement.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... calibration; particulate, methanol, and formaldehyde measurement. 86.1320-90 Section 86.1320-90 Protection of... instrumentation calibration; particulate, methanol, and formaldehyde measurement. (a) Sampling for particulate, methanol and formaldehyde emissions requires the use of gas meters or flow instrumentation to...

  15. 40 CFR 86.1320-90 - Gas meter or flow instrumentation calibration; particulate, methanol, and formaldehyde measurement.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... calibration; particulate, methanol, and formaldehyde measurement. 86.1320-90 Section 86.1320-90 Protection of... instrumentation calibration; particulate, methanol, and formaldehyde measurement. (a) Sampling for particulate, methanol and formaldehyde emissions requires the use of gas meters or flow instrumentation to...

  16. 40 CFR 86.120-94 - Gas meter or flow instrumentation calibration; particulate, methanol and formaldehyde measurement.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 19 2014-07-01 2014-07-01 false Gas meter or flow instrumentation... Procedures § 86.120-94 Gas meter or flow instrumentation calibration; particulate, methanol and formaldehyde measurement. (a) Sampling for particulate, methanol and formaldehyde emissions requires the use of gas...

  17. 40 CFR 86.120-94 - Gas meter or flow instrumentation calibration; particulate, methanol and formaldehyde measurement.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 19 2012-07-01 2012-07-01 false Gas meter or flow instrumentation... Procedures § 86.120-94 Gas meter or flow instrumentation calibration; particulate, methanol and formaldehyde measurement. (a) Sampling for particulate, methanol and formaldehyde emissions requires the use of gas...

  18. 40 CFR 86.120-94 - Gas meter or flow instrumentation calibration; particulate, methanol and formaldehyde measurement.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 19 2013-07-01 2013-07-01 false Gas meter or flow instrumentation... Procedures § 86.120-94 Gas meter or flow instrumentation calibration; particulate, methanol and formaldehyde measurement. (a) Sampling for particulate, methanol and formaldehyde emissions requires the use of gas...

  19. Insights on the effective incorporation of a foam-based methanol reformer in a high temperature polymer electrolyte membrane fuel cell

    NASA Astrophysics Data System (ADS)

    Avgouropoulos, George; Papavasiliou, Joan; Ioannides, Theophilos; Neophytides, Stylianos

    2015-11-01

    Highly active Al-doped CuMnOx catalyst supported on metallic copper foam was prepared via the combustion method and placed adjacent to the anode electrocatalyst of a high temperature PEM fuel cell operating at 200-210 °C. The addition of aluminum oxide in the catalyst composition enhanced the specific surface area (19.1 vs. 8.6 m2 g-1) and the reducibility of the Cu-Mn spinel oxide. Accordingly, the catalytic performance of CuMnOx was also improved. The doped sample is up to 2.5 times more active than the undoped sample at 200 °C, depending on the methanol concentration at the inlet, while CO selectivity is less than 0.8% in all cases. A membrane-electrode assembly comprising the ADVENT cross-linked TPS® high-temperature polymer electrolyte was integrated with the Cu-based methanol reformer in an Internal Reforming Methanol Fuel Cell (IRMFC). In order to avoid extensive poisoning of the reforming catalyst by H3PO4, a thin separation plate was placed between the reforming catalyst and the electrooxidation catalyst. Preliminary results obtained from a single-cell laboratory prototype demonstrated the improved functionality of the unit. Indeed, promising electrochemical performance was obtained during the first 24 h, during which the required H2 for achieving 580 mV at 0.2 A cm-2, was supplied from the reformer.

  20. Effectiveness of heat-integrated methanol steam reformer and polymer electrolyte membrane fuel cell stack systems for portable applications

    NASA Astrophysics Data System (ADS)

    Lotrič, A.; Sekavčnik, M.; Hočevar, S.

    2014-12-01

    Efficiently combining proton exchange membrane fuel cell (PEMFC) stack with methanol steam reformer (MSR) into a small portable system is still quite a topical issue. Using methanol as a fuel in PEMFC stack includes a series of chemical processes where each proceeds at a unique temperature. In a combined MSR-PEMFC-stack system with integrated auxiliary fuel processors (vaporizer, catalytic combustor, etc.) the processes are both endothermic and exothermic hence their proper thermal integration can help raising the system efficiency. A concept of such fully integrated and compact system is proposed in this study. Three separate systems are designed based on different PEMFC stacks and MSR. Low-temperature (LT) and conventional high-temperature (cHT) PEMFC stack characteristics are based on available data from suppliers. Also, a novel high-temperature (nHT) PEMFC stack is proposed because its operating temperature coincides with that of MSR. A comparative study of modelled systems is performed using a mass and energy balances zero-dimensional model, which is interdependently coupled to a physical model based on finite element method (FEM). The results indicate that a system with nHT PEMFC stack is feasible and has the potential to reach higher system efficiencies than systems with LT or cHT PEMFC stacks.

  1. Methanol Emission from Leaves (Enzymatic Detection of Gas-Phase Methanol and Relation of Methanol Fluxes to Stomatal Conductance and Leaf Development).

    PubMed Central

    Nemecek-Marshall, M.; MacDonald, R. C.; Franzen, J. J.; Wojciechowski, C. L.; Fall, R.

    1995-01-01

    We recently reported the detection of methanol emissions from leaves (R. MacDonald, R. Fall [1993] Atmos Environ 27A: 1709-1713). This could represent a substantial flux of methanol to the atmosphere. Leaf methanol production and emission have not been investigated in detail, in part because of difficulties in sampling and analyzing methanol. In this study we used an enzymatic method to convert methanol to a fluorescent product and verified that leaves from several species emit methanol. Methanol was emitted almost exclusively from the abaxial surfaces of hypostomatous leaves but from both surfaces of amphistomatous leaves, suggesting that methanol exits leaves via stomates. The role of stomatal conductance was verified in experiments in which stomates were induced to close, resulting in reduced methanol. Free methanol was detected in bean leaf extracts, ranging from 26.8 [mu]g g-1 fresh weight in young leaves to 10.0 [mu]g g-1 fresh weight in older leaves. Methanol emission was related to leaf development, generally declining with increasing leaf age after leaf expansion; this is consistent with volatilization from a cellular pool that declines in older leaves. It is possible that leaf emission could be a major source of methanol found in the atmosphere of forests. PMID:12228547

  2. First Detection of Gas-phase Methanol in a Protoplanetary Disk

    NASA Astrophysics Data System (ADS)

    Walsh, Catherine; Loomis, Ryan A.; Öberg, Karin I.; Kama, Mihkel; van ’t Hoff, Merel L. R.; Millar, Tom J.; Aikawa, Yuri; Herbst, Eric; Widicus Weaver, Susanna L.; Nomura, Hideko

    2016-05-01

    The first detection of gas-phase methanol in a protoplanetary disk (TW Hya) is presented. In addition to being one of the largest molecules detected in disks to date, methanol is also the first disk organic molecule with an unambiguous ice chemistry origin. The stacked methanol emission, as observed with the Atacama Large Millimeter/submillimeter Array, is spectrally resolved and detected across six velocity channels (\\gt 3σ ), reaching a peak signal-to-noise of 5.5σ , with the kinematic pattern expected for TW Hya. Using an appropriate disk model, a fractional abundance of 3× {10}-12{--}4× {10}-11 (with respect to H2) reproduces the stacked line profile and channel maps, with the favored abundance dependent upon the assumed vertical location (midplane versus molecular layer). The peak emission is offset from the source position, suggesting that the methanol emission has a ring-like morphology: the analysis here suggests it peaks at ≈ 30 {{au}}, reaching a column density ≈ 3{--}6× {10}12 cm‑2. In the case of TW Hya, the larger (up to millimeter-sized) grains, residing in the inner 50 au, may thus host the bulk of the disk ice reservoir. The successful detection of cold gas-phase methanol in a protoplanetary disk implies that the products of ice chemistry can be explored in disks, opening a window into studying complex organic chemistry during planetary system formation.

  3. Non-intrusive detection of methanol in gas phase using infrared degenerate four-wave mixing

    NASA Astrophysics Data System (ADS)

    Zhou, J.; Sahlberg, A. L.; Nilsson, H.; Lundgren, E.; Zetterberg, J.

    2015-11-01

    Sensitive and non-intrusive detection of gas-phase methanol with high spatial and temporal resolution has for the first time been reported using mid-infrared degenerate four-wave mixing (IR-DFWM). IR-DFWM spectra of methanol have been successfully recorded in nitrogen-diluted gas flows at room temperature and at 300 °C, by probing ro-vibrational transitions belonging to the fundamental C-H stretching modes, ν 2 and ν 9, and the O-H stretching mode, ν 1. The detection limit of methanol vapor at room temperature and atmospheric pressure is estimated to be 250 ppm with the present setup. Potential interference from CH4 and CO2 is discussed from recorded IR-DFWM spectra of CH4 and CO2, and it was found that detection of methanol free from CH4 and CO2 interference is possible. These results show the potential of the detection of methanol with IR-DFWM for applications in both combustion and catalytic environments, such as CO2 hydrogenation and CH4 oxidation.

  4. Hydrogen enrichment of synthesis gas for once-through methanol production: Final report

    SciTech Connect

    Cavaliere, G.F.; Riley, C.J.

    1987-04-01

    A previous report, EPRI AP-3749, included the economics of producing methanol fuel from coal gasifiers by a once-through methanol synthesis plant configuration, using the unconverted gas as a gas turbine fuel in a combined-cycle power plant. In that study, the CO-rich gas was adjusted by shift conversion to a composition suitable for methanol synthesis. In the present study, the shift conversion method of gas composition adjustment was compared against several CO-rejection methods, with the rejected CO-rich gas used as fuel for production of power. All cases assumed the same gasification plant size. As a result, the CO-rejection methods produced more electric power and less methanol than the base case of shift conversion. Two alternatives, one based on physical adsorption and one on chemical absorption, were quickly eliminated as uncompetitive on cost grounds and unproven commercially on this scale. The remaining alternatives are membrane separation and cryogenic fractionation. Flowsheets and cost estimates were prepared for these cases and for the shift conversion base case. Total required revenues were calculated for all cases. Then, making reasonable assumptions of the range of unit revenue values of produced methanol and power, competitiveness of the alternatives with the base case was estimated. Some unit revenue combinations gave small revenue advantages for the alternatives, while others gave small advantages for the base case. None of the revenue differentials can be regarded as significant when compared with the accuracy levels of the total cost and income figures being compared. Therefore, both the membrane and cryogenic based process routes are judged to be competitive with the shift-based process, but none of the processes is clearly superior to another using current economic criteria. 1 ref., 32 figs., 19 tabs.

  5. Liquid phase low temperature method for production of methanol from synthesis gas and catalyst formulations therefor

    DOEpatents

    Mahajan, Devinder

    2005-07-26

    The invention provides a homogenous catalyst for the production of methanol from purified synthesis gas at low temperature and low pressure which includes a transition metal capable of forming transition metal complexes with coordinating ligands and an alkoxide, the catalyst dissolved in a methanol solvent system, provided the transition metal complex is not transition metal carbonyl. The coordinating ligands can be selected from the group consisting of N-donor ligands, P-donor ligands, O-donor ligands, C-donor ligands, halogens and mixtures thereof.

  6. Mutagenic effect of methanol in gas station operators from Sao Paulo/Brazil

    SciTech Connect

    Gattas, G.J.F.; Cardoso, L.A.; Faria, M.M.

    1997-10-01

    The frequency of micronucleus (MN) in oral scamous cells of 76 gas station operators was investigated. Subjects were exposed to a fuel called MEG a mix of 33% methanol, 60% ethanol and 7% gasoline. In Brazil the ethyl alcohol, extracted from sugar cane have been used as a fuel since 70`s. In November 1991, for economical reasons, the MEG fuel was introduced in big cities. The MN frequency was evaluated in three different periods: before MEG introduction (1989), and twice after MEG utilization (1992 and 1995). Some individuals were analyzed more than one time. For each individual the frequency of MN was performed in 2000 oral cells. Statistical analysis through non parametric tests revealed a highly significant increase (P=0.001) in the frequency of MN before (1.38/2000 cells) and immediately after methanol introduction (3.0/2000 cells). The frequency of MN returned to be normal (1.4/2000 cells), in the third evaluation when the exposition to methanol decreased. It should represent genetic risk for individuals under occupational exposure and for the population as a whole when methanol has been introduced as a large-scale fuel.

  7. Catalysts prepared from copper-nickel ferrites for the steam reforming of methanol

    NASA Astrophysics Data System (ADS)

    Huang, Yung-Han; Wang, Sea-Fue; Tsai, An-Pang; Kameoka, Satoshi

    2015-05-01

    In this study, Fe3O4-supported Cu and Ni catalysts are prepared through reduction of Cu-Ni (Ni1-xCuxFe2O4) ferrites. The Cu-Ni ferrites, synthesized using a solid-state reaction method, are reduced at temperatures from 240 °C to 500 °C in a H2 atmosphere. All ferrites are characterized with granular morphology and a smooth particle surface before reduction. For the CuFe2O4, Ni0.5Cu0.5Fe2O4 and NiFe2O4 ferrites reduced at 240, 300, and 400 °C, respectively, nanosized Cu and/or Ni particles (5-32 nm) and mesopores (5-30 nm) are distributed and adhered on the surfaces of Fe3O4 supports. After increasing the reduction temperature of NiFe2O4 ferrite to 500 °C, the Ni particles and mesopores disappear from the Fe3O4 surfaces, which is due to the formation of a Fe-Ni alloy covering on the Fe3O4 surfaces. The CuFe2O4 ferrite after H2 reduction at 240 °C exhibits the highest H2 production rate of 149 ml STP/min g-cat at 360 °C. The existence of Ni content in the Cu-Ni ferrites enhances the reverse water gas shift reaction, and raises the CO selectivity while reducing the CO2 selectivity. Formation of a Fe-Ni alloy exaggerates the trend and poisons the H2 production rate.

  8. 40 CFR 86.1320-90 - Gas meter or flow instrumentation calibration; particulate, methanol, and formaldehyde measurement.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 20 2013-07-01 2013-07-01 false Gas meter or flow instrumentation... Heavy-Duty Engines; Gaseous and Particulate Exhaust Test Procedures § 86.1320-90 Gas meter or flow..., methanol and formaldehyde emissions requires the use of gas meters or flow instrumentation to...

  9. 40 CFR 86.1320-90 - Gas meter or flow instrumentation calibration; particulate, methanol, and formaldehyde measurement.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 20 2012-07-01 2012-07-01 false Gas meter or flow instrumentation... Heavy-Duty Engines; Gaseous and Particulate Exhaust Test Procedures § 86.1320-90 Gas meter or flow..., methanol and formaldehyde emissions requires the use of gas meters or flow instrumentation to...

  10. Stabilization of Hydrogen Production via Methanol Steam Reforming in Microreactor by Al2O3 Nano-Film Enhanced Catalyst Adhesion.

    PubMed

    Jeong, Heondo; Na, Jeong-Geol; Jang, Min Su; Ko, Chang Hyun

    2016-05-01

    In hydrogen production by methanol steam reforming reaction with microchannel reactor, Al2O3 thin film formed by atomic layer deposition (ALD) was introduced on the surface of microchannel reactor prior to the coating of catalyst particles. Methanol conversion rate and hydrogen production rate, increased in the presence of Al2O3 thin film. Over-view and cross-sectional scanning electron microscopy study showed that the adhesion between catalyst particles and the surface of microchannel reactor enhanced due to the presence of Al2O3 thin film. The improvement of hydrogen production rate inside the channels of microreactor mainly came from the stable fixation of catalyst particles on the surface of microchannels. PMID:27483762

  11. Methanol incorporation in clathrate hydrates and the implications for oil and gas pipeline flow assurance and icy planetary bodies

    PubMed Central

    Shin, Kyuchul; Udachin, Konstantin A.; Moudrakovski, Igor L.; Leek, Donald M.; Alavi, Saman; Ratcliffe, Christopher I.; Ripmeester, John A.

    2013-01-01

    One of the best-known uses of methanol is as antifreeze. Methanol is used in large quantities in industrial applications to prevent methane clathrate hydrate blockages from forming in oil and gas pipelines. Methanol is also assigned a major role as antifreeze in giving icy planetary bodies (e.g., Titan) a liquid subsurface ocean and/or an atmosphere containing significant quantities of methane. In this work, we reveal a previously unverified role for methanol as a guest in clathrate hydrate cages. X-ray diffraction (XRD) and NMR experiments showed that at temperatures near 273 K, methanol is incorporated in the hydrate lattice along with other guest molecules. The amount of included methanol depends on the preparative method used. For instance, single-crystal XRD shows that at low temperatures, the methanol molecules are hydrogen-bonded in 4.4% of the small cages of tetrahydrofuran cubic structure II hydrate. At higher temperatures, NMR spectroscopy reveals a number of methanol species incorporated in hydrocarbon hydrate lattices. At temperatures characteristic of icy planetary bodies, vapor deposits of methanol, water, and methane or xenon show that the presence of methanol accelerates hydrate formation on annealing and that there is unusually complex phase behavior as revealed by powder XRD and NMR spectroscopy. The presence of cubic structure I hydrate was confirmed and a unique hydrate phase was postulated to account for the data. Molecular dynamics calculations confirmed the possibility of methanol incorporation into the hydrate lattice and show that methanol can favorably replace a number of methane guests. PMID:23661058

  12. Methanol incorporation in clathrate hydrates and the implications for oil and gas pipeline flow assurance and icy planetary bodies.

    PubMed

    Shin, Kyuchul; Udachin, Konstantin A; Moudrakovski, Igor L; Leek, Donald M; Alavi, Saman; Ratcliffe, Christopher I; Ripmeester, John A

    2013-05-21

    One of the best-known uses of methanol is as antifreeze. Methanol is used in large quantities in industrial applications to prevent methane clathrate hydrate blockages from forming in oil and gas pipelines. Methanol is also assigned a major role as antifreeze in giving icy planetary bodies (e.g., Titan) a liquid subsurface ocean and/or an atmosphere containing significant quantities of methane. In this work, we reveal a previously unverified role for methanol as a guest in clathrate hydrate cages. X-ray diffraction (XRD) and NMR experiments showed that at temperatures near 273 K, methanol is incorporated in the hydrate lattice along with other guest molecules. The amount of included methanol depends on the preparative method used. For instance, single-crystal XRD shows that at low temperatures, the methanol molecules are hydrogen-bonded in 4.4% of the small cages of tetrahydrofuran cubic structure II hydrate. At higher temperatures, NMR spectroscopy reveals a number of methanol species incorporated in hydrocarbon hydrate lattices. At temperatures characteristic of icy planetary bodies, vapor deposits of methanol, water, and methane or xenon show that the presence of methanol accelerates hydrate formation on annealing and that there is unusually complex phase behavior as revealed by powder XRD and NMR spectroscopy. The presence of cubic structure I hydrate was confirmed and a unique hydrate phase was postulated to account for the data. Molecular dynamics calculations confirmed the possibility of methanol incorporation into the hydrate lattice and show that methanol can favorably replace a number of methane guests. PMID:23661058

  13. Efficient utilization of greenhouse gas in a gas-to-liquids process combined with carbon dioxide reforming of methane.

    PubMed

    Ha, Kyoung-Su; Bae, Jong Wook; Woo, Kwang-Jae; Jun, Ki-Won

    2010-02-15

    A process model for a gas-to-liquids (GTL) process mainly producing Fischer-Tropsch (FT) synthetic oils has been developed to assess the effects of reforming methods, recycle ratio of unreacted syngas mixture on the process efficiency and the greenhouse gas (GHG) emission. The reforming unit of our study is composed of both steam reforming of methane (SRM) and carbon dioxide reforming of methane (CDR) to form syngas, which gives composition flexibility, reduction in GHG emission, and higher cost-competitiveness. With recycling, it is found that zero emission of CO(2) from the process can be realized and the required amount of natural gas (NG) can be significantly reduced. This GTL process model has been built by using Aspen Plus software, and it is mainly composed of a feeding unit, a reforming unit, an FT synthesis unit, several separation units and a recycling unit. The composition flexibility of the syngas mixture due to the two different types of reforming reactions raises an issue that in order to attain the optimized feed composition of FT synthesis the amount of flow rate of each component in the fresh feed mixture should be determined considering the effects of the recycle and its split ratio. In the FT synthesis unit, the 15 representative reactions for the chain growth and water gas shift on the cobalt-based catalyst are considered. After FT synthesis, the unreacted syngas mixture is recycled to the reforming unit or the FT synthesis unit or both to enhance process efficiency. The effect of the split ratio, the recycle flow rate to the FT reactor over the recycle flow rate to the reforming unit, on the efficiency of the process was also investigated. This work shows that greater recycle to the reforming unit is less effective than that to the FT synthesis unit from the standpoint of the net heat efficiency of the process, since the reforming reactions are greatly endothermic and greater recycle to the reformer requires more energy. PMID:20078033

  14. A study on methanol steam reforming to CO 2 and H 2 over the La 2CuO 4 nanofiber catalyst

    NASA Astrophysics Data System (ADS)

    Gao, Lizhen; Sun, Gebiao; Kawi, Sibudjing

    2008-01-01

    The La 2CuO 4 crystal nanofibers were prepared by using single-walled carbon nanotubes as templates under mild hydrothermal conditions. The steam reforming of methanol (SRM) to CO 2 and H 2 over such nanofiber catalysts was studied. At the low temperature of 150 °C and steam/methanol=1.3, methanol was completely (100%, 13.8 g/h g catalyst) converted to hydrogen and CO 2 without the generation of CO. Within the 60 h catalyst lifespan test, methanol conversion was maintained at 98.6% (13.6 g/h g catalyst) and with 100% CO 2 selectivity. In the meantime, for distinguishing the advantage of nanoscale catalyst, the La 2CuO 4 bulk powder was prepared and tested for the SRM reaction for comparison. Compared with the La 2CuO 4 nanofiber, the bulk powder La 2CuO 4 showed worse catalytic activity for the SRM reaction. The 100% conversion of methanol was achieved at the temperature of 400 °C, with the products being H 2 and CO 2 together with CO. The catalytic activity in terms of methanol conversion dropped to 88.7% (12.2 g/h g catalyst) in 60 h. The reduction temperature for nanofiber La 2CuO 4 was much lower than that for the La 2CuO 4 bulk powder. The nanofibers were of higher specific surface area (105.0 m 2/g), metal copper area and copper dispersion. The in situ FTIR and EPR experiments were employed to study the catalysts and catalytic process. In the nanofiber catalyst, there were oxygen vacancies. H 2-reduction resulted in the generation of trapped electrons [e] on the vacancy sites. Over the nanofiber catalyst, the intermediate H 2CO/HCO was stable and was reformed to CO 2 and H 2 by steam rather than being decomposed directly to CO and H 2. Over the bulk counterpart, apart from the direct decomposition of H 2CO/HCO to CO and H 2, the intermediate H 2COO might go through two decomposition ways: H 2COO=CO+H 2O and H 2COO=CO 2+H 2.

  15. Isobutanol-methanol mixtures from synthesis gas. Quarterly technical progress report, July 1--September 30, 1995

    SciTech Connect

    Eglesia, E.

    1995-10-24

    Mechanistic and kinetic studies of methanol and ethanol coupling reactions on Cs/Cu/ZnO and Cu/ZnO/MnO catalysts using isotopically-labeled compounds have confirmed that coupling reactions proceed via intermediate dehydrogenation of alcohols to aldehydes. Ethanol coupling reactions are much faster than those of methanol because ethanol forms a more thermodynamically favored intermediate (acetaldehyde), with aldol condensation pathways kinetically available for chain growth. Cs decreases the rate of formation of aldehydes in alcohol dehydrogenation reaction and inhibits the undesired conversion of methanol and ethanol to synthesis gas (CO/H{sub 2}). Construction and start-up of the Catalytic Microreactor Unit (CMRU) for high pressure isobutanol synthesis studies have been completed. Initial certification runs have reproduced catalytic CO conversion rates on a standard APCI material (Cs/Cu/ZnO/Al{sub 2}O{sub 3}). Condensation of higher alcohols in the transfer lines appears to be responsible for the observed low apparent selectivity to higher alcohols. The design and construction of the Temperature-Programmed Surface Reaction (TPSR) Unit for the study of the adsorption and reaction properties of alcohols and other oxygenates on isobutanol, synthesis catalysts and components is complete. The reduction of CuO powder and of a Cs/Cu/ZnO catalyst were used to certify the apparatus before proceeding with alcohol adsorption and reaction studies.

  16. Isobutanol-methanol mixtures from synthesis gas. Quarterly technical progress report, 1 January--31 March 1995

    SciTech Connect

    Iglesia, E.

    1995-04-24

    The contract objectives are: to design a catalytic material for the synthesis of isobutanol with a productivity of 200 g isoalcohols/g-cat-h and a molar isobutanol/methanol ratio near unity; and to develop structure-function rules for the design of catalysts for the selective conversion of synthesis gas to isoalcohols. Several catalyst samples have been prepared by controlled co-precipitation from aqueous mixtures of metal nitrates. The composition of these materials is based on reports of best available catalysts for methanol synthesis, for isobutanol synthesis, and for methanol coupling reactions. The mechanical construction and pressure testing of the microreactor system has been completed. The in-situ infrared spectrophotometer equipped with a nitrogen purge is fully operational. The temperature-programmed surface reaction (TPSR) unit has been designed; construction will begin during the third quarter FY`95. Air Products and Chemicals has provided us with a sample of a BASF isobutanol synthesis catalyst and with catalytic data obtained on this catalyst in a LaPorte test run. This catalyst will serve as a benchmark for the certification of our new microreactor system.

  17. Determination of methanol in pulp washing filtrates by desiccated full evaporation headspace gas chromatography.

    PubMed

    Hu, Hui-Chao; Chai, Xin-Sheng

    2012-01-27

    This paper reports on a desiccated full evaporation headspace gas chromatographic (FE HS-GC) technique for determination of the methanol content in dilute mill effluents. Anhydrous K(2)CO(3) was selected as the preferred salt for eliminating the water in the sample in the headspace sample vial. The results showed that the addition of 12 g K(2)CO(3) made it possible to introduce a larger sample size (up to 1 mL) into the FE HS-GC measurement, thereby increasing the sensitivity of the technique. At the given equilibration temperature (105°C), a near-complete mass transfer of methanol from the liquid phase to vapor phase (headspace) was achieved within 10 min. Replicate samples showed that the relative standard deviation of the method was less than 1.5%. Further, the limit of quantification (LOQ) was 0.12 μg and the recovery ranged from 95 to 104%. The present method greatly improves the methanol detection sensitivity in the FE HS-GC method and has the added advantage of being simple, rapid and accurate. PMID:22209356

  18. Gas-phase reactivity of metavanadate [VO3]- towards methanol and ethanol: experiment and theory.

    PubMed

    Waters, Tom; Wedd, Anthony G; O'Hair, Richard A J

    2007-01-01

    The gas-phase reactivity of the metavanadate anion [VO3]- towards methanol and ethanol was examined by a combination of ion-molecule reaction and isotope labelling experiments in a quadrupole ion-trap mass spectrometer. The experimental data were interpreted with the aid of density functional theory calculations. [VO3]- dehydrated methanol to eliminate water and form [VO2(eta2-OCH2)]-, which features an [eta2-C,O-OCH2]2- ligand formed by formal removal of two protons from methanol and which is isoelectronic with peroxide. [VO3]- reacted with ethanol in an analogous manner to form [VO2(eta2-OCHCH3)]-, as well as by loss of ethene to form [VO2(OH)2]-. The calculations predicted that important intermediates in these reactions were the hydroxo alkoxo anions [VO2(OH)(OCH2R)]- (R: H, CH3). These were predicted to undergo intramolecular hydrogen-atom transfer to form [VO(OH)2(eta1-OCHR)]- followed by eta1-O-->eta2-C,O rearrangements to form [VO(OH)2(eta2-OCHR)]-. The latter reacted further to eliminate water and generate the product [VO2(eta2-OCHR)]-. This major product observed for [VO3]- is markedly different from that observed previously for [NbO3]- containing the heavier Group 5 congener niobium. In that case, the major product of the reaction was an ion of stoichiometry [Nb, O3, H2]- arising from the formal dehydrogenation of methanol to formaldehyde. The origin of this difference was examined theoretically and attributed to the intermediate alkoxo anion [NbO2(OH)(OCH3)]- preferring hydride transfer to form [HNbO2(OH)]- with loss of formaldehyde. This contrasts with the hydrogen-atom-transfer pathway observed for [VO2(OH)(OCH3)]-. PMID:17661322

  19. Underground Coal Gasification (UCG) gas to methanol and MTG-gasoline: An economic and sensitivity study, task B

    NASA Astrophysics Data System (ADS)

    1982-06-01

    The technical and economic aspects of the production of methanol and gasoline using gas from an underground coal gasification (UCG) facility are discussed. The economics of producing gasoline is studied as well as a number of other aspects of the economics of upgrading UCG gas. Capital and operating costs for three different capacities of gasoline plants are presented. These are 1600 barrels per day (BPD), 4800 BPD, and 9600 BPD. These capacities are equivalent to fuel grade methanol plants having capacities of 4000 BPD, 12,000 BPD, and 24,000 BPD - the methanol capacities considered in the previous studies. The economics of the gasoline plant were developed using published information and the best estimate of the processing steps in the gasoline process. Several sensitivity studies were undertaken to examine the sensitivity of both methanol and gasoline product costs to changes in technical and economic parameters.

  20. A planar anode-supported Solid Oxide Fuel Cell model with internal reforming of natural gas

    NASA Astrophysics Data System (ADS)

    Chinda, P.; Chanchaona, S.; Brault, P.; Wechsatol, W.

    2011-05-01

    Solid Oxide Fuel Cells (SOFCs) are of great interest due to their high energy efficiency, low emission level, and multiple fuel utilization. SOFC can operate with various kinds of fuels such as natural gas, carbon monoxide, methanol, ethanol, and hydrocarbon compounds, and they are becoming one of the main competitors among environmentally friendly energy sources for the future. In this study, a mathematical model of a co-flow planar anode-supported solid oxide fuel cell with internal reforming of natural gas has been developed. The model simultaneously solves mass, energy transport equations, and chemical as well as electrochemical reactions. The model can effectively predict the compound species distributions as well as the cell performance under specific operating conditions. The main result is a rather small temperature gradient obtained at 800 °C with S/C = 1 in classical operating conditions. The cell performance is reported for several operating temperatures and pressures. The cell performance is specified in terms of cell voltage and power density at any specific current density. The influence of electrode microstructure on cell performance was investigated. The simulation results show that the steady state performance is almost insensitive to microstructure of cells such as porosity and tortuosity unlike the operating pressure and temperature. However, for SOFC power output enhancement, the power output could be maximized by adjusting the pore size to an optimal value, similarly to porosity and tortuosity. At standard operating pressure (1 atm) and 800 °C with 48% fuel utilization, when an output cell voltage was 0.73 V, a current density of 0.38 A cm-2 with a power density of 0.28 W cm-2 was predicted. The accuracy of the model was validated by comparing with existing experimental results from the available literature.

  1. Effect of Gold Particle Size on Steam Reforming of Methanol Over Au/CeO2-ZrO2 Catalysts.

    PubMed

    Lakshmanan, Pandian; Kim, Dong Ha; Park, Eun Duck

    2016-05-01

    We examined the effect of the particle size of gold on steam reforming of methanol over Au/CeO2-ZrO2 catalysts. Gold was loaded onto CeO2-ZrO2 through deposition-precipitation. The average particle size (2-12 nm) of the gold was controlled by thermal reduction under H2 at various temperatures and by chemical reduction with various reducing agents. The catalytic activity decreased significantly with increasing particle size of the gold. The turnover frequency at the interface between gold and a support appeared to be independent of particle size in the range 2-5 nm, which implies that the perimeter of the particle may be the active site for this reaction. Methanol adsorption and conversion over these catalysts were also investigated with in-situ diffuse reflectance infrared Fourier transform spectroscopy. Analytical results for various adsorbed intermediate species during methanol conversion suggests that transformation of methoxy species is facilitated by use of smaller gold particles. PMID:27483761

  2. Analytical methods for measuring the parameters of interstellar gas using methanol observations

    NASA Astrophysics Data System (ADS)

    Kalenskii, S. V.; Kurtz, S.

    2016-08-01

    The excitation of methanol in the absence of external radiation is analyzed, and LTE methods for probing interstellar gas considered. It is shown that rotation diagrams correctly estimate the gas kinetic temperature only if they are constructed using lines whose upper levels are located in the same K-ladders, such as the J 0- J -1 E lines at 157 GHz, the J 1- J 0 E lines at 165 GHz, and the J 2- J 1 E lines at 25 GHz. The gas density must be no less than 107 cm-3. Rotation diagrams constructed from lines with different K values for their upper levels (e.g., 2 K -1 K at 96 GHz, 3 K -2 K at 145 GHz, 5 K -4 K at 241 GHz) significantly underestimate the temperature, but enable estimation of the density. In addition, diagrams based on the 2 K -1 K lines can be used to estimate the methanol column density within a factor of about two to five. It is suggested that rotation diagrams should be used in the following manner. First, two rotation diagrams should be constructed, one from the lines at 96, 145, or 241 GHz, and another from the lines at 157, 165, or 25 GHz. The former diagram is used to estimate the gas density. If the density is about 107 cm-3 or higher, the latter diagram reproduces the temperature fairly well. If the density is around 106 cm-3, the temperature obtained from the latter diagram should be multiplied by a factor of 1.5-2. If the density is about 105 cm-3 or lower, then the latter diagram yields a temperature that is lower than the kinetic temperature by a factor of three or more, and should be used only as a lower limit for the kinetic temperature. The errors in the methanol column density determined from the integrated intensity of a single line can be more than an order of magnitude, even when the gas temperature is well known. However, if the J 0-( J - 1)0 E lines, as well as the J 1-( J - 1)1 A + or A - lines are used, the relative error in the column density is no more than a factor of a few.

  3. Biomass gasification with air in fluidized bed: Reforming of the gas composition with commercial steam reforming catalysts

    SciTech Connect

    Corella, J.; Orio, A.; Aznar, P.

    1998-12-01

    Four commercial catalysts for steam reforming of higher hydrocarbons (naphthas) and three for steam reforming of light hydrocarbons are tested for hot gas clean up and upgrading in biomass gasification with air in fluidized bed. The catalysts used originate from four manufacturers: BASF, AG, ICI-Katalco, Haldor Topsoe a/s, and United Catalysts Inc. The work is performed in a small pilot plant (1--2 kg of biomass fed/h) with three reactors in series: gasifier, guard bed of dolomite, and full flow catalytic bed. Samples of gas are taken before and after the catalytic bed at different times-on-stream. It is shown how the H{sub 2}, CO, CO{sub 2}, CH{sub 4} and steam contents in the flue gas change because of the catalytic bed approaching contents near to the ones corresponding to the equilibrium state. Variations in the heating value of the gas and gas yield as a result of the catalytic bed are also reported.

  4. COAL GASIFICATION/GAS CLEANUP TEST FACILITY: VOLUME II. ENVIRONMENTAL ASSESSMENT OF OPERATION WITH DEVOLATILIZED BITUMINOUS COAL AND CHILLED METHANOL

    EPA Science Inventory

    The report gives results of initial runs of a pilot-scale coal gasification and gas cleaning plant at North Carolina State University. In these runs, a devolatilized Western Kentucky No. 11 bituminous coal was gasified with steam and oxygen, and chilled methanol was used as the a...

  5. Evaluation of the use of UCG gas to produce 4000 BPD and 12,000 BPD of methanol with conversion to M-gasoline

    SciTech Connect

    Carlisle, Donald

    1981-01-01

    This study involves an examination of the technical and economic feasibility of using raw gas from an underground coal gasification facility as feedstock for methanol synthesis, and producing M-gasoline from the methanol. It differs from previous studies in considering facilities smaller than those previously studied. Addressed also is the economic and technical feasibility of using equipment from existing ammonia plants for the production of methanol. Ammonia and methanol plants are very similar in type of equipment used and plant layout. Consequently, it is possible to convert an existing ammonia plant into a methanol facility. Existing ammonia and methanol plants which contain equipment that might be utilized with UCG all use natural gas for feedstock. The processing steps in these plants can be divided into unit operations which are described. The product price analysis shows that significant economies of scale exist for the larger of the two facility sizes considered in this study. The economies of scale are evident for both the methanol/M-gasoline and methanol-only facilities. Compared to current market prices, the calculated product prices for the 4000 BPD and 12,000 BPD methanol-only facilities are within the range of competitiveness with the prices of conventionally produced methanol. The product prices calculated for the 12,000 BPD methanol/4910 BPD M-gasoline facility are, under the most optimistic assumptions, 50% higher than the current market price for unleaded gasoline.

  6. Feasibility of flare gas reformation to practical energy in Farashband gas refinery: no gas flaring.

    PubMed

    Rahimpour, Mohammad Reaza; Jokar, Seyyed Mohammad

    2012-03-30

    A suggested method for controlling the level of hazardous materials in the atmosphere is prevention of combustion in flare. In this work, three methods are proposed to recover flare gas instead of conventional gas-burning in flare at the Farashband gas refinery. These methods aim to minimize environmental and economical disadvantages of burning flare gas. The proposed methods are: (1) gas to liquid (GTL) production, (2) electricity generation with a gas turbine and, (3) compression and injection into the refinery pipelines. To find the most suitable method, the refinery units that send gas to the flare as well as the required equipment for the three aforementioned methods are simulated. These simulations determine the amount of flare gas, the number of GTL barrels, the power generated by the gas turbine and the required compression horsepower. The results of simulation show that 563 barrels/day of valuable GTL products is produced by the first method. The second method provides 25 MW electricity and the third method provides a compressed natural gas with 129 bar pressure for injection to the refinery pipelines. In addition, the economics of flare gas recovery methods are studied and compared. The results show that for the 4.176MMSCFD of gas flared from the Farashband gas refinery, the electricity production gives the highest rate of return (ROR), the lowest payback period, the highest annual profit and mild capital investment. Therefore, the electricity production is the superior method economically. PMID:22305604

  7. CO sub 2 -foam fracturing with methanol successfully stimulates canyon gas sand

    SciTech Connect

    Craft, J.R.; Waddell, S.P. ); McFatridge, D.G. )

    1992-05-01

    Successful stimulation using CO{sub 2} foam with methanol has revived the economically marginal Canyon gas-sand reservoir of Sterling County, TX. Field experience in the Conger (Penn) field demonstrated that CO{sub 2} foam (1) lessened the water required in the fluid and (2) provided a gas assist to help remove water and lower interfacial tension (IFT). The low pH of the fluid, combined with additional clay stabilization, iron control, and enhanced water recovery additives, proved helpful in initial well response and subsequent performances. Since the CO{sub 2}-foam fracture treatments were administered, production from Sterling County Canyon gas sands met or surpassed initial rates, even though formation pressure in the field declined 33.2%. Stimulation is essential for commercial production in these sands. However, water blockage, caused by stimulation, was encountered in designing an effective completion technique for a tight formation with reduced bottomhole pressure (HBP). Production in tight, low-pressure gas wells can be completely blocked if formation pressure does not exceed the capillary pressure increase caused by injected fracture fluid. Original stimulation techniques consisted mainly of gelled-water fracture treatments containing 65,000 lbm of 20/40-mesh sand with a maximum concentration of 2 1/2 lbm/gal. In many cases, several weeks of swabbing were required to ensure continuous flow. After the fracture treatments, about 40% water recovery was realized throughout the field. This paper discusses CO{sub 2}-foam fracture treatments and job design and presents case histories from several Conger (Penn) field CO{sub 2}-foam fracture treatments.

  8. Multifuel reformer R D

    SciTech Connect

    Kumar, R.; Ahmed, S.

    1991-01-01

    The on-board fuel for fuel cell powered vehicles may be one or more of hydrogen, methanol, ethanol, natural gas, propane, or other liquified petroleum gases. To use hydrogen as the fuel, suitable means of storing, and subsequently delivering, adequate quantities of the gas must be developed. For all other fuels suitable reformers must be developed to convert the fuel to hydrogen or a hydrogen-rich gas mixture at rates corresponding to the varying power demand rates of the automotive system; this is especially true for the lower temperature fuel cells, such as the polymer electrolyte fuel cell which operates at 80{degrees}C and the phosphoric acid fuel cell which operates at 190{degrees}C. This paper discusses the key design and performance characteristics of such hydrogen storage and fuel reformer systems for use in stand-alone fuel cell automotive applications.

  9. In situ Gas Conditioning in Fuel Reforming for Hydrogen Generation

    SciTech Connect

    Bandi, A.; Specht, M.; Sichler, P.; Nicoloso, N.

    2002-09-20

    The production of hydrogen for fuel cell applications requires cost and energy efficient technologies. The Absorption Enhanced Reforming (AER), developed at ZSW with industrial partners, is aimed to simplify the process by using a high temperature in situ CO2 absorption. The in situ CO2 removal results in shifting the steam reforming reaction equilibrium towards increased hydrogen concentration (up to 95 vol%). The key part of the process is the high temperature CO2 absorbent. In this contribution results of Thermal Gravimetric Analysis (TGA) investigations on natural minerals, dolomites, silicates and synthetic absorbent materials in regard of their CO2 absorption capacity and absorption/desorption cyclic stability are presented and discussed. It has been found that the inert parts of the absorbent materials have a structure stabilizing effect, leading to an improved cyclic stability of the materials.

  10. Isotope Effects in the Resonant Inelastic Soft X-ray Scattering Maps of Gas-Phase Methanol.

    PubMed

    Benkert, A; Meyer, F; Hauschild, D; Blum, M; Yang, W; Wilks, R G; Bär, M; Reinert, F; Heske, C; Weinhardt, L

    2016-04-14

    The electronic structure of gas-phase methanol molecules (H3COH, H3COD, and D3COD) at atmospheric pressure was investigated using resonant inelastic soft X-ray scattering (RIXS) at the O K and C K edges. We observe strong changes of the relative emission intensities of all valence orbitals as a function of excitation energy, which can be related to the symmetries of the involved orbitals causing an angularly anisotropic RIXS intensity. Furthermore, all observed emission lines are subject to strong spectator shifts of up to -0.9 eV at the O K edge and up to -0.3 eV at the C K edge. At the lowest O K resonance, we find clear evidence for dissociation of the methanol molecule on the time scale of the RIXS process, which is illustrated by comparing X-ray emission spectra of regular and deuterated methanol. PMID:27003748

  11. Control of hydrocarbon content of a reforming gas by using a hydrogenation catalyst.

    PubMed

    Inoue, Kenichiro; Kawamoto, Katsuya

    2010-01-01

    To control of hydrocarbon content in waste pyrolysis-gasification and reforming processes, the use of a hydrogenation catalyst was examined in a test system with a model gas. To reduce the concentration of benzene in the reforming gas, benzene was hydrogenated with a nickel catalyst. The catalyst is usually used to convert gas-phase unsaturated hydrocarbons to saturated hydrocarbons, and the benzene was converted to cyclohexane at a temperature range of about 130 to 180 degrees C in the presence of steam. However, the conversion to methane occurred at about 250 to 300 degrees C. Methane seems to be a useful conversion compound because it does not cohere as a light tar. Sometimes the reforming gas needs to be cooled for use as generator fuel. In this case, it is possible to avoid the tar cohesion if the benzene in the gas is converted to methane at about 300 degrees C after the reforming. Reduction of the efficiency of conversion to methane was not observed over a 60h reaction period. The lower hydrocarbons (ethylene, ethane, and propylene) were also converted to methane at about 300 degrees C. Conversion of benzene was also possible when other hydrocarbons were present at high concentrations. PMID:20022077

  12. Modeling the effect of anisotropy of gas diffusion layer on transport phenomena in a direct methanol fuel cell

    NASA Astrophysics Data System (ADS)

    Miao, Zheng; He, Ya-Ling; Zou, Jin-Qiang

    Transport phenomena in the gas diffusion layer (GDL) are of vital importance for the operation of direct methanol fuel cells (DMFCs). In this work, a two-phase mass transport model is developed to investigate the effects of anisotropic characteristics of a GDL, including the inherent anisotropy, deformation, and electrical and thermal contact resistances, on the coupled species, charges and thermal transport processes in a DMFC. In this model, methanol crossover and non-equilibrium evaporation/condensation of water and methanol are considered. The multistep electrochemical mechanisms are used to obtain a detailed description of the kinetics of methanol oxidization reaction (MOR) in both the anode and cathode catalyst layers (CLs). The numerical results show that the anisotropy of the GDL has a great effect on the distribution of species concentration, overpotential, local current density, and temperature. The deformation of the GDL depresses the transport of species through the GDL, particularly methanol diffusion in anode GDL, but facilitates the transport of electron and the removal of heat. The electrical contact resistance plays an important role in determining the cell performance.

  13. Method for forming synthesis gas using a plasma-catalyzed fuel reformer

    DOEpatents

    Hartvigsen, Joseph J; Elangovan, S; Czernichowski, Piotr; Hollist, Michele

    2015-04-28

    A method of forming a synthesis gas utilizing a reformer is disclosed. The method utilizes a reformer that includes a plasma zone to receive a pre-heated mixture of reactants and ionize the reactants by applying an electrical potential thereto. A first thermally conductive surface surrounds the plasma zone and is configured to transfer heat from an external heat source into the plasma zone. The reformer further includes a reaction zone to chemically transform the ionized reactants into synthesis gas comprising hydrogen and carbon monoxide. A second thermally conductive surface surrounds the reaction zone and is configured to transfer heat from the external heat source into the reaction zone. The first thermally conductive surface and second thermally conductive surface are both directly exposed to the external heat source. A corresponding apparatus and system are also disclosed herein.

  14. Internal reforming for natural gas fueled molten carbonate fuel cells. Final report 1 May 80-30 Jun 81

    SciTech Connect

    Baker, B.; Burns, D.; Lee, C.; Maru, H.; Patel, P.

    1981-12-01

    A natural gas fueled molten carbonate fuel cell (MCFC) is an attractive system for efficient electricity generation. The system yields maximum efficiency while operating on internal reforming mode. Among the various configurations evaluated for internal reforming MCFC, direct internal reforming appears to be most promising. Compared to the conventional baseline external reformer system, it can save as much as 20% natural gas at reduced capital and operating costs. The feasibility of internal reforming in MCFC has been verified through laboratory-scale (10 sq cm) cell tests followed by a successful scale-up to bench-scale (300 sq cm) cell. Bench-scale cells have been operated with direct methane feed up to 2000 hours. The results of system analysis and experimental work show that a successful development of the internal reforming MCFC will result in significant savings of natural gas and a cost effective electricity generation.

  15. Hydrogenolysis of cellulose to C4-C7 alcohols over bi-functional CuO-MO/Al2O3 (M=Ce, Mg, Mn, Ni, Zn) catalysts coupled with methanol reforming reaction.

    PubMed

    Wu, Yanhua; Gu, Fangna; Xu, Guangwen; Zhong, Ziyi; Su, Fabing

    2013-06-01

    This work demonstrates the efficient hydrogenolysis of cellulose to C4-C7 alcohols and gas products (reaction 1) by coupling it with the reforming reaction of methanol (reaction 2) over bi-functional CuO-based catalysts. In this process, the CuO-based catalysts catalyze both the reactions 1 and 2, and the in situ regenerated H2 in the reaction 2 is used for the reaction 1. A series of CuO-MO/Al2O3 (M=Ce, Mg, Mn, Ni, Zn) catalysts were prepared by the co-precipitation method. Among these catalysts, CuO-ZnO/Al2O3 exhibited the highest activity to generate a high cellulose conversion of 88% and a high C4-C7 alcohols content above 95% in the liquid products. The CuO-ZnO/Al2O3 catalyst was stable under the reaction conditions and reusable after 4 runs. This work provides a cost-effective route to convert abundant renewable cellulose to liquid fuels. PMID:23591118

  16. Plasma reforming and partial oxidation of hydrocarbon fuel vapor to produce synthesis gas and/or hydrogen gas

    DOEpatents

    Kong, Peter C.; Detering, Brent A.

    2003-08-19

    Methods and systems for treating vapors from fuels such as gasoline or diesel fuel in an internal combustion engine, to form hydrogen gas or synthesis gas, which can then be burned in the engine to produce more power. Fuel vapor, or a mixture of fuel vapor and exhaust gas and/or air, is contacted with a plasma, to promote reforming reactions between the fuel vapor and exhaust gas to produce carbon monoxide and hydrogen gas, partial oxidation reactions between the fuel vapor and air to produce carbon monoxide and hydrogen gas, or direct hydrogen and carbon particle production from the fuel vapor. The plasma can be a thermal plasma or a non-thermal plasma. The plasma can be produced in a plasma generating device which can be preheated by contact with at least a portion of the hot exhaust gas stream, thereby decreasing the power requirements of the plasma generating device.

  17. Plasma Reforming And Partial Oxidation Of Hydrocarbon Fuel Vapor To Produce Synthesis Gas And/Or Hydrogen Gas

    DOEpatents

    Kong, Peter C.; Detering, Brent A.

    2004-10-19

    Methods and systems are disclosed for treating vapors from fuels such as gasoline or diesel fuel in an internal combustion engine, to form hydrogen gas or synthesis gas, which can then be burned in the engine to produce more power. Fuel vapor, or a mixture of fuel vapor and exhaust gas and/or air, is contacted with a plasma, to promote reforming reactions between the fuel vapor and exhaust gas to produce carbon monoxide and hydrogen gas, partial oxidation reactions between the fuel vapor and air to produce carbon monoxide and hydrogen gas, or direct hydrogen and carbon particle production from the fuel vapor. The plasma can be a thermal plasma or a non-thermal plasma. The plasma can be produced in a plasma generating device which can be preheated by contact with at least a portion of the hot exhaust gas stream, thereby decreasing the power requirements of the plasma generating device.

  18. Efficacy of different methanolic plant extracts on anti-methanogenesis, rumen fermentation and gas production kinetics in vitro

    PubMed Central

    Sirohi, S.K.; Goel, N.; Pandey, P.

    2012-01-01

    The present study was carried out to evaluate the effect of methanolic extracts of three plants, mehandi (Lawsonia inermis), jaiphal (Myristica fragrans) and green chili (Capsicum annuum) on methanogenesis, rumen fermentation and fermentation kinetic parameters by in vitro gas production techniques. Single dose of each plant extract (1 ml / 30 ml buffered rumen fluid) and two sorghum fodder containing diets (high and low fiber diets) were used for evaluating the effect on methanogenesis and rumen fermentation pattern, while sequential incubations (0, 1, 2, 3, 6 9, 12, 24, 36, 48, 60, 72 and 96 h) were carried out for gas production kinetics. Results showed that methane production was reduced, ammonia nitrogen was increased significantly, while no significant effect was found on pH and protozoal population following addition of different plant extracts in both diets except mehandi. Green chili significantly reduced digestibility of dry matter, total fatty acid and acetate concentration at incubation with sorghum based high and low fiber diets. Among all treatments, green chili increased potential gas production, while jaiphal decreased the gas production rate constant significantly. The present results demonstrate that methanolic extracts of different plants are promising rumen modifying agents. They have the potential to modulate the methane production, potential gas production, gas production rate constant, dry matter digestibility and microbial biomass synthesis. PMID:26623296

  19. Vapor-liquid activity coefficients for methanol and ethanol from heat of solution data: application to steam-methane reforming.

    PubMed

    Kunz, R G; Baade, W F

    2001-11-16

    This paper presents equations and curves to calculate vapor-liquid phase equilibria for methanol and ethanol in dilute aqueous solution as a function of temperature, using activity coefficients at infinite dilution. These thermodynamic functions were originally derived to assess the distribution of by-product contaminants in the process condensate and the steam-system deaerator of a hydrogen plant [Paper ENV-00-171 presented at the NPRA 2000 Environmental Conference, San Antonio, TX, 10-12 September 2000], but have general applicability to other systems as well. The functions and calculation method described here are a necessary piece of an overall prediction technique to estimate atmospheric emissions from the deaerator-vent when the process condensate is recycled as boiler feed water (BFW) make-up. Having such an estimation technique is of particular significance at this time because deaerator-vent emissions are already coming under regulatory scrutiny in California [Emissions from Hydrogen Plant Process Vents, Adopted 21 January 2000] followed closely elsewhere in the US, and eventually worldwide. The overall technique will enable a permit applicant to estimate environmental emissions to comply with upcoming regulations, and a regulatory agency to evaluate those estimates. It may also be useful to process engineers as a tool to estimate contaminant concentrations and flow rates in internal process streams such as the steam-generating system. Metallurgists and corrosion engineers might be able to use the results for materials selection. PMID:11606240

  20. Plasma reforming of glycerol for synthesis gas production.

    PubMed

    Zhu, Xinli; Hoang, Trung; Lobban, Lance L; Mallinson, Richard G

    2009-05-28

    Glycerol can be effectively converted to synthesis gas (selectivity higher than 80%) with small amounts of water or no water using plasmas at low temperature and atmospheric pressure, without external heating. PMID:19436906

  1. Plasma steam reforming of E85 for hydrogen rich gas production

    NASA Astrophysics Data System (ADS)

    Zhu, Xinli; Hoang, Trung; Lobban, Lance L.; Mallinson, Richard G.

    2011-07-01

    E85 (85 vol% ethanol and 15 vol% gasoline) is a partly renewable fuel that is increasing in supply availability. Hydrogen production from E85 for fuel cell or internal combustion engine applications is a potential method for reducing CO2 emissions. Steam reforming of E85 using a nonthermal plasma (pulse corona discharge) reactor has been exploited at low temperature (200-300 °C) without external heating, diluent gas, oxidant or catalyst in this work. Several operational parameters, including the discharge current, E85 concentration and feed flow rate, have been investigated. The results show that hydrogen rich gases (63-67% H2 and 22-29% CO, with small amounts of CO2, C2 hydrocarbons and CH4) can be produced by this method. A comparison with ethanol reforming and gasoline reforming under identical conditions has also been made and the behaviour of E85 reforming is found to be close to that of ethanol reforming with slightly higher C2 hydrocarbons yields.

  2. Palladium coated porous anodic alumina membranes for gas reforming processes

    NASA Astrophysics Data System (ADS)

    Wu, Jeremy P.; Brown, Ian W. M.; Bowden, Mark E.; Kemmitt, Timothy

    2010-11-01

    Nanostructured ceramic membranes with ultrathin coatings of palladium metal have been demonstrated to separate hydrogen gas from a gas mixture containing nitrogen with 10% carbon dioxide and 10% hydrogen at temperatures up to 550 °C. The mechanically robust and thermally durable membranes were fabricated using a combination of conventional and high-efficiency anodisation processes on high purity aluminium foils. A pH-neutral plating solution has also been developed to enable electroless deposition of palladium metal on templates which were normally prone to chemical corrosion in strong acid or base environment. Activation and thus seeding of palladium nuclei on the surface of the template were essential to ensure uniform and fast deposition, and the thickness of the metal film was controlled by time of deposition. The palladium coated membranes showed improved hydrogen selectivity with increased temperature as well as after prolonged exposure to hydrogen, demonstrating excellent potential for gas separation technologies.

  3. Methanol Conversion for the Production of Hydrogen

    SciTech Connect

    Taylor, C.E.; Howard, B.H.; Myers, C.R.

    2007-12-19

    The production of methanol from a variety of biomass sources is gaining favor. Several facilities exist or are under construction throughout the world to convert biogenerated methane from the decomposition of biomass into methanol using conventional steam reforming. Methanol is an excellent liquid-hydrogen-transport medium. When powered by hydrogen, fuel cells have the potential to be the cleanest and most efficient source of electricity for use by the automotive industry. On-board reforming of liquid hydrocarbon fuels is a viable alternative to the storage of compressed hydrogen. A problem in current reforming processes is the quantity of carbon monoxide (CO) produced. Our research is geared toward circumventing the production of carbon monoxide in methanol reforming through the development of novel reforming catalysts. By modifying a copper-based catalyst, we have produced several catalysts that retain their activity and high surface area after extended methanol reforming runs both with and without the addition of steam.

  4. Bridging the Gap: From Model Surfaces to Nanoparticle Analogs for Selective Oxidation and Steam Reforming of Methanol and Selective Hydrogenation Catalysis

    NASA Astrophysics Data System (ADS)

    Boucher, Matthew B.

    Most industrial catalysts are very complex, comprising of non-uniform materials with varying structures, impurities, and interaction between the active metal and supporting substrate. A large portion of the ongoing research in heterogeneous catalysis focuses on understanding structure-function relationships in catalytic materials. In parallel, there is a large area of surface science research focused on studying model catalytic systems for which structural parameters can be tuned and measured with high precision. It is commonly argued, however, that these systems are oversimplified, and that observations made in model systems do not translate to robust catalysts operating in practical environments; this discontinuity is often referred to as a "gap." The focus of this thesis is to explore the mutual benefits of surface science and catalysis, or "bridge the gap," by studying two catalytic systems in both ultra-high vacuum (UHV) and near ambient-environments. The first reaction is the catalytic steam reforming of methanol (SRM) to hydrogen and carbon dioxide. The SRM reaction is a promising route for on-demand hydrogen production. For this catalytic system, the central hypothesis in this thesis is that a balance between redox capability and weak binding of reaction intermediates is necessary for high SRM activity and selectivity to carbon dioxide. As such, a new catalyst for the SRM reaction is developed which incorporates very small amounts of gold (<1 atomic %) supported on zinc oxide nanoparticles with controlled crystal structures. The performance of these catalysts was studied in a fixed-bed micro-reactor system at ambient pressures, and their structure was characterized by high-resolution microscopic and spectroscopic techniques. Pre-existing oxygen defects in zinc oxide {0001} surfaces, and those created by a perturbation of the defect equilibrium by addition of gold, provide an anchoring site for highly dispersed gold species. By utilizing shape control of

  5. High-Temperature Desulfurization of Heavy Fuel-Derived Reformate Gas Streams for SOFC Applications

    NASA Technical Reports Server (NTRS)

    Flytzani-Stephanopoulos, Maria; Surgenor, Angela D.

    2007-01-01

    Desulfurization of the hot reformate gas produced by catalytic partial oxidation or autothermal reforming of heavy fuels, such as JP-8 and jet fuels, is required prior to using the gas in a solid oxide fuel cell (SOFC). Development of suitable sorbent materials involves the identification of sorbents with favorable sulfidation equilibria, good kinetics, and high structural stability and regenerability at the SOFC operating temperatures (650 to 800 C). Over the last two decades, a major barrier to the development of regenerable desulfurization sorbents has been the gradual loss of sorbent performance in cyclic sulfidation and regeneration at such high temperatures. Mixed oxide compositions based on ceria were examined in this work as regenerable sorbents in simulated reformate gas mixtures and temperatures greater than 650 C. Regeneration was carried out with dilute oxygen streams. We have shown that under oxidative regeneration conditions, high regeneration space velocities (greater than 80,000 h(sup -1)) can be used to suppress sulfate formation and shorten the total time required for sorbent regeneration. A major finding of this work is that the surface of ceria and lanthanan sorbents can be sulfided and regenerated completely, independent of the underlying bulk sorbent. This is due to reversible adsorption of H2S on the surface of these sorbents even at temperatures as high as 800 C. La-rich cerium oxide formulations are excellent for application to regenerative H2S removal from reformate gas streams at 650 to 800 C. These results create new opportunities for compact sorber/regenerator reactor designs to meet the requirements of solid oxide fuel cell systems at any scale.

  6. Regulatory reform for natural gas pipelines: The effect on pipeline and distribution company share prices

    NASA Astrophysics Data System (ADS)

    Jurman, Elisabeth Antonie

    1997-08-01

    The natural gas shortages in the 1970s focused considerable attention on the federal government's role in altering energy consumption. For the natural gas industry these shortages eventually led to the passage of the Natural Gas Policy Act (NGPA) in 1978 as part of the National Energy Plan. A series of events in the decade of the 1980s has brought about the restructuring of interstate natural gas pipelines which have been transformed by regulators and the courts from monopolies into competitive entities. This transformation also changed their relationship with their downstream customers, the LDCs, who no longer had to deal with pipelines as the only merchants of gas. Regulatory reform made it possible for LDCs to buy directly from producers using the pipelines only for delivery of their purchases. This study tests for the existence of monopoly rents by analyzing the daily returns of natural gas pipeline and utility industry stock price data from 1982 to 1990, a period of regulatory reform for the natural gas industry. The study's main objective is to investigate the degree of empirical support for claims that regulatory reforms increase profits in the affected industry, as the normative theory of regulation expects, or decrease profits, as advocates of the positive theory of regulation believe. I also test Norton's theory of risk which predicts that systematic risk will increase for firms undergoing deregulation. Based on a sample of twelve natural gas pipelines, and 25 utilities an event study concept was employed to measure the impact of regulatory event announcements on daily natural gas pipeline or utility industry stock price data using a market model regression equation. The results of this study provide some evidence that regulatory reforms did not increase the profits of pipeline firms, confirming the expectations of those who claim that excess profits result from regulation and will disappear, once that protection is removed and the firms are operating in

  7. Methanol-reforming reaction over copper-containing catalysts: the effects of anions and copper loading in the preparation of the catalysts by kneading method

    SciTech Connect

    Kobayashi, H.; Takezawa, N.; Minochi, C.

    1981-06-01

    Methanol-reforming reaction CH/sub 3/OH + H/sub 2/O = 3H/sub 2/ + CO/sub 2/ was carried out over copper-containing catalysts which were prepared from hydroxides of copper or from the hydroxide kneaded with various metal oxides. The specific activity (activity per weight of copper used) either of supported or support-free catalyst was markedly increased when the hydroxide was prepared from alkali solution with addition of copper salt solution at higher pH or when the weight percentage of copper on the support was decreased. However, other kinetic parameters such as activation energy and selectivity of the reaction were unaffected by the preparation of the catalyst unless copper chloride was employed as a starting material of the hydroxide preparation at lower pH. DTA, ir, XPS, AES and other chemical analyses of the catalysts revealed that hydroxide ion in the hydroxide precipitate prepared at lower pH exchanged in part with the anionic group of its starting material during the course of the preparation. The anion or its fragment was found to be strongly held on the surface and inhibited the reaction to a great extent. On the other hand, the anion held was markedly decreased when the catalyst was prepared at higher pH. This catalyst was found to be highly active for the title reaction. The surface areas of metallic copper were considerably increased when copper was kneaded with the support. This gave rise to the increase in the specific activity of the catalyst.

  8. A Novel Study of Methane-Rich Gas Reforming to Syngas and Its Kinetics over Semicoke Catalyst

    PubMed Central

    Zhang, Guojie; Su, Aiting; Qu, Jiangwen; Du, Yannian

    2014-01-01

    A small-size gasification unit is improved through process optimization to simulate industrial United Gas Improvement Company gasification. It finds that the reaction temperature has important impacts on semicoke catalyzed methane gas mixture. The addition of water vapor can enhance the catalytic activity of reforming, which is due to the fact that addition of water vapor not only removes carbon deposit produced in the reforming and gasification reaction processes, but also participates in gasification reaction with semicoke to generate some active oxygen-containing functional groups. The active oxygen-containing functional groups provide active sites for carbon dioxide reforming of methane, promoting the reforming reaction. It also finds that the addition of different proportions of methane-rich gas can yield synthesis gas with different H2/CO ratio. The kinetics study shows that the semicoke can reduce the activation energy of the reforming reaction and promote the occurrence of the reforming reaction. The kinetics model of methane reforming under the conditions of steam gasification over semicoke is as follows: k-=5.02×103·pCH40.71·pH20.26·exp(−74200/RT). PMID:24959620

  9. A novel study of methane-rich gas reforming to syngas and its kinetics over semicoke catalyst.

    PubMed

    Zhang, Guojie; Su, Aiting; Qu, Jiangwen; Du, Yannian

    2014-01-01

    A small-size gasification unit is improved through process optimization to simulate industrial United Gas Improvement Company gasification. It finds that the reaction temperature has important impacts on semicoke catalyzed methane gas mixture. The addition of water vapor can enhance the catalytic activity of reforming, which is due to the fact that addition of water vapor not only removes carbon deposit produced in the reforming and gasification reaction processes, but also participates in gasification reaction with semicoke to generate some active oxygen-containing functional groups. The active oxygen-containing functional groups provide active sites for carbon dioxide reforming of methane, promoting the reforming reaction. It also finds that the addition of different proportions of methane-rich gas can yield synthesis gas with different H2/CO ratio. The kinetics study shows that the semicoke can reduce the activation energy of the reforming reaction and promote the occurrence of the reforming reaction. The kinetics model of methane reforming under the conditions of steam gasification over semicoke is as follows: [Formula in text]. PMID:24959620

  10. Thermal analysis of cylindrical natural-gas steam reformer for 5 kW PEMFC

    NASA Astrophysics Data System (ADS)

    Jo, Taehyun; Han, Junhee; Koo, Bonchan; Lee, Dohyung

    2016-01-01

    The thermal characteristics of a natural-gas based cylindrical steam reformer coupled with a combustor are investigated for the use with a 5 kW polymer electrolyte membrane fuel cell. A reactor unit equipped with nickel-based catalysts was designed to activate the steam reforming reaction without the inclusion of high-temperature shift and low-temperature shift processes. Reactor temperature distribution and its overall thermal efficiency depend on various inlet conditions such as the equivalence ratio, the steam to carbon ratio (SCR), and the fuel distribution ratio (FDR) into the reactor and the combustor components. These experiments attempted to analyze the reformer's thermal and chemical properties through quantitative evaluation of product composition and heat exchange between the combustor and the reactor. FDR is critical factor in determining the overall performance as unbalanced fuel injection into the reactor and the combustor deteriorates overall thermal efficiency. Local temperature distribution also influences greatly on the fuel conversion rate and thermal efficiency. For the experiments, the operation conditions were set as SCR was in range of 2.5-4.0 and FDR was in 0.4-0.7 along with equivalence ratio of 0.9-1.1; optimum results were observed for FDR of 0.63 and SCR of 3.0 in the cylindrical steam reformer.

  11. Evaluation of different dielectric barrier discharge plasma configurations as an alternative technology for green C1 chemistry in the carbon dioxide reforming of methane and the direct decomposition of methanol.

    PubMed

    Rico, Víctor J; Hueso, José L; Cotrino, José; González-Elipe, Agustín R

    2010-03-25

    Carbon dioxide reforming of methane and direct decomposition of methanol have been investigated using dielectric barrier discharges (DBD) at atmospheric pressure and reduced working temperatures. Two different plasma reactor configurations are compared and special attention is paid to the influence of the surface roughness of the electrodes on the conversion yields in the first plasma device. The influence of different filling gap dielectric materials (i.e., Al(2)O(3) or BaTiO(3)) in the second packed configuration has been also evaluated. Depending on the experimental conditions of applied voltage, residence time of reactants, feed ratios, or reactor configuration, different conversion yields are achieved ranging from 20 to 80% in the case of methane and 7-45% for the carbon dioxide. The direct decomposition of methanol reaches 60-100% under similar experimental conditions. Interestingly, the selectivity toward the production of hydrogen and carbon monoxide is kept almost constant under all the experimental conditions, and the formation of longer hydrocarbon chains or coke as a byproduct is not detected. The maximum efficiency yields are observed for the packed-bed reactor configuration containing alumina for both reaction processes (approximately 1 mol H(2) per kilowatt hour for dry reforming of methane and approximately 4.5 mol H(2) per kilowatt hour for direct decomposition of methanol). PMID:20184329

  12. Thermodynamic models to predict gas-liquid solubilities in the methanol synthesis, the methanol-higher alcohol synthesis, and the Fischer-Tropsch synthesis via gas-slurry processes

    SciTech Connect

    Breman, B.B.; Beenackers, A.A.

    1996-10-01

    Various thermodynamic models were tested concerning their applicability to predict gas-liquid solubilities, relevant for synthesis gas conversion to methanol, higher alcohols, and hydrocarbons via gas-slurry processes. Without any parameter optimization the group contribution equation of state (GCEOS) turns out to be the best model with an average, relative deviation of 19.0%. If a single binary interaction parameter is optimized for each binary system, the Peng-Robinson equation of state, the regular solutions theory, and the Flory-Staverman model all give good predictions with average, relative deviations 4.0, 10.4, and 10.0%, respectively. As expected, the predictions from these models improve further and agree excellently with the experimental values by optimizing two binary interaction parameters for each binary system (average relative deviations <2% for all models). The gas-liquid solubilities could also be correlated accurately to the temperature (average relative deviation = 2.1%) by assuming a constant enthalpy of solution (CEOS) models. For particular binary systems the Flory-Staverman model and the CEOS model give also reasonably accurate predictions of the gas-liquid solubilities by calculating the binary interaction parameters from pure component properties. Such an approach is promising for predicting as yet unknown gas-liquid solubilities without the need for experimental data.

  13. Optimized fuel cell grade hydrogen from methanol

    NASA Astrophysics Data System (ADS)

    Choi, Yongtaek

    2003-10-01

    To evaluate reaction rates liar making hydrogen from methanol, kinetic studies of methanol decomposition, methanol steam reforming, water gas shift reaction, and CO selective oxidation have been performed. These reactions were studied in a micro reactor testing unit using a commercial Cu-ZnO/Al2O3 catalyst for the first three reactions and Pt-Fe/gamma-alumina catalyst for the last reaction. The activity tests were performed between 120˜325°C and atmospheric pressure with a range of feed rates and compositions. For methanol decomposition, water addition to the feed increased the yield of hydrogen and reduced the formation of by-products. XPS analysis of used catalyst samples and time on-stream data showed that the Cu2+ oxidation state of copper favors methanol decomposition. A simplified reaction network of 5 elementary reactions was proposed and all five rate expressions were obtained using non-linear least squares optimization, numerical integration of a one-dimensional PFR model, and extensive experimental data. Similar numerical analysis was carried out to obtain the rate expressions for methanol steam reaction, the water gas shift reaction, and CO selective oxidation. For the kinetics of the water gas shift reaction, an empirical rate expression was obtained from the experimental data. Based on a review of published work on the WGS reaction mechanism, our study found that a rate expression derived from a regenerative mechanism and another rate expression derived from adsorptive mechanism fit the experimental data equally well. For the kinetics of CO preferential oxidation, a reaction model in which three reactions (CO oxidation, H2 oxidation and the WGS reaction) occur simultaneously was chosen to predict the reactor performance. In particular the reverse water gas shift reaction had an important role when fitting the experimental data precisely and explained the selectivity decrease at higher reaction temperatures. Combining the three reactors and several

  14. The synthesis of methanol and the reverse water-gas shift reaction over Zn-deposited Cu(100) and Cu(110) surfaces: comparison with Zn/Cu(111)

    NASA Astrophysics Data System (ADS)

    Nakamura, I.; Fujitani, T.; Uchijima, T.; Nakamura, J.

    1998-03-01

    The catalytic activity of Zn vapor-deposited Cu(100) and Cu(110) surfaces for methanol synthesis by the hydrogenation of CO 2 and the reverse water-gas shift reaction were studied using an XPS apparatus combined with a high-pressure flow reactor (18 atm). At a reaction temperature of 523 K, no promotional effect of Zn was observed for the methanol synthesis on both Zn/Cu(100) and Zn/Cu(110). The results were quite different from those for Zn/Cu(111), on which a significant promotion of methanol synthesis activity appeared to be due to the deposition of Zn, indicating that the promotional effect of Zn was sensitive to the surface structure of Cu. However, hysteresis was observed in the catalytic activity for methanol synthesis over the Zn/Cu(110) surface upon heating above 543 K in the reaction mixture. The activity became twice that measured before heating, which was close to the methanol synthesis activity of Zn/Cu(111) at the same Zn coverage. On the other hand, no such hysteresis was observed for the reverse water-gas shift reaction on Zn/Cu(110), indicating that the active site for methanol synthesis was not identical to that for the reverse water-gas shift reaction. In the post-reaction surface analysis, formate species was detected on both Zn/Cu(100) and Zn/Cu(110), whose coverage increased with increasing Zn coverage at 0< ΘZn<0.2. No correlation between the formate coverage and the methanol synthesis activity was obtained, which was in contrast to the results for Zn/Cu(111). Thus, the structure sensitivity observed in the catalytic activity of methanol synthesis over Zn-deposited Cu surfaces is ascribed to the significant difference in the reactivity of the formate intermediate.

  15. The Methanol Economy Project

    SciTech Connect

    Olah, George; Prakash, G. K.

    2014-02-01

    The Methanol Economy Project is based on the concept of replacing fossil fuels with methanol generated either from renewable resources or abundant natural (shale) gas. The full methanol cycle was investigated in this project, from production of methanol through bromination of methane, bireforming of methane to syngas, CO2 capture using supported amines, co-electrolysis of CO2 and water to formate and syngas, decomposition of formate to CO2 and H2, and use of formic acid in a direct formic acid fuel cell. Each of these projects achieved milestones and provided new insights into their respective fields.

  16. A rapid method for simultaneously determining ethanol and methanol content in wines by full evaporation headspace gas chromatography.

    PubMed

    Zhang, Chun-Yun; Lin, Neng-Biao; Chai, Xin-Sheng; Zhong-Li; Barnes, Donald G

    2015-09-15

    This work reports on a full evaporation headspace gas chromatographic (FE HS-GC) method for simultaneously determining the ethanol (EtOH) and methanol (MeOH) content in wines. A small sample (10μL) was placed in a headspace sample vial, and a near-complete mass transfer of ethanol and methanol from the liquid sample to the vapor phase was obtained within three minutes at a temperature of 105°C, which allowed the measurement of the EtOH and MeOH content in the sample by GC. The results showed excellent precision and accuracy, as shown by the reproducibilities of 1.02% and 2.11% for EtOH and MeOH, respectively, and recoveries that ranged from 96.1% to 104% for both alcohols. The method is efficient, accurate and suitable for the determination of EtOH and MeOH in wine production and quality control. PMID:25863625

  17. Multi-fuel reformers for fuel cells used in transportation. Phase 1: Multi-fuel reformers

    NASA Astrophysics Data System (ADS)

    1994-05-01

    DOE has established the goal, through the Fuel Cells in Transportation Program, of fostering the rapid development and commercialization of fuel cells as economic competitors for the internal combustion engine. Central to this goal is a safe feasible means of supplying hydrogen of the required purity to the vehicular fuel cell system. Two basic strategies are being considered: (1) on-board fuel processing whereby alternative fuels such as methanol, ethanol or natural gas stored on the vehicle undergo reformation and subsequent processing to produce hydrogen, and (2) on-board storage of pure hydrogen provided by stationary fuel processing plants. This report analyzes fuel processor technologies, types of fuel and fuel cell options for on-board reformation. As the Phase 1 of a multi-phased program to develop a prototype multi-fuel reformer system for a fuel cell powered vehicle, the objective of this program was to evaluate the feasibility of a multi-fuel reformer concept and to select a reforming technology for further development in the Phase 2 program, with the ultimate goal of integration with a DOE-designated fuel cell and vehicle configuration. The basic reformer processes examined in this study included catalytic steam reforming (SR), non-catalytic partial oxidation (POX) and catalytic partial oxidation (also known as Autothermal Reforming, or ATR). Fuels under consideration in this study included methanol, ethanol, and natural gas. A systematic evaluation of reforming technologies, fuels, and transportation fuel cell applications was conducted for the purpose of selecting a suitable multi-fuel processor for further development and demonstration in a transportation application.

  18. Nanoporous gold catalysts for selective gas-phase oxidative coupling of methanol at low temperature.

    PubMed

    Wittstock, A; Zielasek, V; Biener, J; Friend, C M; Bäumer, M

    2010-01-15

    Gold (Au) is an interesting catalytic material because of its ability to catalyze reactions, such as partial oxidations, with high selectivities at low temperatures; but limitations arise from the low O2 dissociation probability on Au. This problem can be overcome by using Au nanoparticles supported on suitable oxides which, however, are prone to sintering. Nanoporous Au, prepared by the dealloying of AuAg alloys, is a new catalyst with a stable structure that is active without any support. It catalyzes the selective oxidative coupling of methanol to methyl formate with selectivities above 97% and high turnover frequencies at temperatures below 80 degrees C. Because the overall catalytic characteristics of nanoporous Au are in agreement with studies on Au single crystals, we deduced that the selective surface chemistry of Au is unaltered but that O2 can be readily activated with this material. Residual silver is shown to regulate the availability of reactive oxygen. PMID:20075249

  19. Review on dry reforming of methane, a potentially more environmentally-friendly approach to the increasing natural gas exploitation

    NASA Astrophysics Data System (ADS)

    Lavoie, Jean-Michel

    2014-11-01

    With the actual growth of the natural gas industry in the US as well as the potential and availability of this non-renewable carbon source worldwide, reforming of methane gas is getting increasing attention. Methane can be used for the production of heat or electricity, as well, it can be converted to syngas, a building block that could lead to the production of liquid fuels and chemical, a very promising pathway in light of the increasing price of oil. Amongst the different reforming techniques, dry reforming could represent a very interesting approach both to valorize a cheap source or carbon (CO2) as well as to reduce the overall carbon footprint of the increasing worldwide fossil-based methane consumption. In this short review, attention will be given on the thermodynamics of dry reforming followed by an investigation on dry reforming using heterogeneous catalyst by focusing on the mots popular elements used in literature for dry reforming. Attention will as well be given to different other emerging techniques that may allow countering at one point the high thermodynamic penalties that accompanies conversion of methane using carbon dioxide.

  20. Review on dry reforming of methane, a potentially more environmentally-friendly approach to the increasing natural gas exploitation.

    PubMed

    Lavoie, Jean-Michel

    2014-01-01

    With the actual growth of the natural gas industry in the US as well as the potential and availability of this non-renewable carbon source worldwide, reforming of methane gas is getting increasing attention. Methane can be used for the production of heat or electricity, as well, it can be converted to syngas, a building block that could lead to the production of liquid fuels and chemicals, a very promising pathway in light of the increasing price of oil. Amongst the different reforming techniques, dry reforming could represent a very interesting approach both to valorize a cheap source or carbon (CO2) as well as to reduce the overall carbon footprint of the increasing worldwide fossil-based methane consumption. In this short review, attention will be given to the thermodynamics of dry reforming followed by an investigation on dry reforming using heterogeneous catalyst by focusing on the most popular elements used in literature for dry reforming. Attention will as well be given to other emerging techniques that may allow countering at one point the high thermodynamic penalties that accompanies conversion of methane using carbon dioxide. PMID:25426488

  1. Review on dry reforming of methane, a potentially more environmentally-friendly approach to the increasing natural gas exploitation

    PubMed Central

    Lavoie, Jean-Michel

    2014-01-01

    With the actual growth of the natural gas industry in the US as well as the potential and availability of this non-renewable carbon source worldwide, reforming of methane gas is getting increasing attention. Methane can be used for the production of heat or electricity, as well, it can be converted to syngas, a building block that could lead to the production of liquid fuels and chemicals, a very promising pathway in light of the increasing price of oil. Amongst the different reforming techniques, dry reforming could represent a very interesting approach both to valorize a cheap source or carbon (CO2) as well as to reduce the overall carbon footprint of the increasing worldwide fossil-based methane consumption. In this short review, attention will be given to the thermodynamics of dry reforming followed by an investigation on dry reforming using heterogeneous catalyst by focusing on the most popular elements used in literature for dry reforming. Attention will as well be given to other emerging techniques that may allow countering at one point the high thermodynamic penalties that accompanies conversion of methane using carbon dioxide. PMID:25426488

  2. Evaluation of Reformer Produced Synthesis Gas for Emissions Reductions in Natural Gas Reciprocating Engines

    SciTech Connect

    Mark Scotto

    2010-05-30

    Rolls-Royce Fuel Cell Systems (US) Inc. (RRFCS) has developed a system that produces synthesis gas from air and natural gas. A near-term application being considered for this technology is synthesis gas injection into reciprocating engines for reducing NO{sub x} emissions. A proof of concept study using bottled synthesis gas and a two-stroke reciprocating engine showed that injecting small amounts of high-flammable content synthesis gas significantly improved combustion stability and enabled leaner engine operation resulting in over 44% reduction in NO{sub x} emissions. The actual NO{sub x} reduction that could be achieved in the field is expected to be engine specific, and in many cases may be even greater. RRFCS demonstrated that its synthesis gas generator could produce synthesis gas with the flammable content that was successfully used in the engine testing. An economic analysis of the synthesis gas approach estimates that its initial capital cost and yearly operating cost are less than half that of a competing NO{sub x} reduction technology, Selective Catalytic Reduction. The next step in developing the technology is an integrated test of the synthesis gas generator with an engine to obtain reliability data for system components and to confirm operating cost. RRFCS is actively pursuing opportunities to perform the integrated test. A successful integrated test would demonstrate the technology as a low-cost option to reduce NO{sub x} emissions from approximately 6,000 existing two-stroke, natural gas-fired reciprocating engines used on natural gas pipelines in North America. NO{sub x} emissions reduction made possible at a reasonable price by this synthesis gas technology, if implemented on 25% of these engines, would be on the order of 25,000 tons/year.

  3. Evaluation of Reformer Produced Synthesis Gas for Emissions Reductions in Natural Gas Reciprocating Engines

    SciTech Connect

    Mark V. Scotto; Mark A. Perna

    2010-05-30

    Rolls-Royce Fuel Cell Systems (US) Inc. (RRFCS) has developed a system that produces synthesis gas from air and natural gas. A near-term application being considered for this technology is synthesis gas injection into reciprocating engines for reducing NOx emissions. A proof of concept study using bottled synthesis gas and a two-stroke reciprocating engine showed that injecting small amounts of highflammables content synthesis gas significantly improved combustion stability and enabled leaner engine operation resulting in over 44% reduction in NOx emissions. The actual NOx reduction that could be achieved in the field is expected to be engine specific, and in many cases may be even greater. RRFCS demonstrated that its synthesis gas generator could produce synthesis gas with the flammables content that was successfully used in the engine testing. An economic analysis of the synthesis gas approach estimates that its initial capital cost and yearly operating cost are less than half that of a competing NOx reduction technology, Selective Catalytic Reduction. The next step in developing the technology is an integrated test of the synthesis gas generator with an engine to obtain reliability data for system components and to confirm operating cost. RRFCS is actively pursuing opportunities to perform the integrated test. A successful integrated test would demonstrate the technology as a low-cost option to reduce NOx emissions from approximately 6,000 existing two-stroke, natural gas-fired reciprocating engines used on natural gas pipelines in North America. NOx emissions reduction made possible at a reasonable price by this synthesis gas technology, if implemented on 25% of these engines, would be on the order of 25,000 tons/year.

  4. Process assessment of small scale low temperature methanol synthesis

    NASA Astrophysics Data System (ADS)

    Hendriyana, Susanto, Herri; Subagjo

    2015-12-01

    Biomass is a renewable energy resource and has the potential to make a significant impact on domestic fuel supplies. Biomass can be converted to fuel like methanol via several step process. The process can be split into following main steps: biomass preparation, gasification, gas cooling and cleaning, gas shift and methanol synthesis. Untill now these configuration still has a problem like high production cost, catalyst deactivation, economy of scale and a huge energy requirements. These problems become the leading inhibition for biomass conversion to methanol, which should be resolved to move towards the economical. To address these issues, we developed various process and new configurations for methanol synthesis via methyl formate. This configuration combining two reactors: the one reactor for the carbonylation of methanol and CO to form methyl formate, and the second for the hydrogenolysis of methyl formate and H2 to form two molecule of methanol. Four plant process configurations were compared with the biomass basis is 300 ton/day. The first configuration (A) is equipped with a steam reforming process for converting methane to CO and H2 for increasing H2/CO ratio. CO2 removal is necessary to avoid poisoning the catalyst. COSORB process used for the purpose of increasing the partial pressure of CO in the feed gas. The steam reforming process in B configuration is not used with the aim of reducing the number of process equipment, so expect lower investment costs. For C configuration, the steam reforming process and COSORB are not used with the aim of reducing the number of process equipment, so expect lower investment costs. D configuration is almost similar to the configuration A. This configuration difference is in the synthesis of methanol which was held in a single reactor. Carbonylation and hydrogenolysis reactions carried out in the same reactor one. These processes were analyzed in term of technical process, material and energy balance and economic

  5. Process assessment of small scale low temperature methanol synthesis

    SciTech Connect

    Hendriyana; Susanto, Herri Subagjo

    2015-12-29

    Biomass is a renewable energy resource and has the potential to make a significant impact on domestic fuel supplies. Biomass can be converted to fuel like methanol via several step process. The process can be split into following main steps: biomass preparation, gasification, gas cooling and cleaning, gas shift and methanol synthesis. Untill now these configuration still has a problem like high production cost, catalyst deactivation, economy of scale and a huge energy requirements. These problems become the leading inhibition for biomass conversion to methanol, which should be resolved to move towards the economical. To address these issues, we developed various process and new configurations for methanol synthesis via methyl formate. This configuration combining two reactors: the one reactor for the carbonylation of methanol and CO to form methyl formate, and the second for the hydrogenolysis of methyl formate and H{sub 2} to form two molecule of methanol. Four plant process configurations were compared with the biomass basis is 300 ton/day. The first configuration (A) is equipped with a steam reforming process for converting methane to CO and H{sub 2} for increasing H{sub 2}/CO ratio. CO{sub 2} removal is necessary to avoid poisoning the catalyst. COSORB process used for the purpose of increasing the partial pressure of CO in the feed gas. The steam reforming process in B configuration is not used with the aim of reducing the number of process equipment, so expect lower investment costs. For C configuration, the steam reforming process and COSORB are not used with the aim of reducing the number of process equipment, so expect lower investment costs. D configuration is almost similar to the configuration A. This configuration difference is in the synthesis of methanol which was held in a single reactor. Carbonylation and hydrogenolysis reactions carried out in the same reactor one. These processes were analyzed in term of technical process, material and energy

  6. Isobutanol-methanol mixtures from synthesis gas. Quarterly report, July 1 - September 30, 1996

    SciTech Connect

    Iglesia, E.

    1996-12-01

    A series of CuMgCeO{sub x} catalysts have been prepared by coprecipitating the corresponding metal nitrates with a mixed solution of potassium carbonate and potassium hydroxide. The bulk composition of the catalyst has been measured by atomic absorption (AA) analysis and the Cu dispersion has been determined by N{sub 2}O titration at 90 {degrees}C. CeO{sub x} does not contribute to the measured copper dispersion in K-CuO{sub 0.5}Mg{sub 5}CeO{sub x} samples and the high dispersion value indeed reflects the presence of Cu metal small crystallites. Kinetic studies of methanol and propionaldehyde coupling reactions on K-Cu/MgO/CeO{sub 2} and MgO/CeO{sub 2} catalysts indicate that Cu enhances the rates of alcohol dehydrogenation. High-pressure isobutanol synthesis from CO/H{sub 2} has been studied on CuO{sub 0.5}Mg{sub 5}O{sub x} catalysts at 593 K and 4.5 MPa. CuO{sub 0.5}Mg{sub 5}O{sub x} catalysts show high hydrocarbon and low isobutanol selectivities compared to K-CuO{sub 0.5}Mg{sub 5}CeO{sub x}, suggesting the presence of residual acidity in CuO{sub 0.5}Mg{sub 5}O{sub x}.

  7. Gas-liquid solubilities of the methanol synthesis components in various solvents

    SciTech Connect

    Graaf, G.H.; Smit, H.J.; Stamhuls, E.J.; Beenackers, A.A.C.M. )

    1992-04-01

    The solubilities of CO, CO{sub 2}, H{sub 2}, CH{sub 3}OH, and H{sub 2}O were measured in hexadecane, octadecane, squalane, and benzophenone at 293-573 K and 1.013-90 bar using volume displacement and material balance techniques. The experimental results, consisting of 260 solubility data for 16 binary mixtures, were used to test the applicability of four solubility models. When using literature model parameters, the Skjold-Jorgensen group-contribution equation of state gives the best agreement with the experimental results with an average deviation of 15%. The Soave-Redlich-Kwong and Peng-Robinson equations of state give an excellent agreement with the experimental results when optimized binary interaction coefficients are used. The regular solutions theory gives reasonable results except for the methanol- and water-containing systems when using no optimized binary parameters. This paper reports that the authors' results show a reasonable agreement with the available literature data.

  8. Isobutanol-methanol mixtures from synthesis gas. Quarterly technical progress report, 1 January--31 March 1996

    SciTech Connect

    1996-04-20

    A series of CuMgCeO{sub x} catalysts have been prepared. Range of Cu dispersion, determined by N{sub 2}O titration, was 19-48% and are among the highest reported in the literature for Cu-based methanol and higher alcohol synthesis catalysts. Kinetics of MeOH and EtOH coupling reactions on Cu/ZnO and K-Cu/MgO/CeO{sub 2} catalysts indicate that Cu promotes alcohol dehydrogenation. Acetaldehyde is a reactive intermediate. High-pressure isobutanol synthesis studies have been carried out on K- and Cs-promoted Cu/MgO/CeO{sub 2} catalysts. The K promoter is more active than Cs for CO conversion, but the Cs promoter activates the C{sub 1} to C{sub 2} step more effectively. Catalysts with high alkali loading resulted in low conversions. Temperature programmed surface reaction studies of MeOH, EtOH, and acetaldehyde on MgO/CeO{sub 2}-based Cu catalysts show evolution of acetone, crotonaldehyde, methyl ethyl ketone, H2, carbon oxides. Neither EtOH nor acetaldehyde produces propionaldehyde or 1- propanol, suggesting that these C{sub 3} species can only form via reactions involving C{sub 1} and C{sub 2} oxygenate species.

  9. Isobutanol-methanol mixtures from synthesis gas. Quarterly technical progress report, October 1--December 31, 1995

    SciTech Connect

    Iglesia, E.

    1996-01-10

    A series of Cu{sub 0.5}CeMe(II)O{sub x} catalysts (Me refers to Group II alkali earth elements) have been prepared by coprecipitating the corresponding metal nitrates with potassium carbonate. The bulk composition of the catalyst has been determined by atomic absorption (AA) analysis. High-pressure isobutanol synthesis studies have been carried out over a standard BASF Cs-promoted Cu/ZnO/Al{sub 2}O{sub 3} catalyst. At a CO conversion level of 32%, the isobutanol carbon selectivity is about 5%; whereas that of methanol is 40.2%. A 100% selectivity sum has now been obtained as a result of using response factors measured by the laboratory. The reactions of ethanol and acetic acid over a number of catalysts have been investigated using a temperature programmed surface reaction (TPSR) technique. Ethanol and acetone are the only desorption products observed over Cs-promoted Cu/ZnO/Al{sub 2}O{sub 3} catalysts. Surface acetate ion is believed to be the precursor for acetone formation. Over calcined hydrotalcites, i.e., MgO/Al{sub 2}O{sub 3}, ethylene is formed instead of acetone. The amount of ethylene formed decreases as Mg/Al ratio increases, suggesting a role of aluminum ions in ethanol dehydration reactions.

  10. Reforming of biogas to synthesis gas by a rotating arc plasma at atmospheric pressure

    NASA Astrophysics Data System (ADS)

    Chung, Woo-Jae; Park, Hyun-Woo; Liu, Jing-Lin; Park, Dong-Wha

    2015-09-01

    In order to produce synthesis gas, reforming of biogas composed with 60 percent for CH4 and 40 percent for CO2 was performed by a novel rotating arc plasma process. The effect of O2/CH4 ratio on the conversion, syngas composition and energy cost was investigated to evaluate the performance of proposed system compared with conventional gliding arc plasma process. When the O2/CH4 ratio was increased from 0.4 to 0.9, the conversions of CH4 and O2 increased up to 97.5 percent and 98.8 percent, respectively, while CO2 conversion was almost constant to be 38.6 percent. This is due to more enhance the partial oxidation of CH4 to CO and H2 than that of dry reforming by increasing the O2/CH4 ratio. In this work, energy cost of 32 kJ/mol was achieved with high syngas composition of 71 percent using pure O2 as oxidant reactant. These are lower than those of different arc plasma processes (energy cost of 122 - 1870 kJ/mol) such as spark, spark-shade and gliding arc plasma. Because, this rotating arc plasma can remain in a long arc length and a large volume of plasma with constant arc length mode.

  11. A novel methanol sensor based on gas-penetration through a porous polypyrrole-coated polyacrylonitrile nanofiber mat.

    PubMed

    Jun, Tae-Sun; Ho, Thi Anh; Rashid, Muhammad; Kim, Yong Shin

    2013-09-01

    In this work, we propose a novel chemoresistive gas sensor operated under a vertical analyte flow passing through a permeable sensing membrane. Such a configuration is different from the use of a planar sensor implemented under a conventional horizontal flow. A highly porous core-shell polyacrylonitrile-polypyrrole (PAN@PPy) nanofiber mat was prepared as the sensing element via electrospinning and two-step vapor-phase polymerization (VPP). Various analysis methods such as SEM, TEM, FT-IR and XPS measurements were employed in order to characterize structural features of the porous sensing mat. These analyses confirmed that very thin (ca. 10 nm) conductive PPy sheath layers were deposited by VPP on electrospun PAN nanofibers with an average diameter of 258 nm. Preliminary results revealed that the gas penetration-type PAN@PPy sensor had a higher sensor response and shorter detection and recovery times upon exposure to methanol analyte when compared with a conventional horizontal flow sensor due to efficient and fast analyte transfer into the sensing layer. PMID:24205639

  12. Effect of cooled EGR on performance and exhaust gas emissions in EFI spark ignition engine fueled by gasoline and wet methanol blends

    NASA Astrophysics Data System (ADS)

    Rohadi, Heru; Syaiful, Bae, Myung-Whan

    2016-06-01

    Fuel needs, especially the transport sector is still dominated by fossil fuels which are non-renewable. However, oil reserves are very limited. Furthermore, the hazardous components produced by internal combustion engine forces many researchers to consider with alternative fuel which is environmental friendly and renewable sources. Therefore, this study intends to investigate the impact of cooled EGR on the performance and exhaust gas emissions in the gasoline engine fueled by gasoline and wet methanol blends. The percentage of wet methanol blended with gasoline is in the range of 5 to 15% in a volume base. The experiment was performed at the variation of engine speeds from 2500 to 4000 rpm with 500 intervals. The re-circulated exhaust gasses into combustion chamber was 5%. The experiment was performed at the constant engine speed. The results show that the use of cooled EGR with wet methanol of 10% increases the brake torque up to 21.3%. The brake thermal efficiency increases approximately 39.6% using cooled EGR in the case of the engine fueled by 15% wet methanol. Brake specific fuel consumption for the engine using EGR fueled by 10% wet methanol decreases up to 23% at the engine speed of 2500 rpm. The reduction of CO, O2 and HC emissions was found, while CO2 increases.

  13. Synthesis gas and olefins from the catalytic autothermal reforming of volatile and non-volatile liquids

    NASA Astrophysics Data System (ADS)

    Dreyer, Bradon Justin

    2007-12-01

    The research presented in this thesis develops an understanding of a clean energy process technology, catalytic partial oxidation (CPO). CPO is a process in which a carbon containing fuel, such as a hydrocarbon, is passed over a noble metal catalyst (e.g. rhodium and platinum) to efficiently generate synthesis gas (H2 and CO) and olefins (e.g. ethylene and propylene) in millisecond contact times. Chapter 1 introduces CPO and compares this technology with conventional methods for synthesis gas and olefin production. CPO has several advantages over the traditional synthesis gas and olefin production methods. One advantage includes autothermal operation, requiring no external heat input from furnaces or heat exchangers. Autothermal operation allows these reactors to be built compactly. The short contact-times associated with CPO further enable for high throughput in relatively small reactor systems, and more compact reactors typically translate to faster response times if transient operation is required. Nobel metal based CPO catalysts are also resistant to deactivation, resulting in less catalyst replacement, regeneration, and maintenance, and an increase in operating efficiency. An overview of the many applications of the chemicals produced from CPO is also presented in Chapter 1. The chemicals produced are crucial in generating valuable chemical intermediates that are eventually incorporated in consumer products, medical devices, building structures, and fertilizers. Additionally, H2 can be used as a source of energy in mobile fuel applications. Fuel cells convert H2 and O2 into electricity and water at higher efficiencies than thermal engine generators. Due to the difficulties in H2 storage, these more efficient energy generators are dependent on hydrogen obtained from synthesis gas production in compact, portable fuel reformers, such as CPO reactors. Furthermore, H2 and CO can be used in reducing environmentally harmful emissions. Particularly, the implementation

  14. Combustion synthesized copper-ion substituted FeAl2O4 (Cu0.1Fe0.9Al2O4): A superior catalyst for methanol steam reforming compared to its impregnated analogue

    NASA Astrophysics Data System (ADS)

    Maiti, Sayantani; Llorca, Jordi; Dominguez, Montserrat; Colussi, Sara; Trovarelli, Alessandro; Priolkar, Kaustubh R.; Aquilanti, Giuliana; Gayen, Arup

    2016-02-01

    A series of copper ion substituted MAl2O4 (M = Mg, Mn, Fe and Zn) spinels is prepared by a single step solution combustion synthesis (SCS) and tested for methanol steam reforming (MSR). The copper ion substituted Cu0.1Fe0.9Al2O4 appears to be the most active, showing ∼98% methanol conversion at 300 °C with ∼5% CO selectivity at GHSV = 30,000 h-1 and H2O:CH3OH = 1.1. The analogous impregnated catalyst, CuO (10 at%)/FeAl2O4, is found to be much less active. These materials are characterized by XRD, H2-TPR, BET, HRTEM, XPS and XANES analyses. Spinel phase formation is highly facilitated upon Cu-ion substitution and Cu loading beyond 10 at% leads to the formation of CuO as an additional phase. The ionic substitution of copper in FeAl2O4 leads to the highly crystalline SCS catalyst containing Cu2+ ion sites that are shown to be more active than the dispersed CuO nano-crystallites on the FeAl2O4 impregnated catalyst, despite its lower surface area. The as prepared SCS catalyst contains also a portion of copper as Cu1+ that increases when subjected to reforming atmosphere. The MSR activity of the SCS catalyst decreases with time-on-stream due to the sintering of catalyst crystallites as established from XPS and HRTEM analyses.

  15. Influence of size-induced oxidation state of platinum nanoparticles on selectivity and activity in catalytic methanol oxidation in the gas phase.

    PubMed

    Wang, Hailiang; Wang, Yihai; Zhu, Zhongwei; Sapi, Andras; An, Kwangjin; Kennedy, Griffin; Michalak, William D; Somorjai, Gabor A

    2013-06-12

    Pt nanoparticles with various sizes of 1, 2, 4, and 6 nm were synthesized and studied as catalysts for gas-phase methanol oxidation reaction toward formaldehyde and carbon dioxide under ambient pressure (10 Torr of methanol, 50 Torr of oxygen, and 710 Torr of helium) at a low temperature of 60 °C. While the 2, 4, and 6 nm nanoparticles exhibited similar catalytic activity and selectivity, the 1 nm nanoparticles showed a significantly higher selectivity toward partial oxidation of methanol to formaldehyde, but a lower total turnover frequency. The observed size effect in catalysis was correlated to the size-dependent structure and oxidation state of the Pt nanoparticles. X-ray photoelectron spectroscopy and infrared vibrational spectroscopy using adsorbed CO as molecular probes revealed that the 1 nm nanoparticles were predominantly oxidized while the 2, 4, and 6 nm nanoparticles were largely metallic. Transmission electron microscopy imaging witnessed the transition from crystalline to quasicrystalline structure as the size of the Pt nanoparticles was reduced to 1 nm. The results highlighted the important impact of size-induced oxidation state of Pt nanoparticles on catalytic selectivity as well as activity in gas-phase methanol oxidation reactions. PMID:23701488

  16. Reduction of carbon dioxide gas formation at the anode of a direct methanol fuel cell using chemically enhanced solubility

    NASA Astrophysics Data System (ADS)

    Lundin, Michael D.; McCready, Mark J.

    The production of CO 2 gas at the DMFC anode leads to dramatic increases in pumping power requirements and reduced power output because of mass transfer limitations as bubble trains form in the channels of larger stacks. Experimental observations taken in a 5 cm 2 DMFC test cell operated at 60 °C, 1 atm, and with a methanol/water fuel flow rates of 5-10 cm 3 min -1 indicate that the rate of bubble formation can be reduced by increasing the fuel flow because more liquid is available for the CO 2 to dissolve in. Further observations indicate that KOH and LiOH added to the fuel eliminates CO 2 gas formation in situ at low concentrations because of the greatly increased solubility that results. A mathematical model for the volumetric rate of CO 2 gas production that includes effects of temperature and solubility is developed and extended to include the effects of hydroxide ions in solution. The model is used to predict the onset location of gas formation in the flow field as well as the void fraction at any point in the flow field. Predictions from the model agree very well with our experiments. Model predictions explain differences in the initial location of bubble formation for fuel solutions pre-saturated with CO 2 as opposed to CO 2-free solutions. Experiments with KOH and LiOH added to fuel solutions confirm the validity of the model extension that includes solubility that is enhanced by chemical reaction. Experiments with LiOH, KOH, and ammonium hydroxide show that the long-term durability of standard Pt-Ru/Nafion ®/Pt membrane electrode assemblies is compromised because of the presence of lithium, potassium, and ammonium cations that interact with the Nafion ® membrane and result in increasing the ohmic limitations of the polymer electrolyte membrane. Experiments with Ca(OH) 2, while reducing gas formation, precipitate the product CaCO 3 out of solution too rapidly for downstream filtering, blocking channels in the flow field.

  17. Multi-fuel reformers for fuel cells used in transportation. Multi-fuel reformers: Phase 1 -- Final report

    SciTech Connect

    Not Available

    1994-05-01

    DOE has established the goal, through the Fuel Cells in Transportation Program, of fostering the rapid development and commercialization of fuel cells as economic competitors for the internal combustion engine. Central to this goal is a safe feasible means of supplying hydrogen of the required purity to the vehicular fuel cell system. Two basic strategies are being considered: (1) on-board fuel processing whereby alternative fuels such as methanol, ethanol or natural gas stored on the vehicle undergo reformation and subsequent processing to produce hydrogen, and (2) on-board storage of pure hydrogen provided by stationary fuel processing plants. This report analyzes fuel processor technologies, types of fuel and fuel cell options for on-board reformation. As the Phase 1 of a multi-phased program to develop a prototype multi-fuel reformer system for a fuel cell powered vehicle, the objective of this program was to evaluate the feasibility of a multi-fuel reformer concept and to select a reforming technology for further development in the Phase 2 program, with the ultimate goal of integration with a DOE-designated fuel cell and vehicle configuration. The basic reformer processes examined in this study included catalytic steam reforming (SR), non-catalytic partial oxidation (POX) and catalytic partial oxidation (also known as Autothermal Reforming, or ATR). Fuels under consideration in this study included methanol, ethanol, and natural gas. A systematic evaluation of reforming technologies, fuels, and transportation fuel cell applications was conducted for the purpose of selecting a suitable multi-fuel processor for further development and demonstration in a transportation application.

  18. Chemical recycling of carbon dioxide to methanol and dimethyl ether: from greenhouse gas to renewable, environmentally carbon neutral fuels and synthetic hydrocarbons.

    PubMed

    Olah, George A; Goeppert, Alain; Prakash, G K Surya

    2009-01-16

    Nature's photosynthesis uses the sun's energy with chlorophyll in plants as a catalyst to recycle carbon dioxide and water into new plant life. Only given sufficient geological time can new fossil fuels be formed naturally. In contrast, chemical recycling of carbon dioxide from natural and industrial sources as well as varied human activities or even from the air itself to methanol or dimethyl ether (DME) and their varied products can be achieved via its capture and subsequent reductive hydrogenative conversion. The present Perspective reviews this new approach and our research in the field over the last 15 years. Carbon recycling represents a significant aspect of our proposed Methanol Economy. Any available energy source (alternative energies such as solar, wind, geothermal, and atomic energy) can be used for the production of needed hydrogen and chemical conversion of CO(2). Improved new methods for the efficient reductive conversion of CO(2) to methanol and/or DME that we have developed include bireforming with methane and ways of catalytic or electrochemical conversions. Liquid methanol is preferable to highly volatile and potentially explosive hydrogen for energy storage and transportation. Together with the derived DME, they are excellent transportation fuels for internal combustion engines (ICE) and fuel cells as well as convenient starting materials for synthetic hydrocarbons and their varied products. Carbon dioxide thus can be chemically transformed from a detrimental greenhouse gas causing global warming into a valuable, renewable and inexhaustible carbon source of the future allowing environmentally neutral use of carbon fuels and derived hydrocarbon products. PMID:19063591

  19. A new headspace gas chromatographic method for the determination of methanol content in paper materials used for food and drink packaging.

    PubMed

    Hu, Hui-Chao; Tian, Ying-Xin; Jin, Hui-Jun; Chai, Xin-Sheng; Barnes, Donald G

    2013-10-01

    This study reports on a method for determination of methanol in paper products by headspace gas chromatography (HS-GC). The method is based on the hydrolysis of the pulp or paper matrix, using a phosphoric acid solution (42.5%) as the medium at 120 °C in 5 h (excluding air contact) in order to release matrix-entrapped methanol, which is then determined by HS-GC. Data show that, under the given conditions of hydrolysis, no methanol was formed from the methoxyl groups in the material. Reproducibility tests of the method generated a relative standard deviation of <3.5%, with recovery in the range of 93.4-102%. The present method is reliable, accurate, and suitable for use in batch testing of the methanol content in paper-related materials. The method can play an important role in addressing food safety concerns that may be raised regarding the use of paper materials in food and beverage packaging. PMID:24020390

  20. Gas-to-liquids synthetic fuels for use in fuel cells : reformability, energy density, and infrastructure compatibility.

    SciTech Connect

    Ahmed, S.; Kopasz, J. P.; Russell, B. J.; Tomlinson, H. L.

    1999-09-08

    The fuel cell has many potential applications, from power sources for electric hybrid vehicles to small power plants for commercial buildings. The choice of fuel will be critical to the pace of its commercialization. This paper reviews the various liquid fuels being considered as an alternative to direct hydrogen gas for the fuel cell application, presents calculations of the hydrogen and carbon dioxide yields from autothermal reforming of candidate liquid fuels, and reports the product gas composition measured from the autothermal reforming of a synthetic fuel in a micro-reactor. The hydrogen yield for a synthetic paraffin fuel produced by a cobalt-based Fischer-Tropsch process was found to be similar to that of retail gasoline. The advantages of the synthetic fuel are that it contains no contaminants that would poison the fuel cell catalyst, is relatively benign to the environment, and could be transported in the existing fuel distribution system.

  1. Isobutanol-methanol mixtures from synthesis gas. Quarterly technical progress report, April 1, 1995--June 30, 1995

    SciTech Connect

    Iglesia, E.

    1995-07-24

    Three types of catalytic materials for alcohol coupling and isobutanol synthesis reactions have been prepared and characterized by BET surface area and x-ray diffraction methods. The materials consist of (1) modified low-temperature methanol synthesis catalysts and their constitutive components, (2) high temperature isobutanol synthesis catalysts consisting of Nb-Zn-Zr mixed oxides promoted with Cu, and (3) high surface area basic oxides prepared from hydrotalcite precursors and active in alcohol coupling reactions. Mechanistic and kinetic studies of methanol and ethanol coupling reactions using labeled compounds have shown that the reaction proceeds via an intermediate dehydrogenation reaction that form aldehydic intermediates. Ethanol is much more reactive than methanol because it forms a more thermodynamically stable acetaldehyde intermediate with kinetically available aldol condensation pathways for the formation of higher oxygenates. The presence of Cs in this catalysts decreases dehydrogenation rates but prevents the decomposition of methanol and ethanol to CO and H{sub 2}.

  2. Fuel cell integrated with steam reformer

    DOEpatents

    Beshty, Bahjat S.; Whelan, James A.

    1987-01-01

    A H.sub.2 -air fuel cell integrated with a steam reformer is disclosed wherein a superheated water/methanol mixture is fed to a catalytic reformer to provide a continuous supply of hydrogen to the fuel cell, the gases exhausted from the anode of the fuel cell providing the thermal energy, via combustion, for superheating the water/methanol mixture.

  3. Utilization of methanol for polymer electrolyte fuel cells in mobile systems

    NASA Astrophysics Data System (ADS)

    Schmidt, V. M.; Brockerhoff, P.; Hohlein, B.; Menzer, R.; Stimming, U.

    1994-04-01

    The constantly growing volume of road traffic requires the introduction of new vehicle propulsion systems with higher efficiency and drastically reduced emission rates. As part of the fuel cell programme of the Research Centre Julich a vehicle propulsion system with methanol as secondary energy carrier and a polymer electrolyte membrane fuel cell (PEMFC) as the main component for energy conversion is developed. The fuel gas is produced by a heterogeneously catalyzed steam reforming reaction in which methanol is converted to H2, CO and CO2. The required energy is provided by the catalytic conversion of methanol for both heating up the system and reforming methanol. The high CO content of the fuel gas requires further processing of the gas or the development of new electrocatalysts for the anode. Various Pt-Ru alloys show promising behaviour as CO-tolerant anodes. The entire fuel cell system is discussed in terms of energy and emission balances. The development of important components is described and experimental results are discussed.

  4. Cooperative Reformable Channel System with Unique Recognition of Small Gas Molecules in a two-dimensional ZIF-membrane

    NASA Astrophysics Data System (ADS)

    Motevalli, Benyamin; Taherifar, Neda; Liu, Zhe

    We report a cooperative reformable channel system in a coordination porous polymer, named as ZIF-L. Three types of local flexible ligands coexist in the crystal structure of this polymer, resulting in ultra-flexibility. The reformable channel is able to regulate permeation of a nonspherical guest molecule, such as N2 or CO2, based on its longer molecular dimension, which is in a striking contrast to conventional molecular sieves that regulate the shorter cross-sectional dimension of the guest molecules. Our density functional theory (DFT) calculations reveal that the guest molecule induces dynamic motion of the flexible ligands, leading to the channel reformation, and then the guest molecule reorientates itself to fit in the reformed channel. Such a unique ``induced fit-in'' mechanism causes the gas molecule to pass through 6 membered-ring windows in the c- crystal direction of ZIF-L with its longer axis parallel to the window plane. Our experimental permeance of N2 through the ZIF-L membranes is about three times greater than that of CO2, supporting the DFT simulation predictions.

  5. Water co-catalyzed selective dehydrogenation of methanol to formaldehyde and hydrogen

    NASA Astrophysics Data System (ADS)

    Shan, Junjun; Lucci, Felicia R.; Liu, Jilei; El-Soda, Mostafa; Marcinkowski, Matthew D.; Allard, Lawrence F.; Sykes, E. Charles H.; Flytzani-Stephanopoulos, Maria

    2016-08-01

    The non-oxidative dehydrogenation of methanol to formaldehyde is considered a promising method to produce formaldehyde and clean hydrogen gas. Although Cu-based catalysts have an excellent catalytic activity in the oxidative dehydrogenation of methanol, metallic Cu is commonly believed to be unreactive for the dehydrogenation of methanol in the absence of oxygen adatoms or oxidized copper. Herein we show that metallic Cu can catalyze the dehydrogenation of methanol in the absence of oxygen adatoms by using water as a co-catalyst both under realistic reaction conditions using silica-supported PtCu nanoparticles in a flow reactor system at temperatures below 250 °C, and in ultra-high vacuum using model PtCu(111) catalysts. Adding small amounts of isolated Pt atoms into the Cu surface to form PtCu single atom alloys (SAAs) greatly enhances the dehydrogenation activity of Cu. Under the same reaction conditions, the yields of formaldehyde from PtCu SAA nanoparticles are more than one order of magnitude higher than on the Cu nanoparticles, indicating a significant promotional effect of individual, isolated Pt atoms. Moreover, this study also shows the unexpected role of water in the activation of methanol. Water, a catalyst for methanol dehydrogenation at low temperatures, becomes a reactant in the methanol steam reforming reactions only at higher temperatures over the same metal catalyst.

  6. Non-catalytic recuperative reformer

    SciTech Connect

    Khinkis, Mark J.; Kozlov, Aleksandr P.; Kurek, Harry

    2015-12-22

    A non-catalytic recuperative reformer has a flue gas flow path for conducting hot flue gas from a thermal process and a reforming mixture flow path for conducting a reforming mixture. At least a portion of the reforming mixture flow path is embedded in the flue gas flow path to permit heat transfer from the hot flue gas to the reforming mixture. The reforming mixture flow path contains substantially no material commonly used as a catalyst for reforming hydrocarbon fuel (e.g., nickel oxide, platinum group elements or rhenium), but instead the reforming mixture is reformed into a higher calorific fuel via reactions due to the heat transfer and residence time. In a preferred embodiment, extended surfaces of metal material such as stainless steel or metal alloy that are high in nickel content are included within at least a portion of the reforming mixture flow path.

  7. Demonstration of a Highly Efficient Solid Oxide Fuel Cell Power System Using Adiabatic Steam Reforming and Anode Gas Recirculation

    SciTech Connect

    Powell, Michael R.; Meinhardt, Kerry D.; Sprenkle, Vincent L.; Chick, Lawrence A.; Mcvay, Gary L.

    2012-05-01

    Solid oxide fuel cells (SOFC) are currently being developed for a wide variety of applications because of their high efficiency at multiple power levels. Applications for SOFCs encompass a large range of power levels including 1-2 kW residential combined heat and power applications, 100-250 kW sized systems for distributed generation and grid extension, and MW-scale power plants utilizing coal. This paper reports on the development of a highly efficient, small-scale SOFC power system operating on methane. The system uses adiabatic steam reforming of methane and anode gas recirculation to achieve high net electrical efficiency. The anode exit gas is recirculated and all of the heat and water required for the endothermic reforming reaction are provided by the anode gas emerging from the SOFC stack. Although the single-pass fuel utilization is only about 55%, because of the anode gas recirculation the overall fuel utilization is up to 93%. The demonstrated system achieved gross power output of 1650 to 2150 watts with a maximum net LHV efficiency of 56.7% at 1720 watts. Overall system efficiency could be further improved to over 60% with use of properly sized blowers.

  8. Heterogeneous Chemistry Involving Methanol in Tropospheric Clouds

    NASA Technical Reports Server (NTRS)

    Tabazadeh, A.; Yokelson, R. J.; Singh, H. B.; Hobbs, P. V.; Crawford, J. H.; Iraci, L. T.

    2004-01-01

    In this report we analyze airborne measurements to suggest that methanol in biomass burning smoke is lost heterogeneously in clouds. When a smoke plume intersected a cumulus cloud during the SAFARI 2000 field project, the observed methanol gas phase concentration rapidly declined. Current understanding of gas and aqueous phase chemistry cannot explain the loss of methanol documented by these measurements. Two plausible heterogeneous reactions are proposed to explain the observed simultaneous loss and production of methanol and formaldehyde, respectively. If the rapid heterogeneous processing of methanol, seen in a cloud impacted by smoke, occurs in more pristine clouds, it could affect the oxidizing capacity of the troposphere on a global scale.

  9. Performance tests for steam methane reformers

    SciTech Connect

    Wang, S.I.; DiMartino, S.P.; Patel, N.M.; Smith, D.D.

    1982-08-01

    Most of the synthesis gas plants in operation in the United States for production of hydrogen, carbon monoxide, methanol, and ammonia use steam methane reforming (SMR). Economic projections indicate that the SMR plant may continue to be the most favorable process choice through the 1980s or until partial oxidation or coal gasification processes are technically proven. The complexity of an efficiently designed SMR plant for production of these chemicals requires a thorough understanding of many unit operations to correctly evaluate the performance of an operating plant. Air Products and Chemicals, Inc. (APCI) owns and operates various types of SMR plants for production of hydrogen and carbon monoxide gases for pipe line sales, liquid hydrogen for merchant sale, methanol and ammonia. Over the past few years, APCI has developed guidelines and procedures for plant performance tests done at its major SMR plants. This article documents the plant test procedure used in conducting onsite SMR plant performance tests.

  10. Direct methanol fuel cell and system

    DOEpatents

    Wilson, Mahlon S.

    2004-10-26

    A fuel cell having an anode and a cathode and a polymer electrolyte membrane located between anode and cathode gas diffusion backings uses a methanol vapor fuel supply. A permeable polymer electrolyte membrane having a permeability effective to sustain a carbon dioxide flux equivalent to at least 10 mA/cm.sup.2 provides for removal of carbon dioxide produced at the anode by reaction of methanol with water. Another aspect of the present invention includes a superabsorpent polymer material placed in proximity to the anode gas diffusion backing to hold liquid methanol or liquid methanol solution without wetting the anode gas diffusion backing so that methanol vapor from the liquid methanol or liquid methanol-water solution is supplied to the membrane.

  11. Slab reformer

    DOEpatents

    Spurrier, Francis R.; DeZubay, Egon A.; Murray, Alexander P.; Vidt, Edward J.

    1984-02-07

    Slab-shaped high efficiency catalytic reformer configurations particularly useful for generation of fuels to be used in fuel cell based generation systems. A plurality of structures forming a generally rectangular peripheral envelope are spaced about one another to form annular regions, an interior annular region containing a catalytic bed and being regeneratively heated on one side by a hot comubstion gas and on the other side by the gaseous products of the reformation. An integrally mounted combustor is cooled by impingement of incoming oxidant.

  12. Slab reformer

    DOEpatents

    Spurrier, Francis R.; DeZubay, Egon A.; Murray, Alexander P.; Vidt, Edward J.

    1985-03-12

    Slab-shaped high efficiency catalytic reformer configurations particularly useful for generation of fuels to be used in fuel cell based generation systems. A plurality of structures forming a generally rectangular peripheral envelope are spaced about one another to form annular regions, an interior annular region containing a catalytic bed and being regeneratively heated on one side by a hot combustion gas and on the other side by the gaseous products of the reformation. An integrally mounted combustor is cooled by impingement of incoming oxidant.

  13. Slab reformer

    NASA Technical Reports Server (NTRS)

    Spurrier, Francis R. (Inventor); DeZubay, Egon A. (Inventor); Murray, Alexander P. (Inventor); Vidt, Edward J. (Inventor)

    1984-01-01

    Slab-shaped high efficiency catalytic reformer configurations particularly useful for generation of fuels to be used in fuel cell based generation systems. A plurality of structures forming a generally rectangular peripheral envelope are spaced about one another to form annular regions, an interior annular region containing a catalytic bed and being regeneratively heated on one side by a hot comubstion gas and on the other side by the gaseous products of the reformation. An integrally mounted combustor is cooled by impingement of incoming oxidant.

  14. Molecular gas dynamics applied to phase change processes at a vapor-liquid interface: shock-tube experiment and MGD computation for methanol

    NASA Astrophysics Data System (ADS)

    Fujikawa, S.; Yano, T.; Kobayashi, K.; Iwanami, K.; Ichijo, M.

    This paper deals with a molecular gas-dynamics method applied to the accurate determination of the condensation coefficient of methanol vapor. The method consisted of an experiment using a shock tube and computations using a molecular gas-dynamics equation. The experiments were performed in such situations where the shift from a vapor-liquid equilibrium state to a nonequilibrium one is realized by a shock wave in a scale of molecular mean free time of vapor molecules. The temporal evolution in thickness of a liquid film formed on the shock-tube endwall behind a reflected shock wave is measured by an optical interferometer. By comparing the measured liquid-film thickness with numerical solutions for a polyatomic version of the Gaussian-BGK model of the Boltzmann equation, the condensation coefficient of methanol vapor is accurately determined in vapor-liquid nonequilibrium states. As a result, it is clear that the condensation coefficient is just unity very near to an equilibrium state, but is smaller far from the equilibrium state.

  15. Efficient utilization of greenhouse gases in a gas-to-liquids process combined with CO2/steam-mixed reforming and Fe-based Fischer-Tropsch synthesis.

    PubMed

    Zhang, Chundong; Jun, Ki-Won; Ha, Kyoung-Su; Lee, Yun-Jo; Kang, Seok Chang

    2014-07-15

    Two process models for carbon dioxide utilized gas-to-liquids (GTL) process (CUGP) mainly producing light olefins and Fischer-Tropsch (F-T) synthetic oils were developed by Aspen Plus software. Both models are mainly composed of a reforming unit, an F-T synthesis unit and a recycle unit, while the main difference is the feeding point of fresh CO2. In the reforming unit, CO2 reforming and steam reforming of methane are combined together to produce syngas in flexible composition. Meanwhile, CO2 hydrogenation is conducted via reverse water gas shift on the Fe-based catalysts in the F-T synthesis unit to produce hydrocarbons. After F-T synthesis, the unreacted syngas is recycled to F-T synthesis and reforming units to enhance process efficiency. From the simulation results, it was found that the carbon efficiencies of both CUGP options were successfully improved, and total CO2 emissions were significantly reduced, compared with the conventional GTL processes. The process efficiency was sensitive to recycle ratio and more recycle seemed to be beneficial for improving process efficiency and reducing CO2 emission. However, the process efficiency was rather insensitive to split ratio (recycle to reforming unit/total recycle), and the optimum split ratio was determined to be zero. PMID:24933030

  16. Rapid starting methanol reactor system

    DOEpatents

    Chludzinski, Paul J.; Dantowitz, Philip; McElroy, James F.

    1984-01-01

    The invention relates to a methanol-to-hydrogen cracking reactor for use with a fuel cell vehicular power plant. The system is particularly designed for rapid start-up of the catalytic methanol cracking reactor after an extended shut-down period, i.e., after the vehicular fuel cell power plant has been inoperative overnight. Rapid system start-up is accomplished by a combination of direct and indirect heating of the cracking catalyst. Initially, liquid methanol is burned with a stoichiometric or slightly lean air mixture in the combustion chamber of the reactor assembly. The hot combustion gas travels down a flue gas chamber in heat exchange relationship with the catalytic cracking chamber transferring heat across the catalyst chamber wall to heat the catalyst indirectly. The combustion gas is then diverted back through the catalyst bed to heat the catalyst pellets directly. When the cracking reactor temperature reaches operating temperature, methanol combustion is stopped and a hot gas valve is switched to route the flue gas overboard, with methanol being fed directly to the catalytic cracking reactor. Thereafter, the burner operates on excess hydrogen from the fuel cells.

  17. Production of syngas via partial oxidation and CO{sub 2} reforming of coke oven gas over a Ni catalyst

    SciTech Connect

    Jianzhong Guo; Zhaoyin Hou; Jing Gao; Xiaoming Zheng

    2008-05-15

    The partial oxidation and CO{sub 2} reforming of coke oven gas (COG) to syngas was investigated on differently sized Ni catalysts in a fluidized-bed reactor. It was found that the catalytic performance of Ni depends strongly on its particle size. The small-sized Ni catalyst exhibited higher activity and higher selectivity in the partial oxidation of COG. The conversion of CH{sub 4} was kept at 80.7% at a lower temperature (750{sup o}C) and a wide space velocity (from 8000 to 80 000 h{sup -1}). CO{sub 2} reforming of COG is also an efficient route for syngas production. The H{sub 2}/CO ratio in the COG-derived syngas could be controlled by manipulating the concentration of O{sub 2} or CO{sub 2} added in the feed. The yield of produced syngas increases with an increase in temperature. 19 refs., 10 figs., 2 tabs.

  18. Acidities of Water and Methanol in Aqueous Solution and DMSO

    ERIC Educational Resources Information Center

    Gao, Daqing

    2009-01-01

    The relative acidities of water and methanol have been a nagging issue. In gas phase, methanol is more acidic than water by 36.0 kJ/mol; however, in aqueous solution, the acidities of methanol and water are almost identical. The acidity of an acid in solution is determined by both the intrinsic gas-phase ionization Gibbs energy and the solvent…

  19. Coke-free dry reforming of model diesel fuel by a pulsed spark plasma at low temperatures using an exhaust gas recirculation (EGR) system

    NASA Astrophysics Data System (ADS)

    Sekine, Yasushi; Furukawa, Naotsugu; Matsukata, Masahiko; Kikuchi, Eiichi

    2011-07-01

    Dry reforming of diesel fuel, an endothermic reaction, is an attractive process for on-board hydrogen/syngas production to increase energy efficiency. For operating this dry reforming process in a vehicle, we can use the exhaust gas from an exhaust gas recirculation (EGR) system as a source of carbon dioxide. Catalytic dry reforming of heavy hydrocarbon is a very difficult reaction due to the high accumulation of carbon on the catalyst. Therefore, we attempted to use a non-equilibrium pulsed plasma for the dry reforming of model diesel fuel without a catalyst. We investigated dry reforming of model diesel fuel (n-dodecane) with a low-energy pulsed spark plasma, which is a kind of non-equilibrium plasma at a low temperature of 523 K. Through the reaction, we were able to obtain syngas (hydrogen and carbon monoxide) and a small amount of C2 hydrocarbon without coke formation at a ratio of CO2/Cfuel = 1.5 or higher. The reaction can be conducted at very low temperatures such as 523 K. Therefore, it is anticipated as a novel and effective process for on-board syngas production from diesel fuel using an EGR system.

  20. Hydrogen production by reforming of liquid hydrocarbons in a membrane reactor for portable power generation-Experimental studies

    NASA Astrophysics Data System (ADS)

    Damle, Ashok S.

    One of the most promising technologies for lightweight, compact, portable power generation is proton exchange membrane (PEM) fuel cells. PEM fuel cells, however, require a source of pure hydrogen. Steam reforming of hydrocarbons in an integrated membrane reactor has potential to provide pure hydrogen in a compact system. Continuous separation of product hydrogen from the reforming gas mixture is expected to increase the yield of hydrogen significantly as predicted by model simulations. In the laboratory-scale experimental studies reported here steam reforming of liquid hydrocarbon fuels, butane, methanol and Clearlite ® was conducted to produce pure hydrogen in a single step membrane reformer using commercially available Pd-Ag foil membranes and reforming/WGS catalysts. All of the experimental results demonstrated increase in hydrocarbon conversion due to hydrogen separation when compared with the hydrocarbon conversion without any hydrogen separation. Increase in hydrogen recovery was also shown to result in corresponding increase in hydrocarbon conversion in these studies demonstrating the basic concept. The experiments also provided insight into the effect of individual variables such as pressure, temperature, gas space velocity, and steam to carbon ratio. Steam reforming of butane was found to be limited by reaction kinetics for the experimental conditions used: catalysts used, average gas space velocity, and the reactor characteristics of surface area to volume ratio. Steam reforming of methanol in the presence of only WGS catalyst on the other hand indicated that the membrane reactor performance was limited by membrane permeation, especially at lower temperatures and lower feed pressures due to slower reconstitution of CO and H 2 into methane thus maintaining high hydrogen partial pressures in the reacting gas mixture. The limited amount of data collected with steam reforming of Clearlite ® indicated very good match between theoretical predictions and

  1. Propane Clathrate Hydrate Formation Accelerated by Methanol.

    PubMed

    Amtawong, Jaruwan; Guo, Jin; Hale, Jared S; Sengupta, Suvrajit; Fleischer, Everly B; Martin, Rachel W; Janda, Kenneth C

    2016-07-01

    The role of methanol as both an inhibitor and a catalyst for the formation of clathrate hydrates (CHs) has been a topic of intense study. We report a new quantitative study of the kinetics of propane CH formation at 253 K from the reaction of propane gas with <75 μm ice particles that have been doped with varying amounts of methanol. We find that methanol significantly accelerates the formation reaction with quite small doping quantities. Even for only 1 methanol molecule per 10 000 water molecules, the maximum uptake rate of propane into CHs is enhanced and the initiation pressure is reduced. These results enable more efficient production of CHs for gas storage. This remarkable acceleration of the CH formation reaction by small quantities of methanol may place constraints on the mechanism of the inhibition effect observed under other conditions, usually employing much larger quantities of methanol. PMID:27275862

  2. Understanding the effect of reformate gas components and stack component impurities on the performance of PEM fuel cells

    NASA Astrophysics Data System (ADS)

    Gu, Tao

    The performance can be lost depending on the concentration and type of reformate components. Gas crossover in PEMFCs can also cause performance loss and these effects are also presented. Impurities such as acetone coming from composite stack components and sealants can also deteriorate the performance severely. Electrochemical impedance spectroscopy (EIS) is used as a diagnostic tool to study the impurity poisoning. Reformate contains N2 and CO2 and these components affect performance differently. These effects were quantified using anode overvoltage. Data for anode overvoltage shows that CO2 yields a significant poisoning effect (about 30 mV) on a Pt electrode. Cyclic voltammetry (CV) data showed that CO was produced in-situ from CO2 and H 2 (reverse water gas shift (RWGS) reaction) on both Pt and Pt/Ru electrodes. The coverage of CO achieved by RWGS can reach 5 x 10-7 mol/cm2 on an electrode with 0.4 mg/cm2 Pt under open circuit with normal operating conditions. This work also investigated how pressure, gas composition, and temperature affect the RWGS reaction in a PEMFC for both Pt and Pt/Ru alloy catalysts. The data are shown to be consistent with a kinetic catalytic model and not with an equilibrium model. Data was presented on H2 and O2 crossover in PEMFCs. Electrochemical techniques and mass balance measurements were used to quantify the crossover under typical working conditions. Mixed potential theory was applied to analyze the effect of gas crossover on open circuit voltage (OCV) of PEMFCs. Off-gassing from bipolar plates previously identified styrene, acetone, t-butyl alcohol, and dimethyl succinate as impurities. The effects of those impurities were quantified with both poisoning-recovery transient curves and steady state VI curves before, during, and after poisoning on anode and cathode side respectively. The poisoning effects of them to the anode side are smaller than to the cathode side. Cyclic voltammetry and electrochemical impedance spectroscopy

  3. Predicted emissions from a methanol-fueled ``electrochemical automobile engine`` based on a PEM fuel cell

    SciTech Connect

    Amphlett, J.C.; Mann, R.F.; Peppley, B.A.

    1995-12-31

    A simulation of a fuel cell engine (FCE) based on a proton exchange membrane (PEM) fuel-cell stack was developed using a process simulation software package. Rates of emissions of unburned methanol, formaldehyde, CO and NO{sub x}, were calculated based on chemical equilibria. The predicted rates of emissions for unburned methanol, formaldehyde and CO were found to all be less than 1 {micro}g/km. This is considerably less than has been reported in the literature but represents a theoretical limit which should be achievable as effective catalytic-combustion systems are developed for hydrogen/methanol fueled burners. The worst-case rate of NO{sub x}, emissions was shown to be less than 0.03 g/km (0.05 g/mi.). It was found that increasing the rate of heat transfer in the steam reformer, which converts the methanol to a hydrogen-rich gas, significantly reduced the rate of NO{sub x}, emission due to the lower burner temperatures which could be used. The results indicate that, in terms of emissions reduction, a methanol fueled FCE is an excellent long-term alternative to the ICE.

  4. Studying the characteristics of a 5 kW power installation on solid-oxide fuel cells with steam reforming of natural gas

    NASA Astrophysics Data System (ADS)

    Munts, V. A.; Volkova, Yu. V.; Plotnikov, N. S.; Dubinin, A. M.; Tuponogov, V. G.; Chernishev, V. A.

    2015-11-01

    The results from tests of a 5 kW power plant on solid-oxide fuel cells (SOFCs), in which natural gas is used as fuel, are presented. The installation's process circuit, the test procedure, and the analysis of the obtained results are described. The characteristics of the power plant developed by the Ural Industrial Company are investigated in four steady-state modes of its operation: with the SOFC nominal power capacity utilized by 40% (2 kW), 60% (3 kW), 90% (4.5 kW) and 110% (5.4 kW) (the peaking mode). The electrical and thermodynamic efficiencies are calculated for all operating modes, and the most efficient mode, in which the electrical efficiency reached almost 70%, is determined. The air excess coefficient and heat loss with flue gases q 2 are determined, and it is revealed that the heat loss q 5 decreases from 40 to 25% with increasing the load. Thermal balances are drawn up for the following components of the system the reformer, the SOFC battery, the catalytic burner for afterburning anode gases, the heat exchanger for heating the cathode air and the mixture of natural gas and steam, and the actual fuel utilization rates in the electrochemical generator are calculated. An equation for the resulting natural gas steam reforming reaction was obtained based on the results from calculating the equilibrium composition of reforming products for the achieved temperatures at the reformer outlet t 3.

  5. Hydrogen-bonded ring closing and opening of protonated methanol clusters H(+)(CH3OH)(n) (n = 4-8) with the inert gas tagging.

    PubMed

    Li, Ying-Cheng; Hamashima, Toru; Yamazaki, Ryoko; Kobayashi, Tomohiro; Suzuki, Yuta; Mizuse, Kenta; Fujii, Asuka; Kuo, Jer-Lai

    2015-09-14

    The preferential hydrogen bond (H-bond) structures of protonated methanol clusters, H(+)(MeOH)n, in the size range of n = 4-8, were studied by size-selective infrared (IR) spectroscopy in conjunction with density functional theory calculations. The IR spectra of bare clusters were compared with those with the inert gas tagging by Ar, Ne, and N2, and remarkable changes in the isomer distribution with the tagging were found for clusters with n≥ 5. The temperature dependence of the isomer distribution of the clusters was calculated by the quantum harmonic superposition approach. The observed spectral changes with the tagging were well interpreted by the fall of the cluster temperature with the tagging, which causes the transfer of the isomer distribution from the open and flexible H-bond network types to the closed and rigid ones. Anomalous isomer distribution with the tagging, which has been recently found for protonated water clusters, was also found for H(+)(MeOH)5. The origin of the anomaly was examined by the experiments on its carrier gas dependence. PMID:26235389

  6. Hydrogen production from alcohol reforming in a microwave ‘tornado’-type plasma

    NASA Astrophysics Data System (ADS)

    Tatarova, E.; Bundaleska, N.; Dias, F. M.; Tsyganov, D.; Saavedra, R.; Ferreira, C. M.

    2013-12-01

    In this work, an experimental investigation of microwave plasma-assisted reforming of different alcohols is presented. A microwave (2.45 GHz) ‘tornado’-type plasma with a high-speed tangential gas injection (swirl) at atmospheric pressure is applied to decompose alcohol molecules, namely methanol, ethanol and propanol, and to produce hydrogen-rich gas. The reforming efficiency is investigated both in Ar and Ar+ water vapor plasma environments. The hydrogen yield dependence on the partial alcohol flux is analyzed. Mass spectrometry and Fourier transform infrared spectroscopy are used to detect the outlet gas products from the decomposition process. Hydrogen, carbon monoxide, carbon dioxide and solid carbon are the main decomposition by-products. A significant increase in the hydrogen production rate is observed with the addition of a small amount of water. Furthermore, optical emission spectroscopy is applied to detect the radiation emitted by the plasma and to estimate the gas temperature and electron density.

  7. Unveiling the gas kinematics at 10 AU scales in high-mass star-forming regions. Milliarcsecond structure of 6.7 GHz methanol masers

    NASA Astrophysics Data System (ADS)

    Moscadelli, L.; Sanna, A.; Goddi, C.

    2011-12-01

    Context. High-mass stars play a prominent role in Galactic evolution, but their formation mechanism is still poorly understood. This lack of knowledge reflects the observational limitations of present instruments, whose angular resolution (at the typical distances of massive protostars) precludes probing circumstellar gas on scales of 1-100 AU, relevant for a detailed investigation of accretion structures and launch/collimation mechanims of outflows in high-mass star formation. Aims: This work presents a study of the milliarcsecond structure of the 6.7 GHz methanol masers at high-velocity resolution (0.09 km s-1) in four high-mass star-forming regions: G16.59-0.05, G23.01-0.41, IRAS 20126 + 4104, and AFGL 5142. Methods: We studied these sources by means of multi-epoch VLBI observations in the 22 GHz water and 6.7 GHz methanol masers, to determine the 3-D gas kinematics within a few thousand AU from the (proto)star. Our results demonstrate the ability of maser emission to trace kinematic structures close to the (proto)star, revealing the presence of fast wide-angle and/or collimated outflows (traced by the H2O masers), and of rotation and infall (indicated by the CH3OH masers). The present work exploits the 6.7 GHz maser data collected so far to investigate the milliarcsecond structure of this maser emission at high-velocity resolution. Results: Most of the detected 6.7 GHz maser features present an ordered (linear, or arc-like) distribution of maser spots on the plane of the sky, together with a regular variation in the spot LSR velocity (VLSR) with position. Typical values for the amplitude of the VLSR gradients (defined in terms of the derivative of the spot VLSR with position) are found to be 0.1-0.2 km s-1 mas-1. In each of the four target sources, the orientation and the amplitude of most of the feature VLSR gradients remain remarkably stable in time, on timescales of (at least) several years. We also find that the data are consistent with having the VLSR

  8. Conversion of glycerol to hydrogen rich gas.

    PubMed

    Tran, Nguyen H; Kannangara, G S Kamali

    2013-12-21

    Presently there is a glut of glycerol as the by-product of biofuel production and it will grow as production increases. The conundrum is how we can consume this material and convert it into a more useful product. One potential route is to reform glycerol to hydrogen rich gas including synthesis gas (CO + H2) and hydrogen. However, there is recent literature on various reforming techniques which may have a bearing on the efficiency of such a process. Hence in this review reforming of glycerol at room temperature (normally photo-catalytic), catalysis at moderate and high temperature and a non-catalytic pyrolysis process are presented. The high temperature processes allow the generation of synthesis gas with the hydrogen to carbon monoxide ratios being suitable for synthesis of dimethyl ether, methanol and for the Fischer-Tropsch process using established catalysts. Efficient conversion of synthesis gas to hydrogen involves additional catalysts that assist the water gas shift reaction, or involves in situ capture of carbon dioxide and hydrogen. Reforming at reduced temperatures including photo-reforming offers the opportunity of producing synthesis gas or hydrogen using single catalysts. Together, these processes will assist in overcoming the worldwide glut of glycerol, increasing the competitiveness of the biofuel production and reducing our dependency on the fossil based, hydrogen rich gas. PMID:24043264

  9. Gas Cell Observations of Methanol from 0.6 to 1.9 Thz Using the Herschel Space Observatory Hifi Instrument

    NASA Astrophysics Data System (ADS)

    Higgins, Ronan D.; Pearson, John C.; Lord, Steve D.; Teyssier, David

    2009-06-01

    The Herschel HIFI instrument, in its ground testing, collected over 6000 spectra of methanol (with natural terrestrial isotopic abundance). These data were gathered primarily to validate the instrument's spectroscopic functionality and proper operation. They have a secondary benefit of increasing the database of methanol lines. Furthermore, the data has enormous and largely untapped potential for a fundamental spectroscopic investigation. We present the analysis of this broad range of methanol spectra and detail the instrument effects seen. Additionally we detail the new insight into the torsional states and self-broadening characteristics of methanol.

  10. Steam reforming of gasification gas tar over dolomite with benzene as a model compound

    SciTech Connect

    Simell, P.A.; Hirvensalo, E.K.; Smolander, V.T.; Krause, A.O.I.

    1999-04-01

    Tar decomposition over a dolomite catalyst in gasification conditions was modeled using benzene as a tar model compound. The reactions of the gas main components were included in the models studied. Kinetic studies were carried out at 750--925 C and under ambient pressure in a plug flow reactor using a mixture of simulated gasification gas. Operation conditions without external or internal mass-transfer limitations were applied. Mechanistic models of the Langmuir-Hinshelwood type describing benzene decomposition were developed and tested. Experimental results could be best described by a kinetic rate equation based on the assumption that single-site adsorption of benzene was the rate-determining step and that adsorption of hydrogen inhibited benzene decomposition.

  11. BHP may scale up methanol production

    SciTech Connect

    Alperowicz, N.

    1993-06-23

    Broken Hill Pty. (BHP: Melbourne) says otherwise uneconomic gas reserves in the Timor Sea off northwest Australia could be developed if the company`s plans to commercialize a novel gas-to-methanol technology prove to be viable. BHP is building an A$70-million ($50 million) research unit in Victoria using ICI`s Leading Concept Methanol gas-to-methanol process. If this unit proves viable, it could be put on a vessel and taken to Timor Sea where BHP has oil exploration and production interests. Timor gas is not economically viable because of lack of nearby markets. The 54,000-m.t./year research plant, located at Werrbee near Melbourne, is scheduled to start production in the second half of 1994, according to BHP manager Joe Evon. The plant is being built by Davy/John Brown. Provided the economic climate is right, BHP is expected to build a world-scale methanol plant offshore.

  12. Neat methanol fuel cell power plant

    NASA Astrophysics Data System (ADS)

    Abens, S.; Farooque, M.

    1985-12-01

    Attention is given to a fuel cell development effort which has been directed, by ease-of-supply, low weight, and low volume criteria toward the use of undiluted methanol. Partial oxidation and internal water recovery concepts are incorporated, allowing the onboard dilution of methanol fuel through mixing with exhaust-recovered water. This scheme is successfully demonstrated for the case of a 3 kW unit employing commercial cross flow heat exchangers, as well as for a 5 kW reformer flue exhaust water recovery design with U.S. Air force baseload stationary applications. The USAF powerplant has an overall thermal efficiency of 32 percent at rated load.

  13. Unusual case of methanol poisoning

    SciTech Connect

    Shapiro, L.; Henderson, M. . Dept. of Chemical Pathology); Madi, S.; Mellor, L. . Dept. of Medicine, and Pharmacy)

    1993-01-09

    A 31-year-old man with a history of alcohol abuse presented to the accident and emergency department complaining of blurred vision. 4 h previously he had drunk 300 mL de-icer fluid. Electrolytes, urea, creatinine, glucose, and blood-gas analysis were normal. Measured osmolality, however, was 368 mosmol/kg with a calculated osmolality of 300 mosmol/kg, which indicated a greatly increased osmolar gap. He was therefore given 150 mL whisky and admitted. Methanol was later reported as 200 mg/dL. Ethylene glycol was not detected, but another glycol, propylene glycol, was present at 47 mg/dL. 10 h after ingestion an intravenous infusion of ethanol was started and he was hemodialysed for 7 h. After dialysis he was given a further 100 mL whisky and the rate of ethanol infusion was reduced to 11 g per h. Methanol and ethanol were measured twice daily until methanol was under 10/mg/dL: The recommendation is that blood ethanol be maintained between 100 and 200 mg/dL during treatment of methanol poisoning. This concentration was not achieved, presumably because of the high rate of ethanol metabolism often found in alcoholics. Antifreeze solutions commonly contain methanol and ethylene glycol. Sometimes propylene glycol is substituted because it has properties similar to those of ethylene glycol but is less toxic. The authors postulate that propylene glycol inhibited the metabolism of methanol in the patient, thus sparing him from the toxic effects of methanol.

  14. Look what you can make from methanol

    SciTech Connect

    King, D.L.; Grate, J.H.

    1985-04-01

    In a synthetic gas based chemicals industry there are many advantages in using an indirect methanol-based route for producing two carbon or higher oxygenated chemicals. Because of poor product selectivity and low production rates, direct syngas mechanisms are not commercially viable. Specific examples of indirect methanol-based routes and also routes from formaldehyde are given. These include the production of ethanol by reductive carbonylation of methanol and the production of vinyl acetate, although more work needs to be done on the methanol-syngas route to vinyl acetate. The chemistry of ethylene glycol from formaldehyde is discussed. It is concluded that the success of syngas-based technologies will be linked to the economics of ethylene production and new methanol-based processes will contribute to this success. 35 references.

  15. Homogeneous catalyst formulations for methanol production

    DOEpatents

    Mahajan, Devinder; Sapienza, Richard S.; Slegeir, William A.; O'Hare, Thomas E.

    1991-02-12

    There is disclosed synthesis of CH.sub.3 OH from carbon monoxide and hydrogen using an extremely active homogeneous catalyst for methanol synthesis directly from synthesis gas. The catalyst operates preferably between 100.degree.-150.degree. C. and preferably at 100-150 psia synthesis gas to produce methanol. Use can be made of syngas mixtures which contain considerable quantities of other gases, such as nitrogen, methane or excess hydrogen. The catalyst is composed of two components: (a) a transition metal carbonyl complex and (b) an alkoxide component. In the simplest formulation, component (a) is a complex of nickel tetracarbonyl and component (b) is methoxide (CH.sub.3 O.sup.-), both being dissolved in a methanol solvent system. The presence of a co-solvent such as p-dioxane, THF, polyalcohols, ethers, hydrocarbons, and crown ethers accelerates the methanol synthesis reaction.

  16. Homogeneous catalyst formulations for methanol production

    DOEpatents

    Mahajan, Devinder; Sapienza, Richard S.; Slegeir, William A.; O'Hare, Thomas E.

    1990-01-01

    There is disclosed synthesis of CH.sub.3 OH from carbon monoxide and hydrogen using an extremely active homogeneous catalyst for methanol synthesis directly from synthesis gas. The catalyst operates preferably between 100.degree.-150.degree. C. and preferably at 100-150 psia synthesis gas to produce methanol. Use can be made of syngas mixtures which contain considerable quantities of other gases, such as nitrogen, methane or excess hydrogen. The catalyst is composed of two components: (a) a transition metal carbonyl complex and (b) an alkoxide component. In the simplest formulation, component (a) is a complex of nickel tetracarbonyl and component (b) is methoxide (CH.sub.3 O.sup.13 ), both being dissolved in a methanol solvent system. The presence of a co-solvent such as p-dioxane, THF, polyalcohols, ethers, hydrocarbons, and crown ethers accelerates the methanol synthesis reaction.

  17. Standalone ethanol micro-reformer integrated on silicon technology for onboard production of hydrogen-rich gas.

    PubMed

    Pla, D; Salleras, M; Morata, A; Garbayo, I; Gerbolés, M; Sabaté, N; Divins, N J; Casanovas, A; Llorca, J; Tarancón, A

    2016-08-01

    A novel design of a silicon-based micro-reformer for onboard hydrogen generation from ethanol is presented in this work. The micro-reactor is fully fabricated with mainstream MEMS technology and consists of an active low-thermal-mass structure suspended by an insulating membrane. The suspended structure includes an embedded resistive metal heater and an array of ca. 20k vertically aligned through-silicon micro-channels per square centimetre. Each micro-channel is 500 μm in length and 50 μm in diameter allowing a unique micro-reformer configuration that presents a total surface per projected area of 16 cm(2) cm(-2) and per volume of 320 cm(2) cm(-3). The walls of the micro-channels become the active surface of the micro-reformer when coated with a homogenous thin film of Rh-Pd/CeO2 catalyst. The steam reforming of ethanol under controlled temperature conditions (using the embedded heater) and using the micro-reformer as a standalone device are evaluated. Fuel conversion rates above 94% and hydrogen selectivity values of ca. 70% were obtained when using operation conditions suitable for application in micro-solid oxide fuel cells (micro-SOFCs), i.e. 750 °C and fuel flows of 0.02 mlL min(-1) (enough to feed a one watt power source). PMID:27378399

  18. Tri-reforming and combined reforming of methane for producing syngas with desired hydrogen/carbon monoxide ratios

    NASA Astrophysics Data System (ADS)

    Pan, Wei

    This dissertation is an exploratory study of a new process concept for direct production of synthesis gas (CO + H2) with desired H 2/CO ratios (1.5--2.0) for methanol synthesis and F-T synthesis, using CO2 together with steam and unconverted O2 in flue gas from fossil fuel-fired electric power plants to react with methane or natural gas. This new process is called tri-reforming, referring to simultaneous CO2-steam-O2 reforming of methane or natural gas. This study included (1) The investigation of carbon formation in the tri-reforming process. For comparison, carbon formation in the combined reforming and CO2 reforming reaction was studied as well. (2) The effect of reaction conditions and feed compositions on equilibrium composition (e.g. H2/CO ratio) and equilibrium conversions in the tri-reforming process. (3) The role of catalysts in the tri-reforming process, especially the effect of catalysts on CO2 conversion in the presence of H 2O and O2. It was clearly evidenced from this study that CO in the product stream is probably the major source of carbon over Ni/Al2O3 in the equimolar CO2-CH4 reforming at 650°C and 1 atm. Addition of either O2 or H2O into the CO 2 reforming reaction system can suppress carbon formation. It was demonstrated that carbon-free operation can be achieved in the tri-reforming process. A thermodynamic comparison of tri-reforming with feed compositions of (H2O+CO2+0.5O2)/CH4 (mol ratio) = 1 showed that O2 improves equilibrium CH4 conversion, yet greatly decreases equilibrium CO2 conversion. H2O in tri-reforming has a significant effect on the H2/CO ratio in the products, while O2 has a minor effect. A kinetic study and catalytic performance tests indicated that the support in a supported catalyst has a significant role in enhancing CO2 conversion to CO in the presence of H2O and O2 in tri-reforming. The Ni/MgO catalyst showed superior performance with close to equilibrium CH4 and CO2 conversions at 850°C, 1 atm, and 32,000 ml

  19. Vacuum-ultraviolet (VUV) photoionization of small methanol and methanol-water clusters

    SciTech Connect

    Ahmed, Musahid; Ahmed, Musahid; Wilson, Kevin R.; Belau, Leonid; Kostko, Oleg

    2008-05-12

    In this work we report on thevacuum-ultraviolet (VUV) photoionization of small methanol and methanol-water clusters. Clusters of methanol with water are generated via co-expansion of the gas phase constituents in a continuous supersonic jet expansion of methanol and water seeded in Ar. The resulting clusters are investigated by single photon ionization with tunable vacuumultraviolet synchrotron radiation and mass analyzed using reflectron mass spectrometry. Protonated methanol clusters of the form (CH3OH)nH + (n=1-12) dominate the mass spectrum below the ionization energy of the methanol monomer. With an increase in water concentration, small amounts of mixed clusters of the form (CH3OH)n(H2O)H + (n=2-11) are detected. The only unprotonated species observed in this work are the methanol monomer and dimer. Appearance energies are obtained from the photoionization efficiency (PIE) curves for CH3OH +, (CH 3OH)2 +, (CH3OH)nH + (n=1-9), and (CH 3OH)n(H2O)H + (n=2-9 ) as a function of photon energy. With an increase in the water content in the molecular beam, there is an enhancement of photoionization intensity for methanol dimer and protonated methanol monomer at threshold. These results are compared and contrasted to previous experimental observations.

  20. Vacuum-Ultraviolet (VUV) Photoionization of Small Methanol and Methanol-Water Clusters

    SciTech Connect

    Kostko, Oleg; Belau, Leonid; Wilson, Kevin R.; Ahmed, Musahid

    2008-04-24

    In this work, we report on the vacuum-ultraviolet (VUV) photoionization of small methanol and methanol-water clusters. Clusters of methanol with water are generated via co-expansion of the gas phase constituents in a continuous supersonic jet expansion of methanol and water seeded in Ar. The resulting clusters are investigated by single photon ionization with tunable vacuum-ultraviolet synchrotron radiation and mass analyzed using reflectron mass spectrometry. Protonated methanol clusters of the form (CH3OH)nH+(n = 1-12) dominate the mass spectrum below the ionization energy of the methanol monomer. With an increase in water concentration, small amounts of mixed clusters of the form (CH3OH n(H2O)H+ (n = 2-11) are detected. The only unprotonated species observed in this work are the methanol monomer and dimer. Appearance energies are obtained from the photoionization efficiency (PIE) curves for CH3OH+, (CH3OH)2+, (CH3OH)nH+ (n = 1-9), and (CH3OH)n(H2O)H+ (n = 2-9) as a function of photon energy. With an increasein the water content in the molecular beam, there is an enhancement of photoionization intensity for the methanol dimer and protonated methanol monomer at threshold. These results are compared and contrasted to previous experimental observations.

  1. Methane reforming in a temperature-controlled DBD reactor

    NASA Astrophysics Data System (ADS)

    Levko, Dmitry; Raja, Laxminarayan

    2015-09-01

    Methane and carbon dioxide are among the main products of human activity. Therefore, they are considered among greenhouse gases, which may cause the global warming. On the other hand, methane is widely used in everyday life as an energy source and in industry for the synthesis of different chemicals. In order to utilize greenhouse gases or to generate chemicals from methane, one needs first to dissociate it. Then, this gas converts into desired products such as methanol, gasoline, syn-gas etc. Nowadays, there are several methods for CH4 conversion. Steam reforming, partial oxidation, thermal and non-thermal plasmas are among them. During the last decades, the use of non-thermal plasma for methane reforming attracts more and more attention. This is caused by the possibility to control the process of methane conversion as well as the gas component content at the reactor outlet. In addition, the use of non-thermal plasma facilitates the control of reactor start up. The goal of the present work is the deep understanding of the plasma chemical processes accompanying the methane-air conversion in a temperature-controlled DBD reactor. To do this, we have developed the kinetic mechanism of CH4/N2/O2 conversion for the gas temperature range 300-800 K and applied it to the global model.

  2. Development of alternative fuels from coal-derived synthesis gas: Final topical report, demonstration of one-step slurry-phase process for the co-production of methanol and isobutanol

    SciTech Connect

    1996-06-01

    Liquid phase co-production of methanol and isobutanol (LPIBOH) was de, demonstrated at DOE`s Alternative Fuels Development Unit (AFDU) in LaPorte, Texas. Methanol and isobutanol are key intermediates in a synthesis gas-based route to methyl t-butyl ether (MTBE). The technology was demonstrated in a new 18 in. slurry bubble-column reactor that was designed to demonstrate higher pressures and temperatures,higher gas superficial velocities, and lower gas hourly space velocities--all of which are conducive to obtaining optimal isobutanol yield. The integration of the new reactor into the AFDU included the addition of a high-pressure synthesis gas compressor, a high-pressure hydrogen feed source, and a closed-loop methanol- solvent absorption system to remove CO{sub 2} from the unconverted synthesis gas. These modifications were completed in January 1994. The LPIBOH run followed after a short turnaround. It employed a cesium- promoted Cu/ZnO/Al{sub 2}O{sub 3} catalyst developed in Air Products` laboratories and subsequently scaled up to a production- sized batch. Over a thirteen day campaign on simulated Shell gasifier gas, the catalyst and reactor system were tested at a matrix of pressures (750, 1300, 1735 psig) and space velocities (3000, 5000, 8200 sL/kg-hr), representing numerous first-of-a-kind run conditions for the AFDU. Inlet gas superficial velocities spanned an impressive 0.16 to 1.0 ft/sec. Stable reactor performance for a full twelve-hour data period at 1.0 ft/sec was another significant milestone for the liquid phase technology program. Apart from the catalyst deactivation, the run successfully demonstrated mixed alcohol synthesis in a slurry bubble-column reactor, as well as all of the new equipment installed for the trial. Although the full capabilities of the new oxygenates system will not be tested until future runs, the design objectives for the modifications were met with respect to the LPIBOH run.

  3. Structure and energetics of hydrogen-bonded networks of methanol on close packed transition metal surfaces

    NASA Astrophysics Data System (ADS)

    Murphy, Colin J.; Carrasco, Javier; Lawton, Timothy J.; Liriano, Melissa L.; Baber, Ashleigh E.; Lewis, Emily A.; Michaelides, Angelos; Sykes, E. Charles H.

    2014-07-01

    Methanol is a versatile chemical feedstock, fuel source, and energy storage material. Many reactions involving methanol are catalyzed by transition metal surfaces, on which hydrogen-bonded methanol overlayers form. As with water, the structure of these overlayers is expected to depend on a delicate balance of hydrogen bonding and adsorbate-substrate bonding. In contrast to water, however, relatively little is known about the structures methanol overlayers form and how these vary from one substrate to another. To address this issue, herein we analyze the hydrogen bonded networks that methanol forms as a function of coverage on three catalytically important surfaces, Au(111), Cu(111), and Pt(111), using a combination of scanning tunneling microscopy and density functional theory. We investigate the effect of intermolecular interactions, surface coverage, and adsorption energies on molecular assembly and compare the results to more widely studied water networks on the same surfaces. Two main factors are shown to direct the structure of methanol on the surfaces studied: the surface coverage and the competition between the methanol-methanol and methanol-surface interactions. Additionally, we report a new chiral form of buckled hexamer formed by surface bound methanol that maximizes the interactions between methanol monomers by sacrificing interactions with the surface. These results serve as a direct comparison of interaction strength, assembly, and chirality of methanol networks on Au(111), Cu(111), and Pt(111) which are catalytically relevant for methanol oxidation, steam reforming, and direct methanol fuel cells.

  4. Methanol production method and system

    DOEpatents

    Chen, Michael J.; Rathke, Jerome W.

    1984-01-01

    Ethanol is selectively produced from the reaction of methanol with carbon monoxide and hydrogen in the presence of a transition metal carbonyl catalyst. Methanol serves as a solvent and may be accompanied by a less volatile co-solvent. The solution includes the transition metal carbonyl catalysts and a basic metal salt such as an alkali metal or alkaline earth metal formate, carbonate or bicarbonate. A gas containing a high carbon monoxide to hydrogen ratio, as is present in a typical gasifer product, is contacted with the solution for the preferential production of ethanol with minimal water as a byproduct. Fractionation of the reaction solution provides substantially pure ethanol product and allows return of the catalysts for reuse.

  5. Reformer Fuel Injector

    NASA Technical Reports Server (NTRS)

    Suder, Jennifer L.

    2004-01-01

    Today's form of jet engine power comes from what is called a gas turbine engine. This engine is on average 14% efficient and emits great quantities of green house gas carbon dioxide and air pollutants, Le. nitrogen oxides and sulfur oxides. The alternate method being researched involves a reformer and a solid oxide fuel cell (SOFC). Reformers are becoming a popular area of research within the industry scale. NASA Glenn Research Center's approach is based on modifying the large aspects of industry reforming processes into a smaller jet fuel reformer. This process must not only be scaled down in size, but also decrease in weight and increase in efficiency. In comparison to today's method, the Jet A fuel reformer will be more efficient as well as reduce the amount of air pollutants discharged. The intent is to develop a 10kW process that can be used to satisfy the needs of commercial jet engines. Presently, commercial jets use Jet-A fuel, which is a kerosene based hydrocarbon fuel. Hydrocarbon fuels cannot be directly fed into a SOFC for the reason that the high temperature causes it to decompose into solid carbon and Hz. A reforming process converts fuel into hydrogen and supplies it to a fuel cell for power, as well as eliminating sulfur compounds. The SOFC produces electricity by converting H2 and CO2. The reformer contains a catalyst which is used to speed up the reaction rate and overall conversion. An outside company will perform a catalyst screening with our baseline Jet-A fuel to determine the most durable catalyst for this application. Our project team is focusing on the overall research of the reforming process. Eventually we will do a component evaluation on the different reformer designs and catalysts. The current status of the project is the completion of buildup in the test rig and check outs on all equipment and electronic signals to our data system. The objective is to test various reformer designs and catalysts in our test rig to determine the most

  6. Methanol production from fermentor off-gases

    NASA Astrophysics Data System (ADS)

    Dale, B. E.; Moreira, A. R.

    The off gases from an acetone butanol fermentation facility are composed mainly of CO2 and H2. Such a gas stream is an ideal candidate as a feed to a methanol synthesis plant utilizing modern technology recently developed and known as the CDH-methanol process. A detailed economic analysis for the incremental cost of a methanol synthesis plant utilizing the off gases from an acetone butanol fermentation indicates a profitable rate of return of 25 to 30% under the most likely production conditions. Bench scale studies at different fermentor mixing rates indicate that the volume of gases released during the fermentation is a strong function of the agitation rate and point to a potential interaction between the volume of H2 evolved and the levels of butanol present in the final fermented broth. Such interaction may require establishing optimum operating conditions for an integrated butanol fermentation methanol synthesis plant.

  7. Single-Pass Catalytic Conversion of Syngas into Olefins via Methanol.

    PubMed

    Olsbye, Unni

    2016-06-20

    All together now: Combination in a single reactor of the catalysts for converting syngas into methanol and methanol into olefins was recently reported by Cheng et al. This approach considerably simplifies the catalytic conversion of natural gas. PMID:27213983

  8. First methanol-to-gasoline plant nears startup in New Zealand

    SciTech Connect

    Haggin, J.

    1985-03-25

    Sometime during the summer 1985, New Zealand Synthetic Fuels Co. was scheduled to begin operating its new plant at Motunui, New Zealand. It marks the first commercial application of the Mobil methanol-to-gasoline (MTG) process. Moreover, as the result of a modular approach directed by Bechtel Corp. personnel, the plant represents a major construction success. It is also the first example of a new technology that may seriously challenge traditional Fischer-Tropsch chemistry as a route to synthetic fuels and organic feedstocks. The MTG plant will produce 14,000 barrels per day of gasoline with an octane number rating of 92 to 94 (according to research results). This amount is about one third of present New Zealand demand. The gasoline will be made by catalytic conversion of methanol coming from two plants, each producing about 220 metric tons per day for the single-train MTG plant. The methanol, in turn, is derived from reforming of natural gas from offshore fields in the Tasman Sea.

  9. Direct and Highly Selective Conversion of Synthesis Gas into Lower Olefins: Design of a Bifunctional Catalyst Combining Methanol Synthesis and Carbon-Carbon Coupling.

    PubMed

    Cheng, Kang; Gu, Bang; Liu, Xiaoliang; Kang, Jincan; Zhang, Qinghong; Wang, Ye

    2016-04-01

    The direct synthesis of lower (C2 to C4) olefins, key building-block chemicals, from syngas (H2/CO), which can be derived from various nonpetroleum carbon resources, is highly attractive, but the selectivity for lower olefins is low because of the limitation of the Anderson-Schulz-Flory distribution. We report that the coupling of methanol-synthesis and methanol-to-olefins reactions with a bifunctional catalyst can realize the direct conversion of syngas to lower olefins with exceptionally high selectivity. We demonstrate that the choice of two active components and the integration manner of the components are crucial to lower olefin selectivity. The combination of a Zr-Zn binary oxide, which alone shows higher selectivity for methanol and dimethyl ether even at 673 K, and SAPO-34 with decreased acidity offers around 70% selectivity for C2-C4 olefins at about 10% CO conversion. The micro- to nanoscale proximity of the components favors the lower olefin selectivity. PMID:26961855

  10. Hydrogen production by steam reforming of liquefied natural gas (LNG) over nickel catalysts supported on cationic surfactant-templated mesoporous aluminas

    NASA Astrophysics Data System (ADS)

    Seo, Jeong Gil; Youn, Min Hye; Park, Sunyoung; Jung, Ji Chul; Kim, Pil; Chung, Jin Suk; Song, In Kyu

    Two types of mesoporous γ-aluminas (denoted as A-A and A-S) are prepared by a hydrothermal method under different basic conditions using cationic surfactant (cetyltrimethylammonium bromide, CTAB) as a templating agent. A-A and A-S are synthesized in a medium of ammonia solution and sodium hydroxide solution, respectively. Ni/γ-Al 2O 3 catalysts (Ni/A-A and Ni/A-S) are then prepared by an impregnation method, and are applied to hydrogen production by steam reforming of liquefied natural gas (LNG). The effect of a mesoporous γ-Al 2O 3 support on the catalytic performance of Ni/γ-Al 2O 3 is investigated. The identity of basic solution strongly affects the physical properties of the A-A and A-S supports. The high surface-area of the mesoporous γ-aluminas and the strong metal-support interaction of supported catalysts greatly enhance the dispersion of nickel species on the catalyst surface. The well-developed mesopores of the Ni/A-A and Ni/A-S catalysts prohibit the polymerization of carbon species on the catalyst surface during the reaction. In the steam reforming of LNG, both Ni/A-A and Ni/A-S catalysts give better catalytic performance than the nickel catalyst supported on commercial γ-Al 2O 3 (Ni/A-C). In addition, the Ni/A-A catalyst is superior to the Ni/A-S catalyst. The relatively strong metal-support interaction of Ni/A-A catalyst effectively suppresses the sintering of metallic nickel and the carbon deposition in the steam reforming of LNG. The large pores of the Ni/A-A catalyst also play an important role in enhancing internal mass transfer during the reaction.

  11. Biofiltration of methanol vapor

    SciTech Connect

    Shareefdeen, Z.; Baltzis, B.C. ); Oh, Youngsook; Bartha, R. )

    1993-03-05

    Biofiltration of solvent and fuel vapors may offer a cost-effective way to comply with increasingly strict air emission standards. An important step in the development of this technology is to derive and validate mathematical models of the biofiltration process for predictive and scaleup calculations. For the study of methanol vapor biofiltration, an 8-membered bacterial consortium was obtained from methanol-exposed soil. The bacteria were immobilized on solid support and packed into a 5-cm diameter, 60-cm-high column provided with appropriate flowmeters and sampling ports. The solid support was prepared by mixing two volumes of peat with three volumes of perlite particles. Two series of experiments were performed. In the first, the inlet methanol concentration was kept constant while the superficial air velocity was varied from run to run. In the second series, the air flow rate (velocity) was kept constant while the inlet methanol concentration was varied. The unit proved effective in removing methanol at rates up to 112.8 g h[sup [minus]1] m[sup [minus]3] packing. A mathematical model has been derived and validated. The model described and predicted experimental results closely. Both experimental data and model predictions suggest that the methanol biofiltration process was limited by oxygen diffusion and methanol degradation kinetics.

  12. Hydrogen production by reforming of simulated hot coke oven gas over nickel catalysts promoted with lanthanum and cerium in a membrane reactor

    SciTech Connect

    Hongwei Cheng; Xionggang Lu; Yuwen Zhang; Weizhong Ding

    2009-05-15

    Catalysts of Ni/Mg(Al)O promoted with lanthanum and cerium were tested in a BaCo{sub 0.7}Fe{sub 0.2}Nb{sub 0.1}O{sub 3{delta}} (BCFNO) membrane reactor by catalytic partial oxidation of simulated hot coke oven gas (COG) with toluene as a model tar compound under atmospheric pressure. Analysis of the catalysts suggested that the hydrotalcite precursor after thermal treatment lead to a good dispersion of nickel forming the solid solution NiO-MgO and spinel (Ni,Mg)Al{sub 2}O{sub 4}. The promoted catalysts had higher oxygen permeation flux, better catalytic activity, and better resistance to carbon formation, which will be promising catalysts in the catalytic partial oxidation reforming of hot COG. 29 refs., 11 figs., 2 tabs.

  13. Microfluidic distillation chip for methanol concentration detection.

    PubMed

    Wang, Yao-Nan; Liu, Chan-Chiung; Yang, Ruey-Jen; Ju, Wei-Jhong; Fu, Lung-Ming

    2016-03-17

    An integrated microfluidic distillation system is proposed for separating a mixed ethanol-methanol-water solution into its constituent components. The microfluidic chip is fabricated using a CO2 laser system and comprises a serpentine channel, a boiling zone, a heating zone, and a cooled collection chamber filled with de-ionized (DI) water. In the proposed device, the ethanol-methanol-water solution is injected into the microfluidic chip and driven through the serpentine channel and into the collection chamber by means of a nitrogen carrier gas. Following the distillation process, the ethanol-methanol vapor flows into the collection chamber and condenses into the DI water. The resulting solution is removed from the collection tank and reacted with a mixed indicator. Finally, the methanol concentration is inversely derived from the absorbance measurements obtained using a spectrophotometer. The experimental results show the proposed microfluidic system achieves an average methanol distillation efficiency of 97%. The practicality of the proposed device is demonstrated by detecting the methanol concentrations of two commercial fruit wines. It is shown that the measured concentration values deviate by no more than 3% from those obtained using a conventional bench top system. PMID:26920777

  14. Removal of sulfur contaminants in methanol for fuel cell applications

    SciTech Connect

    Lee, S.H.D.; Kumar, R.; Sederquist, R.

    1996-12-31

    Fuel cell power plants are being developed for transit bus and passenger car applications that use methanol as the on-board fuel. Commodity methanol by itself contains very little sulfur; however, it may occasionally be contaminated with up to about 1% diesel fuel or gasoline in current liquid-fuel distribution systems, leading to the presence of sulfur in the methanol fuel. This sulfur must be removed because of its deleterious effect on the reforming catalysts. International Fuel Cells has set the allowable sulfur limit in the methanol fuel at less than 1 ppm. The equilibrium adsorption isotherm and breakthrough data were used to assess the feasibility of developing a granular activated carbon adsorber for the removal of sulfur from transportation fuel cell systems.

  15. The Methanol Multibeam Survey

    NASA Astrophysics Data System (ADS)

    Green, James A.; Cohen, R. J.; Caswell, J. L.; Fuller, G. A.; Brooks, K.; Burton, M. G.; Chrysostomou, A.; Diamond, P. J.; Ellingsen, S. P.; Gray, M. D.; Hoare, M. G.; Masheder, M. R. W.; McClure-Griffiths, N.; Pestalozzi, M.; Phillips, C.; Quinn, L.; Thompson, M. A.; Voronkov, M.; Walsh, A.; Ward-Thompson, D.; Wong-McSweeney, D.; Yates, J. A.; Cox, J.

    2007-03-01

    A new 7-beam methanol multibeam receiver is being used to survey the Galaxy for newly forming massive stars, that are pinpointed by strong methanol maser emission at 6.668 GHz. The receiver, jointly constructed by Jodrell Bank Observatory (JBO) and the Australia Telescope National Facility (ATNF), was successfully commissioned at Parkes in January 2006. The Parkes-Jodrell survey of the Milky Way for methanol masers is two orders of magnitude faster than previous systematic surveys using 30-m class dishes, and is the first systematic survey of the entire Galactic plane. The first 53 days of observations with the Parkes telescope have yielded 518 methanol sources, of which 218 are new discoveries. We present the survey methodology as well as preliminary results and analysis.

  16. Methanol Cannon Demonstrations Revisited.

    ERIC Educational Resources Information Center

    Dolson, David A.; And Others

    1995-01-01

    Describes two variations on the traditional methanol cannon demonstration. The first variation is a chain reaction using real metal chains. The second example involves using easily available components to produce sequential explosions that can be musical in nature. (AIM)

  17. Biological Methanol Production by a Type II Methanotroph Methylocystis bryophila.

    PubMed

    Patel, Sanjay K S; Mardina, Primata; Kim, Sang-Yong; Lee, Jung-Kul; Kim, In-Won

    2016-04-28

    Methane (CH₄) is the most abundant component in natural gas. To reduce its harmful environmental effect as a greenhouse gas, CH₄ can be utilized as a low-cost feed for the synthesis of methanol by methanotrophs. In this study, several methanotrophs were examined for their ability to produce methanol from CH₄; including Methylocella silvestris, Methylocystis bryophila, Methyloferula stellata, and Methylomonas methanica. Among these methanotrophs, M. bryophila exhibited the highest methanol production. The optimum process parameters aided in significant enhancement of methanol production up to 4.63 mM. Maximum methanol production was observed at pH 6.8, 30°C, 175 rpm, 100 mM phosphate buffer, 50 mM MgCl₂ as a methanol dehydrogenase inhibitor, 50% CH₄ concentration, 24 h of incubation, and 9 mg of dry cell mass ml(-1) inoculum load, respectively. Optimization of the process parameters, screening of methanol dehydrogenase inhibitors, and supplementation with formate resulted in significant improvements in methanol production using M. bryophila. This report suggests, for the first time, the potential of using M. bryophila for industrial methanol production from CH₄. PMID:26838340

  18. The Asian methanol market

    SciTech Connect

    Nagase, Hideki

    1995-12-31

    For the purpose of this presentation, Asia has been broadly defined as a total of 15 countries, namely Japan, Korea, Taiwan, China, Hong Kong, the Philippines, Thailand, Malaysia, Singapore, Indonesia, Myanmar, India, Vietnam, Australia and New Zealand. In 1994 and the first half of 1995, the methanol industry and its derivative industries experienced hard time, because of extraordinarily high methanol prices. In spite of this circumstance, methanol demand in Asian countries has been growing steadily and remarkably, following Asian high economic growth. Most of this growth in demand has been and will continue to be met by outside supply. However, even with increased import of methanol from outside of Asia, as a result of this growth, Asian trade volume will be much larger in the coming years. Asian countries must turn their collective attention to making logistics and transportation for methanol and its derivatives more efficient in the Asian region to make better use of existing supply resources. The author reviews current economic growth as his main topic, and explains the forecast of the growth of methanol demand and supply in Asian countries in the near future.

  19. Experimental Evaluation of SI Engine Operation Supplemented by Hydrogen Rich Gas from a Compact Plasma Boosted Reformer

    SciTech Connect

    J. B. Green, Jr.; N. Domingo; J. M. E. Storey; R.M. Wagner; J.S. Armfield; L. Bromberg; D. R. Cohn; A. Rabinovich; N. Alexeev

    2000-06-19

    It is well known that hydrogen addition to spark-ignited (SI) engines can reduce exhaust emissions and increase efficiency. Micro plasmatron fuel converters can be used for onboard generation of hydrogen-rich gas by partial oxidation of a wide range of fuels. These plasma-boosted microreformers are compact, rugged, and provide rapid response. With hydrogen supplement to the main fuel, SI engines can run very lean resulting in a large reduction in nitrogen oxides (NO x ) emissions relative to stoichiometric combustion without a catalytic converter. This paper presents experimental results from a microplasmatron fuel converter operating under variable oxygen to carbon ratios. Tests have also been carried out to evaluate the effect of the addition of a microplasmatron fuel converter generated gas in a 1995 2.3-L four-cylinder SI production engine. The tests were performed with and without hydrogen-rich gas produced by the plasma boosted fuel converter with gasoline. A one hundred fold reduction in NO x due to very lean operation was obtained under certain conditions. An advantage of onboard plasma-boosted generation of hydrogen-rich gas is that it is used only when required and can be readily turned on and off. Substantial NO x reduction should also be obtainable by heavy exhaust gas recirculation (EGR) facilitated by use of hydrogen-rich gas with stoichiometric operation.

  20. IGNITION IMPROVEMENT OF LEAN NATURAL GAS MIXTURES

    SciTech Connect

    Jason M. Keith

    2005-02-01

    This report describes work performed during a thirty month project which involves the production of dimethyl ether (DME) on-site for use as an ignition-improving additive in a compression-ignition natural gas engine. A single cylinder spark ignition engine was converted to compression ignition operation. The engine was then fully instrumented with a cylinder pressure transducer, crank shaft position sensor, airflow meter, natural gas mass flow sensor, and an exhaust temperature sensor. Finally, the engine was interfaced with a control system for pilot injection of DME. The engine testing is currently in progress. In addition, a one-pass process to form DME from natural gas was simulated with chemical processing software. Natural gas is reformed to synthesis gas (a mixture of hydrogen and carbon monoxide), converted into methanol, and finally to DME in three steps. Of additional benefit to the internal combustion engine, the offgas from the pilot process can be mixed with the main natural gas charge and is expected to improve engine performance. Furthermore, a one-pass pilot facility was constructed to produce 3.7 liters/hour (0.98 gallons/hour) DME from methanol in order to characterize the effluent DME solution and determine suitability for engine use. Successful production of DME led to an economic estimate of completing a full natural gas-to-DME pilot process. Additional experimental work in constructing a synthesis gas to methanol reactor is in progress. The overall recommendation from this work is that natural gas to DME is not a suitable pathway to improved natural gas engine performance. The major reasons are difficulties in handling DME for pilot injection and the large capital costs associated with DME production from natural gas.

  1. Methanol as a gasoline extender: a critique.

    PubMed

    Wigg, E E

    1974-11-29

    The tests conducted with the three vehicles at different emission control levels suggest that, in the area of fuel economy and emissions, potential benefits with methanol blends are related to carburetion and are only significant in the case of the rich-operating cars built before emission control standards were imposed. Theoretical considerations related to methanol's leaning effect on carburetion support this conclusion. Potential advantages for methanol in these areas are therefore continuously diminishing as the older cars leave the roads. At present, these older cars use only about one-fourth of the totalc motor gasoline consumed and, before methanol could be used on a large scale, this fraction would be much smaller. The use of methanol in gasoline would almost certainly create severe product quality problems. Water contamination could lead to phase separation in the distribution system and possibly in the car tank as well, and this would require additional investment in fuel handling and blending equipment. Excess fuel volatility in hot weather may also have adverse effects on car performance if the methanol blends include typical concentrations of butanes and pentanes. Removal of these light hydrocarbon components would detract from methanol's role as a gasoline extender and if current fuel volatility specifications were maintained, its use could lead to a net loss in the total available energy for use in motor fuels. Car performance problems associated with excessively lean operation would also be expected in the case of a significant proportion of late-model cars which are adjusted to operate on lean fuel-air mixtures. If methanol does become available in large quantities, these factors suggest that it would be more practical to use it for purposes other than those related to the extending of motor gasoline, such as for gas turbines used for electric power generation. In this case, the "pure" methanol would act as a cleanburning fuel, having none of the

  2. Modern Processes of Hydrocarbon Migration and Re-Formation of Oil and Gas Fields (Based on the Results of Monitoring and Geochemical Studies)

    NASA Astrophysics Data System (ADS)

    Plotnikova, Irina; Salakhidinova, Gulmira; Nosova, Fidania; Pronin, Nikita; Ostroukhov, Sergey

    2015-04-01

    Special geochemical studies of oils allowed to allocate a movable migration component of oils in the industrial oil deposits. In the field the migration component of oils varies in different parts of the field. The largest percentage of the light migration component (gas condensate of the oil) was detected in the central part of the Kama-Kinel troughs system. Monitoring of the composition of water, oil and gas (condensate light oil component) in the sedimentary cover and ni crystalline basement led to the conclusion of modern migration of hydrocarbons in sedimentary cover. This proves the existence of the modern processes of formation and reformation of oil and gas fields. This presentation is dedicated to the problem of definition of geochemical criteria of selection of hydrocarbons deposit reformation zone in the sample wells of Minibaevskaya area of Romashkinskoye field. While carrying out this work we examined 11 samples of oil from the Upper Devonian Pashiysky horizon. Four oil samples were collected from wells reckoned among the "anomalous" zones that were marked out according to the results of geophysical, oil field and geological research. Geochemical studies of oils were conducted in the laboratory of geochemistry of the Kazan (Volga-region) Federal University. The wells where the signs of hydrocarbons influx from the deep zones of the crust were recorded are considered to be "anomalous". A number of scientists connect this fact to the hypothesis about periodic influx of deep hydrocarbons to the oil deposits of Romashkinskoye field. Other researchers believe that the source rocks of the adjacent valleys sedimentary cover generate gases when entering the main zone of gas formation, which then migrate up the section and passing through the previously formed deposits of oil, change and "lighten" their composition. Regardless of the point of view on the source of the hydrocarbons, the study of the process of deposits refilling with light hydrocarbons is an

  3. Opportunities for coal to methanol conversion

    SciTech Connect

    Not Available

    1980-04-01

    The accumulations of mining residues in the anthracite coal regions of Pennsylvania offer a unique opportunity to convert the coal content into methanol that could be utilized in that area as an alternative to gasoline or to extend the supplies through blending. Additional demand may develop through the requirements of public utility gas turbines located in that region. The cost to run this refuse through coal preparation plants may result in a clean coal at about $17.00 per ton. After gasification and synthesis in a 5000 ton per day facility, a cost of methanol of approximately $3.84 per million Btu is obtained using utility financing. If the coal is to be brought in by truck or rail from a distance of approximately 60 miles, the cost of methanol would range between $4.64 and $5.50 per million Btu depending upon the mode of transportation. The distribution costs to move the methanol from the synthesis plant to the pump could add, at a minimum, $2.36 per million Btu to the cost. In total, the delivered cost at the pump for methanol produced from coal mining wastes could range between $6.20 and $7.86 per million Btu.

  4. A passive fuel delivery system for portable direct methanol fuel cells

    NASA Astrophysics Data System (ADS)

    Guo, Z.; Cao, Y.

    A passive device is utilized for transferring methanol into water through a wick material. The wick material preferentially has a higher wicking capability with respect to methanol than water, and operates in a siphon fashion with the intake end in contact with methanol and the discharge end in contact with water. Due to the difference of wicking capabilities, a net amount of methanol is pumped into water. The device described above is used as a fuel delivery component for a liquid-feed fuel cell system, such as a direct methanol fuel cell (DMFC), which directly utilizes a liquid fuel without an intermediate reforming process. In the present experimental study, methanol and water are stored separately in two containers and a wick is positioned between the containers as a siphon, with the aqueous methanol solution communicating with the anode of the DMFC. Methanol is siphoned from the methanol container to the water container in situ when the methanol in the water is consumed during the operation of the fuel cell. Through a proper selection of the wick and the containers, the methanol concentration near the anode of the DMFC was maintained within a preferred range.

  5. Methanol in dark clouds

    NASA Technical Reports Server (NTRS)

    Friberg, P.; Hjalmarson, A.; Madden, S. C.; Irvine, W. M.

    1988-01-01

    The first observation of methanol in cold dark clouds TMC 1, L 134 N, and B 335 is reported. In all three clouds, the relative abundance of methanol was found to be in the range of 10 to the -9th (i.e., almost an order of magnitude more abundant than acetaldehyde), with no observable variation between the clouds. Methanol emission showed a complex velocity structure; in TMC 1, clear indications of non-LTE were observed. Dimethyl ether was searched for in L 134 N; the upper limit of the column density of dimethyl ether in L 134 N was estimated to be 4 x 10 to the 12th/sq cm, assuming 5 K rotation temperature and LTE. This limit makes the abundance ratio (CH3)2O/CH3OH not higher than 1/5, indicating that dimethyl ether is not overabundant in this dark cloud.

  6. Methanol synthesis studies using in situ FTIR spectroscopy

    SciTech Connect

    Edwards, J.F.; Schrader, G.L.

    1986-04-01

    Future demand for methanol could expand multifold as coal assumes a greater proportion of energy needs. Although methanol is presently economically unattractive as a substitute for gasoline, the State of California has begun a program to operate 550 vehicles with methanol because it produces fewer pollutants than gasoline. More than 300 privately-owned vehicles, converted by Future Fuels of America, Inc., are running on methanol in the Sacramento, San Francisco, and Los Angeles areas. Even if gasoline remains the major automotive fuel into the next century, methanol production could increase significantly if technology such as Mobil Oil's M-Gasoline process is used to produce gasoline. This process uses a zeolite catalyst (ZSM-5) to convert methanol into a blend of paraffins, cycloparaffins, and aromatics with a research octane number of 93, i.e., an unleaded premium gasoline. New Zealand will use this technology to convert natural gas into approximately 12,500 bbl/d of gasoline. Utilities using coal gasification technology for power generation will probably also manufacture methanol. During off-peak hours, part of the syngas would be converted to methanol and stored; during peak hours, the methanol would be used as fuel in gas turbines to meet the high electrical demand. And finally, there is great potential for future development of methanol as a primary feedstock in the chemical industry, especially as supplies of ethylene and propylene decrease. An example is the manufacture of acetic acid, where methanol has replaced ethylene as the primary feedstock in new technologies by BASF and Monsanto.

  7. Process Design and Economics for the Conversion of Lignocellulosic Biomass to High Octane Gasoline: Thermochemical Research Pathway with Indirect Gasification and Methanol Intermediate

    SciTech Connect

    Tan, Eric; Talmadge, M.; Dutta, Abhijit; Hensley, Jesse; Schaidle, Josh; Biddy, Mary J.; Humbird, David; Snowden-Swan, Lesley J.; Ross, Jeff; Sexton, Danielle; Yap, Raymond; Lukas, John

    2015-03-01

    The U.S. Department of Energy (DOE) promotes research for enabling cost-competitive liquid fuels production from lignocellulosic biomass feedstocks. The research is geared to advance the state of technology (SOT) of biomass feedstock supply and logistics, conversion, and overall system sustainability. As part of their involvement in this program, the National Renewable Energy Laboratory (NREL) and the Pacific Northwest National Laboratory (PNNL) investigate the economics of conversion pathways through the development of conceptual biorefinery process models. This report describes in detail one potential conversion process for the production of high octane gasoline blendstock via indirect liquefaction (IDL). The steps involve the conversion of biomass to syngas via indirect gasification followed by gas cleanup and catalytic syngas conversion to a methanol intermediate; methanol is then further catalytically converted to high octane hydrocarbons. The conversion process model leverages technologies previously advanced by research funded by the Bioenergy Technologies Office (BETO) and demonstrated in 2012 with the production of mixed alcohols from biomass. Biomass-derived syngas cleanup via tar and hydrocarbons reforming was one of the key technology advancements as part of that research. The process described in this report evaluates a new technology area with downstream utilization of clean biomass-syngas for the production of high octane hydrocarbon products through a methanol intermediate, i.e., dehydration of methanol to dimethyl ether (DME) which subsequently undergoes homologation to high octane hydrocarbon products.

  8. Multi-fuel reformers for fuel cells used in transportation: Assessment of hydrogen storage technologies. Phase 1, Final report

    SciTech Connect

    Not Available

    1994-03-01

    This report documents a portion of the work performed Multi-fuel Reformers for Fuel Cells Used in Transportation. One objective for development is to develop advanced fuel processing systems to reform methanol, ethanol, natural gas, and other hydrocarbons into hydrogen for use in transportation fuel cell systems, while a second objective is to develop better systems for on-board hydrogen storage. This report examines techniques and technology available for storage of pure hydrogen on board a vehicle as pure hydrogen of hydrides. The report focuses separately on near- and far-term technologies, with particular emphasis on the former. Development of lighter, more compact near-term storage systems is recommended to enhance competitiveness and simplify fuel cell design. The far-term storage technologies require substantial applied research in order to become serious contenders.

  9. Hydrogen from catalytic reforming of biomass-derived hydrocarbons in liquid water

    NASA Astrophysics Data System (ADS)

    Cortright, R. D.; Davda, R. R.; Dumesic, J. A.

    2002-08-01

    Concerns about the depletion of fossil fuel reserves and the pollution caused by continuously increasing energy demands make hydrogen an attractive alternative energy source. Hydrogen is currently derived from nonrenewable natural gas and petroleum, but could in principle be generated from renewable resources such as biomass or water. However, efficient hydrogen production from water remains difficult and technologies for generating hydrogen from biomass, such as enzymatic decomposition of sugars, steam-reforming of bio-oils and gasification, suffer from low hydrogen production rates and/or complex processing requirements. Here we demonstrate that hydrogen can be produced from sugars and alcohols at temperatures near 500K in a single-reactor aqueous-phase reforming process using a platinum-based catalyst. We are able to convert glucose-which makes up the major energy reserves in plants and animals-to hydrogen and gaseous alkanes, with hydrogen constituting 50% of the products. We find that the selectivity for hydrogen production increases when we use molecules that are more reduced than sugars, with ethylene glycol and methanol being almost completely converted into hydrogen and carbon dioxide. These findings suggest that catalytic aqueous-phase reforming might prove useful for the generation of hydrogen-rich fuel gas from carbohydrates extracted from renewable biomass and biomass waste streams.

  10. Hydrogen from catalytic reforming of biomass-derived hydrocarbons in liquid water.

    PubMed

    Cortright, R D; Davda, R R; Dumesic, J A

    2002-08-29

    Concerns about the depletion of fossil fuel reserves and the pollution caused by continuously increasing energy demands make hydrogen an attractive alternative energy source. Hydrogen is currently derived from nonrenewable natural gas and petroleum, but could in principle be generated from renewable resources such as biomass or water. However, efficient hydrogen production from water remains difficult and technologies for generating hydrogen from biomass, such as enzymatic decomposition of sugars, steam-reforming of bio-oils and gasification, suffer from low hydrogen production rates and/or complex processing requirements. Here we demonstrate that hydrogen can be produced from sugars and alcohols at temperatures near 500 K in a single-reactor aqueous-phase reforming process using a platinum-based catalyst. We are able to convert glucose -- which makes up the major energy reserves in plants and animals -- to hydrogen and gaseous alkanes, with hydrogen constituting 50% of the products. We find that the selectivity for hydrogen production increases when we use molecules that are more reduced than sugars, with ethylene glycol and methanol being almost completely converted into hydrogen and carbon dioxide. These findings suggest that catalytic aqueous-phase reforming might prove useful for the generation of hydrogen-rich fuel gas from carbohydrates extracted from renewable biomass and biomass waste streams. PMID:12198544

  11. Methanol from coal

    NASA Technical Reports Server (NTRS)

    Miller, D. R.

    1978-01-01

    Economic feasibility of methanol or methyl fuel produced from coal using existing technology is discussed. Other factors considered include environmental, safety, toxicity, transportation, so storage, ease of burning, and retrofitting of present boilers. Demonstrations of its uses as a boiler fuel and as a turbine fuel are cited.

  12. Comparison of Bond Scission Sequence of Methanol on Tungsten Monocarbide and Pt-Modified Tungsten Monocarbide

    SciTech Connect

    Liu, P.; Stottlemyer, A.L.; Chen, J.G.

    2010-09-14

    The ability to control the bond scission sequence of O-H, C-H, and C-O bonds is of critical importance in the effective utilization of oxygenate molecules, such as in reforming reactions and in alcohol fuel cells. In the current study, we use methanol as a probe molecule to demonstrate the possibility to control the decomposition pathways by supporting monolayer coverage of Pt on a tungsten monocarbide (WC) surface. Density functional theory (DFT) results reveal that on the WC and Pt/WC surfaces CH{sub 3}OH decomposes via O-H bond scission to form the methoxy (*CH{sub 3} O) intermediate. The subsequent decomposition of methoxy on the WC surface occurs through the C-O bond scission to form *CH{sub 3}, which reacts with surface *H to produce CH{sub 4}. In contrast, the decomposition of methoxy on the Pt/WC surface favors the C-H bond scission to produce *CH{sub 2} O, which prevents the formation of the *CH{sub 3} species and leads to the formation of a *CO intermediate through subsequent deprotonation steps. The DFT predictions are validated using temperature programmed desorption to quantify the gas-phase product yields and high resolution electron energy loss spectroscopy to determine the surface intermediates from methanol decomposition on Pt, WC, and Pt/WC surfaces.

  13. Comparison of bond scission sequence of methanol on tungsten monocarbide and Pt-modified tungsten monocarbide

    NASA Astrophysics Data System (ADS)

    Stottlemyer, Alan Lee; Liu, Ping; Chen, Jingguang G.

    2010-09-01

    The ability to control the bond scission sequence of OH, CH, and CO bonds is of critical importance in the effective utilization of oxygenate molecules, such as in reforming reactions and in alcohol fuel cells. In the current study, we use methanol as a probe molecule to demonstrate the possibility to control the decomposition pathways by supporting monolayer coverage of Pt on a tungsten monocarbide (WC) surface. Density functional theory (DFT) results reveal that on the WC and Pt/WC surfaces CH3OH decomposes via OH bond scission to form the methoxy (C∗H3 O) intermediate. The subsequent decomposition of methoxy on the WC surface occurs through the CO bond scission to form C∗H3, which reacts with surface H∗ to produce CH4. In contrast, the decomposition of methoxy on the Pt/WC surface favors the CH bond scission to produce C∗H2 O, which prevents the formation of the C∗H3 species and leads to the formation of a C∗O intermediate through subsequent deprotonation steps. The DFT predictions are validated using temperature programmed desorption to quantify the gas-phase product yields and high resolution electron energy loss spectroscopy to determine the surface intermediates from methanol decomposition on Pt, WC, and Pt/WC surfaces.

  14. What Reform?

    ERIC Educational Resources Information Center

    Welsh, Patrick

    1986-01-01

    A teacher explores the recent educational reform movement and discusses the studies of schools done by Sociologist Christopher Jencks in the 1970s. An important idea that can be extrapolated from Jencks' studies is that schools should function more like families than factories. This would empower teachers and make schooling more equitable,…

  15. Toothless Reform?

    ERIC Educational Resources Information Center

    Smarick, Andy

    2010-01-01

    To many education reformers, the passage of the federal government's massive stimulus plan, the American Recovery and Reinvestment Act (ARRA), appeared to be a final bright star falling into alignment. The ARRA seemed to complete the constellation: an astounding $100 billion of new federal funds--nearly twice the annual budget of the U.S.…

  16. Rethinking Reform

    ERIC Educational Resources Information Center

    Garland, James C.

    2010-01-01

    As president of Miami University of Ohio from 1996 until 2006, James C. Garland redefined the public institution as a "semi-private" university by implementing the same tuition for both in-state and out-of-state students. Students from Ohio with need received large scholarships--but those who could afford to pay more did so. The reform, which…

  17. A techno-economic & environmental analysis of a novel technology utilizing an internal combustion engine as a compact, inexpensive micro-reformer for a distributed gas-to-liquids system

    NASA Astrophysics Data System (ADS)

    Browne, Joshua B.

    Anthropogenic greenhouse gas emissions (GHG) contribute to global warming, and must be mitigated. With GHG mitigation as an overarching goal, this research aims to study the potential for newfound and abundant sources of natural gas to play a role as part of a GHG mitigation strategy. However, recent work suggests that methane leakage in the current natural gas system may inhibit end-use natural gas as a robust mitigation strategy, but that natural gas as a feedstock for other forms of energy, such as electricity generation or liquid fuels, may support natural-gas based mitigation efforts. Flaring of uneconomic natural gas, or outright loss of natural gas to the atmosphere results in greenhouse gas emissions that could be avoided and which today are very large in aggregate. A central part of this study is to look at a new technology for converting natural gas into methanol at a unit scale that is matched to the size of individual natural gas wells. The goal is to convert stranded or otherwise flared natural gas into a commercially valuable product and thereby avoid any unnecessary emission to the atmosphere. A major part of this study is to contribute to the development of a novel approach for converting natural gas into methanol and to assess the environmental impact (for better or for worse) of this new technology. This Ph. D. research contributes to the development of such a system and provides a comprehensive techno-economic and environmental assessment of this technology. Recognizing the distributed nature of methane leakage associated with the natural gas system, this work is also intended to advance previous research at the Lenfest Center for Sustainable Energy that aims to show that small, modular energy systems can be made economic. This thesis contributes to and analyzes the development of a small-scale gas-to-liquids (GTL) system aimed at addressing flared natural gas from gas and oil wells. This thesis includes system engineering around a design that

  18. A techno-economic & environmental analysis of a novel technology utilizing an internal combustion engine as a compact, inexpensive micro-reformer for a distributed gas-to-liquids system

    NASA Astrophysics Data System (ADS)

    Browne, Joshua B.

    Anthropogenic greenhouse gas emissions (GHG) contribute to global warming, and must be mitigated. With GHG mitigation as an overarching goal, this research aims to study the potential for newfound and abundant sources of natural gas to play a role as part of a GHG mitigation strategy. However, recent work suggests that methane leakage in the current natural gas system may inhibit end-use natural gas as a robust mitigation strategy, but that natural gas as a feedstock for other forms of energy, such as electricity generation or liquid fuels, may support natural-gas based mitigation efforts. Flaring of uneconomic natural gas, or outright loss of natural gas to the atmosphere results in greenhouse gas emissions that could be avoided and which today are very large in aggregate. A central part of this study is to look at a new technology for converting natural gas into methanol at a unit scale that is matched to the size of individual natural gas wells. The goal is to convert stranded or otherwise flared natural gas into a commercially valuable product and thereby avoid any unnecessary emission to the atmosphere. A major part of this study is to contribute to the development of a novel approach for converting natural gas into methanol and to assess the environmental impact (for better or for worse) of this new technology. This Ph. D. research contributes to the development of such a system and provides a comprehensive techno-economic and environmental assessment of this technology. Recognizing the distributed nature of methane leakage associated with the natural gas system, this work is also intended to advance previous research at the Lenfest Center for Sustainable Energy that aims to show that small, modular energy systems can be made economic. This thesis contributes to and analyzes the development of a small-scale gas-to-liquids (GTL) system aimed at addressing flared natural gas from gas and oil wells. This thesis includes system engineering around a design that

  19. Applications of solar reforming technology

    SciTech Connect

    Spiewak, I.; Tyner, C.E.; Langnickel, U.

    1993-11-01

    Research in recent years has demonstrated the efficient use of solar thermal energy for driving endothermic chemical reforming reactions in which hydrocarbons are reacted to form synthesis gas (syngas). Closed-loop reforming/methanation systems can be used for storage and transport of process heat and for short-term storage for peaking power generation. Open-loop systems can be used for direct fuel production; for production of syngas feedstock for further processing to specialty chemicals and plastics and bulk ammonia, hydrogen, and liquid fuels; and directly for industrial processes such as iron ore reduction. In addition, reforming of organic chemical wastes and hazardous materials can be accomplished using the high-efficiency destruction capabilities of steam reforming. To help identify the most promising areas for future development of this technology, we discuss in this paper the economics and market potential of these applications.

  20. Methanol synthesis using a catalyst combination of alkali or alkaline earth salts and reduced copper chromite for methanol synthesis

    DOEpatents

    Tierney, John W.; Wender, Irving; Palekar, Vishwesh M.

    1993-01-01

    The present invention relates to a novel route for the synthesis of methanol, and more specifically to the production of methanol by contacting synthesis gas under relatively mild conditions in a slurry phase with a catalyst combination comprising reduced copper chromite and basic alkali salts or alkaline earth salts. The present invention allows the synthesis of methanol to occur in the temperature range of approximately 100.degree.-160.degree. C. and the pressure range of 40-65 atm. The process produces methanol with up to 90% syngas conversion per pass and up to 95% methanol selectivity. The only major by-product is a small amount of easily separated methyl formate. Very small amounts of water, carbon dioxide and dimethyl ether are also produced. The present catalyst combination also is capable of tolerating fluctuations in the H.sub.2 /CO ratio without major deleterious effect on the reaction rate. Furthermore, carbon dioxide and water are also tolerated without substantial catalyst deactivation.

  1. Competitive adsorption-driven separation of water/methanol mixtures using hydrogen as a third competitor.

    PubMed

    Lee, Dong-Wook; Yu, Chang-Yeol; Lee, Kew-Ho

    2009-12-01

    In this study, we report competitive adsorption-driven separation of a water/methanol mixture in Pd-deposited silica membranes, which is induced by introducing hydrogen carrier gas as a third competitor. After replacing helium carrier gas by hydrogen carrier gas, water vapor permeance showed a slight decrease, whereas methanol vapor permeance significantly decreased. The water/methanol separation factor remarkably increased from 1.7-16.5 to 6.8-58.2 in the feed water content of 5.8-83.0 wt.%. From single vapor permeation tests in the presence of carrier gas (hydrogen or helium), it was confirmed that those permeation behavior was derived from stronger effect of the competitive adsorption between hydrogen and methanol vapor than that between hydrogen and water vapor. That is, hydrogen carrier gas dominantly inhibits adsorption of methanol vapor on the membrane surface, and the partial pressure of methanol on the membrane surface decreases, which leads to a decrease in methanol permeance with reduced driving force. In addition, temperature programmed desorption (TPD) results of water and methanol from Pd/silica particles also demonstrated that hydrogen carrier gas suppresses methanol adsorption on Pd/silica surface more dominantly than water adsorption. PMID:19772967

  2. Teaching Reform and Union Reform.

    ERIC Educational Resources Information Center

    Kerchner, Charles T.; Mitchell, Douglas E.

    1986-01-01

    Reviews present labor statutes and examines three alternatives to current practices; proposes that teaching, by its nature, is not well administered by industrial standards or well adjudicated through industrial unionism. Suggests "professional unionism" as a means of effecting educational reform. (DR)

  3. Photolysis of oxyfluorfen in aqueous methanol.

    PubMed

    Chakraborty, Subhasish K; Chakraborty, Savitri; Bhattacharyya, Anjan; Chowdhury, Ashim

    2013-01-01

    Photolysis of oxyfluorfen, an herbicide of the nitrodiphenyl ether class, was studied in aqueous methanol under UV and sunlight. UV irradiation was carried out in a borosilicate glass photoreactor (containing 250 ppm oxyfluorfen in 50% aqueous methanol) equipped with a quartz filter and 125 watt mercury lamp (maximum output 254 nm) at 25 ± 1°C. Sunlight irradiation was conducted at 28 ± 1°C in borosilicate Erlenmeyer flasks containing 250 ppm oxyfluorfen in 50% aqueous methanol. The samples from both the irradiated conditions were withdrawn at a definite time interval and extracted to measure oxyfluorfen content by gas chromatography-flame ionization detector for rate study. The half-life values were 20 hours and 2.7 days under UV and sunlight exposure, respectively. Photolysis of oxyfluorfen yielded 13 photoproducts of which three were characterized by infrared spectrophotometer and (1)H NMR and (13)C NMR spectroscopy. The rest of the photoproducts were identified by gas chromatography-mass spectrometry (GC-MS) and thin layer chromatography (TLC). An ionization potential 70 eV was used for electron impact-mass spectrometry (EI-MS) and methane was used as reagent gas for chemical ionization-mass spectrometry (CI-MS). Two of the photoproducts were also synthesized for comparison. The main phototransformation pathways of oxyfluorfen involved nitro reduction, dechlorination, and hydrolysis as well as nucleophiles displacement reaction. PMID:23998303

  4. Atmospheric deposition of methanol over the Atlantic Ocean

    PubMed Central

    Yang, Mingxi; Nightingale, Philip D.; Beale, Rachael; Liss, Peter S.; Blomquist, Byron; Fairall, Christopher

    2013-01-01

    In the troposphere, methanol (CH3OH) is present ubiquitously and second in abundance among organic gases after methane. In the surface ocean, methanol represents a supply of energy and carbon for marine microbes. Here we report direct measurements of air–sea methanol transfer along a ∼10,000-km north–south transect of the Atlantic. The flux of methanol was consistently from the atmosphere to the ocean. Constrained by the aerodynamic limit and measured rate of air–sea sensible heat exchange, methanol transfer resembles a one-way depositional process, which suggests dissolved methanol concentrations near the water surface that are lower than what were measured at ∼5 m depth, for reasons currently unknown. We estimate the global oceanic uptake of methanol and examine the lifetimes of this compound in the lower atmosphere and upper ocean with respect to gas exchange. We also constrain the molecular diffusional resistance above the ocean surface—an important term for improving air–sea gas exchange models. PMID:24277830

  5. California methanol assessment. Volume 2: Technical report

    NASA Technical Reports Server (NTRS)

    Otoole, R.; Dutzi, E.; Gershman, R.; Heft, R.; Kalema, W.; Maynard, D.

    1983-01-01

    Energy feedstock sources for methanol; methanol and other synfuels; transport, storage, and distribution; air quality impact of methanol use in vehicles, chemical methanol production and use; methanol utilization in vehicles; methanol utilization in stationary applications; and environmental and regulatory constraints are discussed.

  6. Methanol in dark clouds

    NASA Astrophysics Data System (ADS)

    Friberg, P.; Hjalmarson, A.; Madden, S. C.; Irvine, W. M.

    1988-04-01

    The authors report observations, for the first time, of the 20 - 10A+ and E, 2-1 - 1-1 E, and 10 - 00A+ lines of methanol (CH3OH) in three dark cold clouds, TMC 1, L 134N, and B 335. The CH3OH emission is extended in these clouds and shows a complex velocity structure. Clear indications of non LTE excitation are observed in TMC 1. Estimated column densities are a few×1013cm-2. Although less abundant than formaldehyde (H2CO), methanol is almost an order of magnitude more abundant than acetaldehyde (CH3CHO), in these clouds. Dimethyl ether was searched for in L 134N, to an upper limit of 4×1012cm-2 (3σ). Implications for dark cloud excitation and chemistry are discussed.

  7. Eucomic acid methanol monosolvate

    PubMed Central

    Li, Guo-Qiang; Li, Yao-Lan; Wang, Guo-Cai; Liang, Zhi-Hong; Jiang, Ren-Wang

    2011-01-01

    In the crystal structure of the title compound [systematic name: 2-hy­droxy-2-(4-hy­droxy­benz­yl)butane­dioic acid methanol monosolvate], C11H12O6·CH3OH, the dihedral angles between the planes of the carboxyl groups and the benzene ring are 51.23 (9) and 87.97 (9)°. Inter­molecular O—H⋯O hydrogen-bonding inter­actions involving the hy­droxy and carb­oxy­lic acid groups and the methanol solvent mol­ecule give a three-dimensional structure. PMID:22091200

  8. A molecular beam scattering investigation of methanol-noble gas complexes: Characterization of the isotropic potential and insights into the nature of the interaction

    NASA Astrophysics Data System (ADS)

    Cappelletti, D.; Candori, P.; Falcinelli, S.; Albertí, M.; Pirani, F.

    2012-08-01

    Integral cross section experiments involving rotationally hot CH3OH projectiles and noble gas (Ng = Ne, Ar, Kr and Xe) targets are reported for the first time. Measured data have been exploited to characterize the phenomenological radial interaction in the CH3OH-Ng weakly bound complexes. Potential energy surfaces for all the systems have been formulated on the basis of a pairwise additive multicenter model. The comparison of model predictions with the most relevant experimental findings suggests that in CH3OH-Ng complexes, at variance with the behavior of the analogous complexes involving water or ammonia, the interaction is mainly due to van der Waals and induction components.

  9. Methanol sensing characteristics of conducting polypyrrole-silver nanocomposites

    NASA Astrophysics Data System (ADS)

    Kabir, L.; Mandal, S. K.

    2012-05-01

    Methanol sensing characteristics of conducting polypyrrole-silver nanocomposites are reported here. The nanocomposites are synthesized by wet chemical technique with different amount of silver loadings (5-15 mol%). The sensitivity of the nanocomposites upon exposure to gas molecules is critically dependent on the silver loadings and the concentration of the exposed gas. This is possibly instigated by the modified metal-polymer interface and the polar nature of the constituent metal and the exposed gas. Interaction of the alcohol gas with the polypyrrole chains in the presence of silver effectively determines the change in resistance and hence the sensitivity of the nanocomposites upon exposure to methanol. The adsorption of methanol molecules within the nanocomposites and the subsequent chemical reactions are studied by Fourier transform infrared (FTIR) spectroscopy.

  10. The toxicity of methanol

    SciTech Connect

    Tephly, T.R. )

    1991-01-01

    Methanol toxicity in humans and monkeys is characterized by a latent period of many hours followed by a metabolic acidosis and ocular toxicity. This is not observed in most lower animals. The metabolic acidosis and blindness is apparently due to formic acid accumulation in humans and monkeys, a feature not seen in lower animals. The accumulation of formate is due to a deficiency in formate metabolism which is, in turn, related, in part, to low hepatic tetrahydrofolate (H{sub 4}folate). An excellent correlation between hepatic H{sub 4} folate and formate oxidation rates has been shown within and across species. Thus, humans and monkeys possess low hepatic H{sub 4}folate levels, low rates of formate oxidation and accumulation of formate after methanol. Formate, itself, produces blindness in monkeys in the absence of metabolic acidosis. In addition to low hepatic H{sub 4}folate concentrations, monkeys and humans also have low hepatic 10-formyl H{sub 4}folate dehydrogenase levels, the enzyme which is the ultimate catalyst for conversion of formate to carbon dioxide. This review presents the basis for the role of folic acid-dependent reactions in the regulation of methanol toxicity.