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Sample records for co2 chemical upgrading

  1. A review on optimization production and upgrading biogas through CO2 removal using various techniques.

    PubMed

    Andriani, Dian; Wresta, Arini; Atmaja, Tinton Dwi; Saepudin, Aep

    2014-02-01

    Biogas from anaerobic digestion of organic materials is a renewable energy resource that consists mainly of CH4 and CO2. Trace components that are often present in biogas are water vapor, hydrogen sulfide, siloxanes, hydrocarbons, ammonia, oxygen, carbon monoxide, and nitrogen. Considering the biogas is a clean and renewable form of energy that could well substitute the conventional source of energy (fossil fuels), the optimization of this type of energy becomes substantial. Various optimization techniques in biogas production process had been developed, including pretreatment, biotechnological approaches, co-digestion as well as the use of serial digester. For some application, the certain purity degree of biogas is needed. The presence of CO2 and other trace components in biogas could affect engine performance adversely. Reducing CO2 content will significantly upgrade the quality of biogas and enhancing the calorific value. Upgrading is generally performed in order to meet the standards for use as vehicle fuel or for injection in the natural gas grid. Different methods for biogas upgrading are used. They differ in functioning, the necessary quality conditions of the incoming gas, and the efficiency. Biogas can be purified from CO2 using pressure swing adsorption, membrane separation, physical or chemical CO2 absorption. This paper reviews the various techniques, which could be used to optimize the biogas production as well as to upgrade the biogas quality.

  2. Microbial Electrolytic Capture, Separation and Regeneration of CO2 for Biogas Upgrading.

    PubMed

    Jin, Xiangdan; Zhang, Yifeng; Li, Xiaohu; Zhao, Nannan; Angelidaki, Irini

    2017-08-15

    Biogas upgrading to natural gas quality is essential for the efficient use of biogas in various applications. Carbon dioxide (CO2) which constitutes a major part of the biogas is generally removed by physicochemical methods. However, most of the methods are expensive and often present environmental challenges. In this study, an innovative microbial electrolytic system was developed to capture, separate and regenerate CO2 for biogas upgrading without external supply of chemicals, and potentially to treat wastewater. The new system was operated at varied biogas flow rates and external applied voltages. CO2 was effectively separated from the raw biogas and the CH4 content in the outlet reached as high as 97.0 ± 0.2% at the external voltage of 1.2 V and gas flow rate of 19.6 mL/h. Regeneration of CO2 was also achieved in the regeneration chamber with low pH (1.34 ± 0.04). The relatively low electric energy consumption (≤0.15 kWh/m(3) biogas) along with the H2 production which can contribute to the energy input makes the overall energy need of the system low, and thereby makes the technology promising. This work provides the first attempt for development of a sustainable biogas upgrading technology and potentially expands the application of microbial electrochemical technologies.

  3. Bioelectrochemical removal of carbon dioxide (CO2): an innovative method for biogas upgrading.

    PubMed

    Xu, Heng; Wang, Kaijun; Holmes, Dawn E

    2014-12-01

    Innovative methods for biogas upgrading based on biological/in-situ concepts have started to arouse considerable interest. Bioelectrochemical removal of CO2 for biogas upgrading was proposed here and demonstrated in both batch and continuous experiments. The in-situ biogas upgrading system seemed to perform better than the ex-situ one, but CO2 content was kept below 10% in both systems. The in-situ system's performance was further enhanced under continuous operation. Hydrogenotrophic methanogenesis and alkali production with CO2 absorption could be major contributors to biogas upgrading. Molecular studies showed that all the biocathodes associated with biogas upgrading were dominated by sequences most similar to the same hydrogenotrophic methanogen species, Methanobacterium petrolearium (97-99% sequence identity). Conclusively, bioelectrochemical removal of CO2 showed great potential for biogas upgrading. Copyright © 2014 Elsevier Ltd. All rights reserved.

  4. Remote sensing of chemical warfare agent by CO2 -lidar

    NASA Astrophysics Data System (ADS)

    Geiko, Pavel P.; Smirnov, Sergey S.

    2014-11-01

    The possibilities of remote sensing of chemical warfare agent by differential absorption method were analyzed. The CO2 - laser emission lines suitable for sounding of chemical warfare agent with provision for disturbing absorptions by water vapor were choose. The detection range of chemical warfare agents was estimated for a lidar based on CO2 - laser The other factors influencing upon echolocation range were analyzed.

  5. Metal-Organic Frameworks for CO2 Chemical Transformations.

    PubMed

    He, Hongming; Perman, Jason A; Zhu, Guangshan; Ma, Shengqian

    2016-12-01

    Carbon dioxide (CO2 ), as the primary greenhouse gas in the atmosphere, triggers a series of environmental and energy related problems in the world. Therefore, there is an urgent need to develop multiple methods to capture and convert CO2 into useful chemical products, which can significantly improve the environment and promote sustainable development. Over the past several decades, metal-organic frameworks (MOFs) have shown outstanding heterogeneous catalytic activity due in part to their high internal surface area and chemical functionalities. These properties and the ability to synthesize MOF platforms allow experiments to test structure-function relationships for transforming CO2 into useful chemicals. Herein, recent developments are highlighted for MOFs participating as catalysts for the chemical fixation and photochemical reduction of CO2 . Finally, opportunities and challenges facing MOF catalysts are discussed in this ongoing research area.

  6. CO2 solvation free energy using quasi-chemical theory

    NASA Astrophysics Data System (ADS)

    Jiao, Dian; Rempe, Susan B.

    2011-06-01

    Accumulation of greenhouse gases, especially carbon dioxide, is believed to be the key factor in global climate change. To develop effective ways to remove CO2 from the atmosphere, it is helpful to understand the mechanism of CO2 solvation first. Here we investigate the thermodynamics of CO2 hydration using quasi-chemical theory. Two approaches for estimating hydration free energy are carried out. Both agree reasonably well with experimental measurements. Analysis of the free energy components reveals that the weak hydration free energy results from a balance of unfavorable molecular packing and favorable chemical association.

  7. Chemical looping for syngas & hydrogen production with parallel CO2 activation

    NASA Astrophysics Data System (ADS)

    More, Amey Sudhir

    The anticipated rise in global population and the rapidly growing economies of the developing world will dramatically increase the demand for consumer products, which are derived mostly from commodity chemicals. While the abundant natural gas (>95% CH4) reserves can potentially enable bulk chemical production, all commercial routes for methane (CH4) upgrading require its conversion to syngas (mixture of CO+H2) as a first step. Not only are current syngas production technologies highly energy and capital intensive, but they also result in large CO2 emissions. Overall, rising environmental concerns, increase demand for bulk chemicals and availability of abundant natural gas reserves together motivate the need to develop alternative processes for syngas production with CO2 utilization. 'Chemical Looping Combustion' is a clean combustion technology, which enables fossil fuel combustion with inherent CO2 capture based on the cyclic oxidation and reduction of an oxygen carrier. While most efforts in chemical looping (CL) are focused on combustion, we demonstrate the application of the "CL principle"--the periodic oxidation and reduction of a metal oxide to couple two independent redox reactions--to the activation of CO2 via reduction to CO (a chemical feedstock) and upgrading of CH4 to syngas or hydrogen. In this work, we investigate and compare CO2 activation via CL in two different operating modes: In the first scheme, CO2 reduction is coupled with CH4 oxidation by using mixtures of Fe and Ni (as alloys or simple physical mixtures) to produce CO and syngas product streams. In the second operating scheme, monometallic Ni carriers are utilized to catalytically crack CH4, producing pure H2 streams. The solid carbon deposits are then burnt off with CO2, overall producing separate CO and H2 product streams. Our investigations demonstrate the potential of CO2 as a "soft" oxidant which enables selective oxidation reactions in all the configurations, and thereby establish the

  8. Evaporative CO2 microchannel cooling for the LHCb VELO pixel upgrade

    NASA Astrophysics Data System (ADS)

    de Aguiar Francisco, O. A.; Buytaert, J.; Collins, P.; Dumps, R.; John, M.; Mapelli, A.; Romagnoli, G.

    2015-05-01

    The LHCb Vertex Detector (VELO) will be upgraded in 2018 to a lightweight pixel detector capable of 40 MHz readout and operation in very close proximity to the LHC beams. The thermal management of the system will be provided by evaporative CO2 circulating in microchannels embedded within thin silicon plates. This solution has been selected due to the excellent thermal efficiency, the absence of thermal expansion mismatch with silicon ASICs and sensors, the radiation hardness of CO2, and very low contribution to the material budget. Although microchannel cooling is gaining considerable attention for applications related to microelectronics, it is still a novel technology for particle physics experiments, in particular when combined with evaporative CO2 cooling. The R&D effort for LHCb is focused on the design and layout of the channels together with a fluidic connector and its attachment which must withstand pressures up to 170 bar. Even distribution of the coolant is ensured by means of the use of restrictions implemented before the entrance to a race track like layout of the main cooling channels. The coolant flow and pressure drop have been simulated as well as the thermal performance of the device. This proceeding describes the design and optimization of the cooling system for LHCb and the latest prototyping results.

  9. Development and test of the CO2 evaporative cooling system for the LHCb UT Tracker Upgrade

    NASA Astrophysics Data System (ADS)

    Coelli, S.

    2017-03-01

    The LHCb upgrade requires a new silicon strip tracker detector placed between the vertex locator and the magnet. The new detector will have improved performance in charged particle tracking and triggering. The front-end electronics will be in the active area, close to the sensors: this is a key feature driving the mechanical and cooling detector design, together with the requirement to make the sensors work below -5°C, to withstand radiation damage. The new design exploits a cooling system based on CO2 evaporation at temperatures around -25°C. The support structure for the sensor modules is a lightweight carbon fiber mechanical structure embedding a cooling pipe, designed to pass underneath the read-out ASICs, which are the main thermal power sources to be cooled down. Here a description of the detector will be given, with a main focus on the cooling system and on the progress done to its qualification.

  10. [Chemical constituents from supercritical CO2 extraction of Schisandra chinensis].

    PubMed

    Zhu, Hong-yan; Lin, Hai-cheng; Wang, Guo-li; Zhang, Lian-xue

    2014-11-01

    To study the chemical constituents from the supercritical CO2 extraction of Schisandra chinensis. The compounds were separated and purified by conventional column chromatography and their structures were identified by spectroscopic methods. Nine compounds were isolated from the supercritical CO2 extraction of Schisandra chinensis, and their structures were identified as chrysophanol(1),schisandrin B(2), β-sitosterol(3), schisandrin C(4),schisandrol A(5), angeloylgomisin H(6), daucosterol(7) 1, 5-dimethyl citrate (8), and shikimic acid (9). Compounds 1, 8 and 9 are isolated from Schisandra chinensis for the first time,and compound 1 as an anthraquinone is isolated from this genus for the first time.

  11. Does atmospheric CO2 police the rate of chemical weathering?

    NASA Astrophysics Data System (ADS)

    Broecker, Wallace S.; Sanyal, Abhijit

    1998-09-01

    A case is made that in the absence of an effective feedback control on the rate of delivery of CaO to the oceans, the CO2 content of the Earth's atmosphere would have wandered over a large range threatening life either by overheating or by carbon dioxide starvation. In this paper, we defend the suggestion by Walker et al. [1981] that control is exerted by the interaction between the CO2 content of the atmosphere and the continental weathering rates. We contend that in spite of the arguments raised against it [Raymo and Ruddiman, 1992; Edmond and Huh, 1997] the CO2- chemical weathering feedback is the dominant mechanism that stabilizes the atmospheric carbon dioxide content.

  12. Effective CO2 adsorption on pristine and chemically functionalized MWCNTs

    NASA Astrophysics Data System (ADS)

    Shukrullah, Shazia; Mohamed, Norani Muti; Shaharun, Maizatul Shima; Ullah, Sami; Naz, Muhammad Yasin

    2016-11-01

    Carbon dioxide is one of the major greenhouse gases, which directly links to global warming. In this study, the laboratory produced multi-walled carbon nanotubes (MWCNTs) were amine-functionalized and tested for their potential as a CO2 adsorbent material. The CVD grown MWCNTs were treated with H2SO4/HNO3 and functionalized with 30% of 3-aminopropyltriethoxysilane (APTS). Both the pristine and functionalized MWCNTs were characterized for their surface morphology, chemical composition and functional groups by using FESEM, EDX and FTIR techniques. The acidic and APTS treatment to MWCNTs resulted in unbundling and loosening of the nanotubes from their bundled, agglomerated and entangled forms. Furthermore, oxidation and functionalization also significantly influenced the CO2 adsorption capacity of MWCNTs. The breakthrough curves (adsorption isotherms) revealed that the modified MWCNTs exhibit higher capacity for CO2 adsorption as compared to the pristine MWCNTs. Overall, CO2 uptake by the pristine and modified MWCNTs was found about 0.00025 mol/g and 0.00038 mol/g, respectively.

  13. Carbon and energy footprint of the hydrate-based biogas upgrading process integrated with CO2 valorization.

    PubMed

    Castellani, Beatrice; Rinaldi, Sara; Bonamente, Emanuele; Nicolini, Andrea; Rossi, Federico; Cotana, Franco

    2017-10-04

    The present paper aims at assessing the carbon and energy footprint of an energy process, in which the energy excess from intermittent renewable sources is used to produce hydrogen which reacts with the CO2 previously separated from an innovative biogas upgrading process. The process integrates a hydrate-based biogas upgrading section and a CO2 methanation section, to produce biomethane from the biogas enrichment and synthetic methane from the CO2 methanation. Clathrate hydrates are crystalline compounds, formed by gas enclathrated in cages of water molecules and are applied to the selective separation of CO2 from biogas mixtures. Data from the experimental setup were analyzed in order to evaluate the green-house gas emissions (carbon footprint CF) and the primary energy consumption (energy footprint EF) associated to the two sections of the process. The biosynthetic methane production during a single-stage process was 0.962Nm(3), obtained mixing 0.830Nm(3) of methane-enriched biogas and 0.132Nm(3) of synthetic methane. The final volume composition was: 73.82% CH4, 19.47% CO2, 0.67% H2, 1.98% O2, 4.06% N2 and the energy content was 28.0MJ/Nm(3). The functional unit is the unitary amount of produced biosynthetic methane in Nm(3). Carbon and energy footprints are 0.7081kgCO2eq/Nm(3) and 28.55MJ/Nm(3), respectively, when the electric energy required by the process is provided by photovoltaic panels. In this scenario, the overall energy efficiency is about 0.82, higher than the worldwide average energy efficiency for fossil methane, which is 0.75. Copyright © 2017 Elsevier B.V. All rights reserved.

  14. Hydroquinone and Quinone-Grafted Porous Carbons for Highly Selective CO2 Capture from Flue Gases and Natural Gas Upgrading.

    PubMed

    Wang, Jun; Krishna, Rajamani; Yang, Jiangfeng; Deng, Shuguang

    2015-08-04

    Hydroquinone and quinone functional groups were grafted onto a hierarchical porous carbon framework via the Friedel-Crafts reaction to develop more efficient adsorbents for the selective capture and removal of carbon dioxide from flue gases and natural gas. The oxygen-doped porous carbons were characterized with scanning electron microscopy, transmission electron microscopy, X-ray powder diffraction, Fourier transform infrared spectroscopy, and Raman spectroscopy. CO2, CH4, and N2 adsorption isotherms were measured and correlated with the Langmuir model. An ideal adsorbed solution theory (IAST) selectivity for the CO2/N2 separation of 26.5 (298 K, 1 atm) was obtained on the hydroquinone-grafted carbon, which is 58.7% higher than that of the pristine porous carbon, and a CO2/CH4 selectivity value of 4.6 (298 K, 1 atm) was obtained on the quinone-grafted carbon (OAC-2), which represents a 28.4% improvement over the pristine porous carbon. The highest CO2 adsorption capacity on the oxygen-doped carbon adsorbents is 3.46 mmol g(-1) at 298 K and 1 atm. In addition, transient breakthrough simulations for CO2/CH4/N2 mixture separation were conducted to demonstrate the good separation performance of the oxygen-doped carbons in fixed bed adsorbers. Combining excellent adsorption separation properties and low heats of adsorption, the oxygen-doped carbons developed in this work appear to be very promising for flue gas treatment and natural gas upgrading.

  15. HF chemical lasers ignited by CO2-laser irradiation

    NASA Astrophysics Data System (ADS)

    Cummings, J. C.

    HF gas mixtures lasing performances were examined by means of CO2 laser excitation of SF6:H2 and S2F10:H2 gas mixtures enclosed in an optical resonator cell. Variations in the mixing ratio, pressure, CO2 laser frequency, fluence, and pulse duration were monitored for effects on the HF lasing. A TEA CO2 laser was focussed on a 1 cm spot at the entrance to a 30 cm HF cell at a 1.4 deg angle. CO2 laser energy was absorbed at a rate of 310 mJ/torr of SF6 and 390 mJ/torr of S2F10, independent of the total pressure and mixing ratio. Nearly 6 times more energy was produced with the S2F10 mixture than the SF6 gas, and a linear increase in the HF laser energy followed increases in the CO2 laser fluence and mixture pressure. Both mixtures performed better with longer duration CO2 pulses, and the optimum CO2 frequency with the S2F6:H2 mixtures was blue-shifted.

  16. Low-temperature upgrading of low-calorific biogas for CO2 mitigation using DBD-catalyst hybrid reactor

    NASA Astrophysics Data System (ADS)

    Nozaki, Tomohiro; Tsukijihara, Hiroyuki; Fukui, Wataru; Okazaki, Ken

    2006-10-01

    Although huge amounts of biogas, which consists of 20-60% of CH4 in CO2/N2, can be obtained from landfills, coal mines, and agricultural residues, most of them are simply flared and wasted: because global warming potential of biogas is 5-15 times as potent as CO2. Poor combustibility of such biogas makes it difficult to utilize in conventional energy system. The purpose of this project is to promote the profitable recovery of methane from poor biogas via non-thermal plasma technology. We propose low-temperature steam reforming of biogas using DBD generated in catalyst beds. Methane is partially converted into hydrogen, and then fed into internal combustion engines for improved ignition stability as well as efficient operation. Low-temperature steam reforming is beneficial because exhaust gas from an engine can be used to activate catalyst beds. Space velocity (3600-15000 hr-1), reaction temperature (300-650^oC), and energy cost (30-150 kJ per mol CH4) have been investigated with simulated biogas (20-60% CH4 in mixtures of CO2/N2). The DBD enhances reaction rate of CH4 by a factor of ten at given catalyst temperatures, which is a rate-determining step of methane steam reforming, while species concentration of upgraded biogas was governed by thermodynamic equilibrium in the presence of catalyst.

  17. Carbon recycling by cyanobacteria: improving CO2 fixation through chemical production.

    PubMed

    Zhang, Angela; Carroll, Austin L; Atsumi, Shota

    2017-09-01

    Atmospheric CO2 levels have reached an alarming level due to industrialization and the burning of fossil fuels. In order to lower the level of atmospheric carbon, strategies to sequester excess carbon need to be implemented. The CO2-fixing mechanism in photosynthetic organisms enables integration of atmospheric CO2 into biomass. Additionally, through exogenous metabolic pathways in these photosynthetic organisms, fixed CO2 can be routed to produce various commodity chemicals that are currently produced from petroleum. This review will highlight studies and modifications to different components of cyanobacterial CO2-fixing systems, as well as the application of these systems toward CO2-derived chemical production. 2,3-Butanediol is given particular focus as one of the most thoroughly studied systems for conversion of CO2 to a bioproduct. © FEMS 2017. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

  18. CO2 adsorption on chemically modified activated carbon.

    PubMed

    Caglayan, Burcu Selen; Aksoylu, A Erhan

    2013-05-15

    CO2 adsorption capacity of a commercial activated carbon was improved by using HNO3 oxidation, air oxidation, alkali impregnation and heat treatment under helium gas atmosphere. The surface functional groups produced were investigated by diffuse reflectance infrared Fourier transform spectrometer (DRIFTS). CO2 adsorption capacities of the samples were determined by gravimetric analyses for 25-200°C temperature range. DRIFTS studies revealed the formation of carboxylic acid groups on the HNO3 oxidized adsorbents. Increased aromatization and uniform distribution of the Na particles were observed on the samples prepared by Na2CO3 impregnation onto HNO3 oxidized AC support. The adsorption capacities of the nonimpregnated samples were increased by high temperature helium treatments or by increasing the adsorption temperature; both leading to decomposition of surface oxygen groups, forming sites that can easily adsorb CO2. The adsorption capacity loss due to cyclic adsorption/desorption procedures was overcome with further surface stabilization of Na2CO3 modified samples with high temperature He treatments. With Na2CO3 impregnation the mass uptakes of the adsorbents at 20 bars and 25 °C were improved by 8 and 7 folds and at 1 bar were increased 15 and 16 folds, on the average, compared to their air oxidized and nitric acid oxidized supports, respectively.

  19. Will chemical defenses become more effective against specialist herbivores under elevated CO2?

    PubMed

    Landosky, John M; Karowe, David N

    2014-10-01

    Elevated atmospheric CO2 is known to affect plant-insect herbivore interactions. Elevated CO2 causes leaf nitrogen to decrease, the ostensible cause of herbivore compensatory feeding. CO2 may also affect herbivore consumption by altering chemical defenses via changes in plant hormones. We considered the effects of elevated CO2, in conjunction with soil fertility and damage (simulated herbivory), on glucosinolate concentrations of mustard (Brassica nigra) and collard (B. oleracea var. acephala) and the effects of leaf nitrogen and glucosinolate groups on specialist Pieris rapae consumption. Elevated CO2 affected B. oleracea but not B. nigra glucosinolates; responses to soil fertility and damage were also species-specific. Soil fertility and damage also affected B. oleracea glucosinolates differently under elevated CO2. Glucosinolates did not affect P. rapae consumption at either CO2 concentration in B. nigra, but had CO2-specific effects on consumption in B. oleracea. At ambient CO2, leaf nitrogen had strong effects on glucosinolate concentrations and P. rapae consumption but only gluconasturtiin was a feeding stimulant. At elevated CO2, direct effects of leaf nitrogen were weaker, but glucosinolates had stronger effects on consumption. Gluconasturtiin and aliphatic glucosinolates were feeding stimulants and indole glucosinolates were feeding deterrents. These results do not support the compensatory feeding hypothesis as the sole driver of changes in P. rapae consumption under elevated CO2. Support for hormone-mediated CO2 response (HMCR) was mixed; it explained few treatment effects on constitutive or induced glucosinolates, but did explain patterns in SEMs. Further, the novel feeding deterrent effect of indole glucosinolates under elevated CO2 in B. oleracae underscores the importance of defensive chemistry in CO2 response. We speculate that P. rapae indole glucosinolate detoxification mechanisms may have been overwhelmed under elevated CO2 forcing slowed

  20. Enhancement of field emission of CNTs array by CO2-assisted chemical vapor deposition.

    PubMed

    Wu, Jun; Ma, Yanfeng; Tang, Daiming; Liu, Chang; Huang, Qinwen; Huang, Yi; Cheng, Huiming; Chen, Dapeng; Chen, Yongsheng

    2009-05-01

    We present a new process to get in-situ-growth carbon nanotubes (CNTs) array device with good FE properties by CO2-assisted thermal chemical vapor deposition (CVD). Field Emission measurement shows that introducing CO2 into CNTs growth system leads to a significant enhancement in the emission properties, both the turn-on field and threshold field decrease. Raman, SEM and TEM investigation results showed that in this CO2-assisted thermal CVD, CO2 can remove amorphous carbon during CNTs growth process, and at the same time, it also creates more defects on the CNTs wall. Both can enhance FE properties of the CNTs at suitable CO2 concentrations.

  1. Chemical transformation of CO2 during its capture by waste biomass derived biochars.

    PubMed

    Xu, Xiaoyun; Kan, Yue; Zhao, Ling; Cao, Xinde

    2016-06-01

    Biochar is a porous carbonaceous material with high alkalinity and rich minerals, making it possible for CO2 capture. In this study, biochars derived from pig manure, sewage sludge, and wheat straw were evaluated for their CO2 sorption behavior. All three biochars showed high sorption abilities for CO2, with the maximum capacities reaching 18.2-34.4 mg g(-1) at 25 °C. Elevating sorption temperature and moisture content promoted the transition of CO2 uptake from physical to chemical process. Mineral components such as Mg, Ca, Fe, K, etc. in biochar induced the chemical sorption of CO2 via the mineralogical reactions which occupied 17.7%-50.9% of the total sorption. FeOOH in sewage sludge biochar was transformed by sorbed CO2 into Fe(OH)2CO3, while the sorbed CO2 in pig manure biochar was precipitated as K2Ca(CO3)2 and CaMg(CO3)2, which resulted in a dominant increase of insoluble inorganic carbon in both biochars. For wheat straw biochar, sorbed CO2 induced CaCO3 transformed into soluble Ca(HCO3)2, which led to a dominant increase of soluble inorganic carbons. The results obtained from this study demonstrated that biochar as a unique carbonaceous material could distinctly be a promising sorbent for CO2 capture in which chemical sorption induced by mineralogical reactions played an important role.

  2. Encapsulated Ionic Liquids for CO2 Capture: Using 1-Butyl-methylimidazolium Acetate for Quick and Reversible CO2 Chemical Absorption.

    PubMed

    Moya, Cristian; Alonso-Morales, Noelia; Gilarranz, Miguel A; Rodriguez, Juan J; Palomar, Jose

    2016-12-05

    The potential advantages of applying encapsulated ionic liquid (ENIL) to CO2 capture by chemical absorption with 1-butyl-3-methylimidazolium acetate [bmim][acetate] are evaluated. The [bmim][acetate]-ENIL is a particle material with solid appearance and 70 % w/w in ionic liquid (IL). The performance of this material as CO2 sorbent was evaluated by gravimetric and fixed-bed sorption experiments at different temperatures and CO2 partial pressures. ENIL maintains the favourable thermodynamic properties of the neat IL regarding CO2 absorption. Remarkably, a drastic increase of CO2 sorption rates was achieved using ENIL, related to much higher contact area after discretization. In addition, experiments demonstrate reversibility of the chemical reaction and the efficient ENIL regeneration, mainly hindered by the unfavourable transport properties. The common drawback of ILs as CO2 chemical absorbents (low absorption rate and difficulties in solvent regeneration) are overcome by using ENIL systems.

  3. CO2 utilization: an enabling element to move to a resource- and energy-efficient chemical and fuel production.

    PubMed

    Ampelli, Claudio; Perathoner, Siglinda; Centi, Gabriele

    2015-03-13

    CO(2) conversion will be at the core of the future of low-carbon chemical and energy industry. This review gives a glimpse into the possibilities in this field by discussing (i) CO(2) circular economy and its impact on the chemical and energy value chain, (ii) the role of CO(2) in a future scenario of chemical industry, (iii) new routes for CO(2) utilization, including emerging biotechnology routes, (iv) the technology roadmap for CO(2) chemical utilization, (v) the introduction of renewable energy in the chemical production chain through CO(2) utilization, and (vi) CO(2) as a suitable C-source to move to a low-carbon chemical industry, discussing in particular syngas and light olefin production from CO(2). There are thus many stimulating possibilities offered by using CO(2) and this review shows this new perspective on CO(2) at the industrial, societal and scientific levels.

  4. Porous MOF with Highly Efficient Selectivity and Chemical Conversion for CO2.

    PubMed

    Wang, Hai-Hua; Hou, Lei; Li, Yong-Zhi; Jiang, Chen-Yu; Wang, Yao-Yu; Zhu, Zhonghua

    2017-05-31

    A new Co(II)-based MOF, {[Co2(tzpa)(OH)(H2O)2]·DMF}n (1) (H3tzpa = 5-(4-(tetrazol-5-yl)phenyl)isophthalic acid), was constructed by employing a tetrazolyl-carboxyl ligand H3tzpa. 1 possesses 1D tubular channels that are decorated by μ3-OH groups, uncoordinated carboxylate O atoms, and open metal centers generated by the removal of coordinated water molecules, leading to high CO2 adsorption capacity and significantly selective capture for CO2 over CH4 and CO in the temperature range of 298-333 K. Moreover, 1 shows the chemical stability in acidic and basic aqueous solutions. Grand canonical Monte Carlo simulations identified multiple CO2-philic sites in 1. In addition, the activated 1 as the heterogeneous Lewis and Brønsted acid bifunctional catalyst facilitates the chemical fixation of CO2 coupling with epoxides into cyclic carbonates under ambient conditions.

  5. Organic reactions for the electrochemical and photochemical production of chemical fuels from CO2--The reduction chemistry of carboxylic acids and derivatives as bent CO2 surrogates.

    PubMed

    Luca, Oana R; Fenwick, Aidan Q

    2015-11-01

    The present review covers organic transformations involved in the reduction of CO2 to chemical fuels. In particular, we focus on reactions of CO2 with organic molecules to yield carboxylic acid derivatives as a first step in CO2 reduction reaction sequences. These biomimetic initial steps create opportunities for tandem electrochemical/chemical reductions. We draw parallels between long-standing knowledge of CO2 reactivity from organic chemistry, organocatalysis, surface science and electrocatalysis. We point out some possible non-faradaic chemical reactions that may contribute to product distributions in the production of solar fuels from CO2. These reactions may be accelerated by thermal effects such as resistive heating and illumination.

  6. Nanoscale Chemical Processes Affecting Storage Capacities and Seals during Geologic CO2 Sequestration.

    PubMed

    Jun, Young-Shin; Zhang, Lijie; Min, Yujia; Li, Qingyun

    2017-07-18

    Geologic CO2 sequestration (GCS) is a promising strategy to mitigate anthropogenic CO2 emission to the atmosphere. Suitable geologic storage sites should have a porous reservoir rock zone where injected CO2 can displace brine and be stored in pores, and an impermeable zone on top of reservoir rocks to hinder upward movement of buoyant CO2. The injection wells (steel casings encased in concrete) pass through these geologic zones and lead CO2 to the desired zones. In subsurface environments, CO2 is reactive as both a supercritical (sc) phase and aqueous (aq) species. Its nanoscale chemical reactions with geomedia and wellbores are closely related to the safety and efficiency of CO2 storage. For example, the injection pressure is determined by the wettability and permeability of geomedia, which can be sensitive to nanoscale mineral-fluid interactions; the sealing safety of the injection sites is affected by the opening and closing of fractures in caprocks and the alteration of wellbore integrity caused by nanoscale chemical reactions; and the time scale for CO2 mineralization is also largely dependent on the chemical reactivities of the reservoir rocks. Therefore, nanoscale chemical processes can influence the hydrogeological and mechanical properties of geomedia, such as their wettability, permeability, mechanical strength, and fracturing. This Account reviews our group's work on nanoscale chemical reactions and their qualitative impacts on seal integrity and storage capacity at GCS sites from four points of view. First, studies on dissolution of feldspar, an important reservoir rock constituent, and subsequent secondary mineral precipitation are discussed, focusing on the effects of feldspar crystallography, cations, and sulfate anions. Second, interfacial reactions between caprock and brine are introduced using model clay minerals, with focuses on the effects of water chemistries (salinity and organic ligands) and water content on mineral dissolution and surface

  7. Soil CO2 dynamics, acidification, and chemical weathering in a temperate forest with experimental CO2 enrichment

    NASA Astrophysics Data System (ADS)

    Andrews, Jeffrey A.; Schlesinger, William H.

    2001-03-01

    Soils constitute a major component of the global carbon cycle that will be affected by anthropogenic additions of CO2 to the atmosphere. As part of the Duke Forest Free-Air CO2 Enrichment (FACE) experiment, we examined how forest growth at elevated (+200 ppmv) atmospheric CO2 concentration affects CO2 dynamics in the soil. Soil respiration and the concentration of CO2 in the soil pore space to a depth of 200 cm were measured over a 3-year period. Soil CO2 production was linked to soil acidification and mineral weathering by measuring changes in the composition of the soil solution, including alkalinity, Si, and major cations. The total flux of dissolved inorganic carbon to groundwater was then calculated from field measurements. The FACE fumigation gas contained a unique 13C signature that labeled newly fixed carbon, which was monitored in the soil system. As a result of CO2 enrichment, annual soil respiration increased by 27% and was accompanied by higher CO2 concentrations in the soil pore space. These changes to soil CO2 dynamics were most likely the result of increased root and rhizosphere respiration, as suggested by the changes to the δ13C of soil CO2. Increased soil CO2 under FACE accelerated the rates of soil acidification and mineral weathering. Thus an increase of 55% in atmospheric CO2 concentration over 2 years resulted in a 271% increase in soil solution cation concentration, a 162% increase in alkalinity, and a 25% increase in Si concentration at 200-cm depth. The flux of dissolved inorganic carbon to groundwater increased by 33%, indicating a negative feedback to changes in atmospheric CO2 that could regulate the global carbon cycle over geological time.

  8. Early opportunities of CO2 geological storage deployment in coal chemical industry in China

    SciTech Connect

    Wei, Ning; Li, Xiaochun; Liu, Shengnan; Dahowski, Robert T.; Davidson, Casie L.

    2014-11-12

    Abstract: Carbon dioxide capture and geological storage (CCS) is regarded as a promising option for climate change mitigation; however, the high capture cost is the major barrier to large-scale deployment of CCS technologies. High-purity CO2 emission sources can reduce or even avoid the capture requirements and costs. Among these high-purity CO2 sources, certain coal chemical industry processes are very important, especially in China. In this paper, the basic characteristics of coal chemical industries in China is investigated and analyzed. As of 2013 there were more than 100 coal chemical plants in operation or in late planning stages. These emission sources together emit 430 million tons CO2 per year, of which about 30% are emit high-purity and pure CO2 (CO2 concentration >80% and >99% respectively).Four typical source-sink pairs are studied by a techno-economic evaluation, including site screening and selection, source-sink matching, concept design, and experienced economic evaluation. The technical-economic evaluation shows that the levelized cost of a CO2 capture and aquifer storage project in the coal chemistry industry ranges from 14 USD/t to 17 USD/t CO2. When a 15USD/t CO2 tax and 15USD/t for CO2 sold to EOR are considered, the levelized cost of CCS project are negative, which suggests a net economic benefit from some of these CCS projects. This might provide China early opportunities to deploy and scale-up CCS projects in the near future.

  9. Thermo-chemical process with sewage sludge by using CO2.

    PubMed

    Kwon, Eilhann E; Yi, Haakrho; Kwon, Hyun-Han

    2013-10-15

    This work proposed a novel methodology for energy recovery from sewage sludge via the thermo-chemical process. The impact of CO2 co-feed on the thermo-chemical process (pyrolysis and gasification) of sewage sludge was mainly investigated to enhance thermal efficiency and to modify the end products from the pyrolysis and gasification process. The CO2 injected into the pyrolysis and gasification process enhance the generation of CO. As compared to the thermo-chemical process in an inert atmosphere (i.e., N2), the generation of CO in the presence of CO2 was enhanced approximately 200% at the temperature regime from 600 to 900 °C. The introduction of CO2 into the pyrolysis and gasification process enabled the condensable hydrocarbons (tar) to be reduced considerably by expediting thermal cracking (i.e., approximately 30-40%); thus, exploiting CO2 as chemical feedstock and/or reaction medium for the pyrolysis and gasification process leads to higher thermal efficiency, which leads to environmental benefits. This work also showed that sewage sludge could be a very strong candidate for energy recovery and a raw material for chemical feedstock.

  10. Feasibility study of a novel pressure recovery system for CO2-COIL based on chemical absorption

    NASA Astrophysics Data System (ADS)

    Li, Qingwei; Jin, Yuqi; Geng, Zicai; Li, Yongzhao; Zhang, Yuelong; Sang, Fengting

    2015-02-01

    A chemical oxygen-iodine laser (COIL) is an electronic transition, low pressure, high throughput system. The use of this laser demands a suitable pressure recovery system. This paper proposed a novel pressure recovery system based on chemical absorption and the feasibility for COIL with CO2 as buffer gas (CO2-COIL) was investigated. The novel pressure recovery system works by chemisorbing the CO2-COIL effluents into two fixed-beds maintained at initial temperature of around 293-323K. Compared with the cryosorption system for N2-COIL based on physical absorption, the novel chemisorptions based pressure recovery system has a simpler logistics and a shorter run-to-run preparation time. Two kinds of solid chemo-sorbents were designed and synthesized. One was used for chemisorbing the oxidizing gases such as O2 ,Cl2 and I2, another was used for chemisorbing the acidic gas such as CO2. The capacities of the two sorbents were measured to be 3.12 mmol(O2)/g and 3.84 mmol (CO2) /g, respectively. It indicated that the synthesized sorbents could effectively chemosorb the CO2-COIL effluents. Secondly, analog test equipment was set up and used to study the feasibility of the novel pressure recovery system used for CO2-COIL. The test results showed that the novel pressure recovery system could maintain the pressure under 6 Torr for tens seconds under the continuous gas flow. It showed that the novel pressure recovery system for CO2-COIL based on chemical absorption is feasible.

  11. Biocatalysis for the application of CO2 as a chemical feedstock

    PubMed Central

    Easton, Christopher J

    2015-01-01

    Summary Biocatalysts, capable of efficiently transforming CO2 into other more reduced forms of carbon, offer sustainable alternatives to current oxidative technologies that rely on diminishing natural fossil-fuel deposits. Enzymes that catalyse CO2 fixation steps in carbon assimilation pathways are promising catalysts for the sustainable transformation of this safe and renewable feedstock into central metabolites. These may be further converted into a wide range of fuels and commodity chemicals, through the multitude of known enzymatic reactions. The required reducing equivalents for the net carbon reductions may be drawn from solar energy, electricity or chemical oxidation, and delivered in vitro or through cellular mechanisms, while enzyme catalysis lowers the activation barriers of the CO2 transformations to make them more energy efficient. The development of technologies that treat CO2-transforming enzymes and other cellular components as modules that may be assembled into synthetic reaction circuits will facilitate the use of CO2 as a renewable chemical feedstock, greatly enabling a sustainable carbon bio-economy. PMID:26734087

  12. Biocatalysis for the application of CO2 as a chemical feedstock.

    PubMed

    Alissandratos, Apostolos; Easton, Christopher J

    2015-01-01

    Biocatalysts, capable of efficiently transforming CO2 into other more reduced forms of carbon, offer sustainable alternatives to current oxidative technologies that rely on diminishing natural fossil-fuel deposits. Enzymes that catalyse CO2 fixation steps in carbon assimilation pathways are promising catalysts for the sustainable transformation of this safe and renewable feedstock into central metabolites. These may be further converted into a wide range of fuels and commodity chemicals, through the multitude of known enzymatic reactions. The required reducing equivalents for the net carbon reductions may be drawn from solar energy, electricity or chemical oxidation, and delivered in vitro or through cellular mechanisms, while enzyme catalysis lowers the activation barriers of the CO2 transformations to make them more energy efficient. The development of technologies that treat CO2-transforming enzymes and other cellular components as modules that may be assembled into synthetic reaction circuits will facilitate the use of CO2 as a renewable chemical feedstock, greatly enabling a sustainable carbon bio-economy.

  13. Global metabolic rewiring for improved CO2 fixation and chemical production in cyanobacteria.

    PubMed

    Kanno, Masahiro; Carroll, Austin L; Atsumi, Shota

    2017-03-13

    Cyanobacteria have attracted much attention as hosts to recycle CO2 into valuable chemicals. Although cyanobacteria have been engineered to produce various compounds, production efficiencies are too low for commercialization. Here we engineer the carbon metabolism of Synechococcus elongatus PCC 7942 to improve glucose utilization, enhance CO2 fixation and increase chemical production. We introduce modifications in glycolytic pathways and the Calvin Benson cycle to increase carbon flux and redirect it towards carbon fixation. The engineered strain efficiently uses both CO2 and glucose, and produces 12.6 g l(-1) of 2,3-butanediol with a rate of 1.1 g l(-1) d(-1) under continuous light conditions. Removal of native regulation enables carbon fixation and 2,3-butanediol production in the absence of light. This represents a significant step towards industrial viability and an excellent example of carbon metabolism plasticity.

  14. Global metabolic rewiring for improved CO2 fixation and chemical production in cyanobacteria

    NASA Astrophysics Data System (ADS)

    Kanno, Masahiro; Carroll, Austin L.; Atsumi, Shota

    2017-03-01

    Cyanobacteria have attracted much attention as hosts to recycle CO2 into valuable chemicals. Although cyanobacteria have been engineered to produce various compounds, production efficiencies are too low for commercialization. Here we engineer the carbon metabolism of Synechococcus elongatus PCC 7942 to improve glucose utilization, enhance CO2 fixation and increase chemical production. We introduce modifications in glycolytic pathways and the Calvin Benson cycle to increase carbon flux and redirect it towards carbon fixation. The engineered strain efficiently uses both CO2 and glucose, and produces 12.6 g l-1 of 2,3-butanediol with a rate of 1.1 g l-1 d-1 under continuous light conditions. Removal of native regulation enables carbon fixation and 2,3-butanediol production in the absence of light. This represents a significant step towards industrial viability and an excellent example of carbon metabolism plasticity.

  15. Global CO2-consumption by chemical weathering: What is the contribution of highly active weathering regions?

    NASA Astrophysics Data System (ADS)

    Hartmann, Jens; Jansen, Nils; Dürr, Hans H.; Kempe, Stephan; Köhler, Peter

    2010-05-01

    CO2-consumption by chemical weathering of silicates and resulting silicate/carbonate weathering ratios influences the terrestrial lateral inorganic carbon flux to the ocean and long-term climate changes. However, little is known of the spatial extension of highly active weathering regions and their proportion of global CO2-consumption. As those regions may be of significant importance for global climate change, global CO2-consumption is calculated here at high resolution, to adequately represent them. In previous studies global CO2-consumption is estimated using two different approaches: i) a reverse approach based on hydrochemical fluxes from large rivers and ii) a forward approach applying spatially explicit a function for CO2-consumption. The first approach results in an estimate without providing a spatial resolution for highly active regions and the second approach applied six lithological classes while including three sediment classes (shale, sandstone and carbonate rock) based at a 1° or 2° grid resolution. It remained uncertain, if the applied lithological classification schemes represent adequately CO2-consumption from sediments on a global scale (as well as liberation of other elements like phosphorus or silicon by chemical weatheirng). This is due to the large variability of sediment properties, their diagenetic history and the contribution from carbonates apparent in silicate dominated lithological classes. To address these issues, a CO2-consumption model, trained at high-resolution data, is applied here to a global vector based lithological map with 15 lithological classes. The calibration data were obtained from areas representing a wide range of weathering rates. Resulting global CO2-consumption by chemical weathering is similar to earlier estimates (237 Mt C a-1) but the proportion of silicate weathering is 63%, and thus larger than previous estimates (49 to 60%). The application of the enhanced lithological classification scheme reveals that it

  16. Physico-Chemical Behavior of Nanoparticles at CO2-Water-Rock Interfaces

    NASA Astrophysics Data System (ADS)

    Jun, Y.; Shao, H.; Hu, Y.; Matos, R.

    2009-12-01

    Recently, to help mitigate global climate-change and energy problems, much effort has recently been devoted to developing methods for sequestering anthropogenic CO2 from coal-fired power plants. One of the most promising methods is geological CO2 sequestration (GS). Some prior studies of geological CO2 sequestration have mainly examined the physical processes that occur during the sequestration of CO2. However, most of the relevant studies are based on hydrological transport, using simulation models rather than studying actual interfacial chemical reactions in the ground. The mechanisms, kinetics, and environmental impact of interfacial reactions among CO2-H2O-mineral surfaces at the molecular scale have not been well understood. Changes in the porosity of the mineral phases at the geological formation sites, especially the dissolution of the mineral phase or precipitation of secondary minerals in the pores, will affect the fate and transport of CO2 and the integrity of seals and the matrix within the reservoirs. So far, little is known about the kinetics of the possible geochemical reactions of supercritical CO2 in brine and pre-existing mineral interfaces, or about the ultimate fate and transport of the injected CO2. We investigated the physico-chemical property changes of reference mineral samples (clay minerals) as well as field site samples (sandstone and caprock from the Illinois Basin) by chemical reactions at CO2-H2O-mineral interfaces. We investigated whether reactions between caprock and CO2 can change the integrity of caprock. Our experimental results with caprock samples (CONSOL coal mine sites, West Virginia) indicate that after 14 days in contact with 1 atm CO2 saturated saline water at 80°C, the concentrations of dissolved metals have increased from zero to as high as 47,000 ppm. In our experiments with caprocks and sandstones from GS sites of the Midwest Geological Sequestration Consortium, we found that the most significant extent of dissolution

  17. O3, CO2 and chemical fractionation in ponderosa pine saplings

    EPA Science Inventory

    Environmental factors can affect plant tissue quality which is important for quality of organic matter inputs into soil food webs and decomposition of soil organic matter. Thus the effects of increases in CO2 and O3 and their interactions were determined for various chemical fra...

  18. O3, CO2 and chemical fractionation in ponderosa pine saplings

    EPA Science Inventory

    Environmental factors can affect plant tissue quality which is important for quality of organic matter inputs into soil food webs and decomposition of soil organic matter. Thus the effects of increases in CO2 and O3 and their interactions were determined for various chemical fra...

  19. CO2 recycling: a key strategy to introduce green energy in the chemical production chain.

    PubMed

    Perathoner, Siglinda; Centi, Gabriele

    2014-05-01

    The introduction of renewable energy in the chemical production chain is a key strategic factor both to realize a sustainable, resource-efficient, low-carbon economy and society and to drive innovation and competiveness in the chemical production. This Concept discusses this concept in terms of motivations, perspectives, and impact as well as technical barriers to achieve this goal. It is shown how an important element to realize this scenario is to foster the paths converting carbon dioxide (CO2) into feedstock for the chemical/process industry, which is one of the most efficient methods to rapidly introduce renewable energy into the chemical production chain. Some of the possible options to proceed in this direction are discussed, with focus on the technical barriers and enabling factors such as catalysis. The tight interconnection between CO2 management and the use of renewable energy is evidenced.

  20. Sorbents with high efficiency for CO2 capture based on amines-supported carbon for biogas upgrading.

    PubMed

    Pino, Lidia; Italiano, Cristina; Vita, Antonio; Fabiano, Concetto; Recupero, Vincenzo

    2016-10-01

    Sorbents for CO2 capture have been prepared by wet impregnation of a commercial active carbon (Ketjen-black, Akzo Nobel) with two CO2-philic compounds, polyethylenimine (PEI) and tetraethylenepentamine (TEPA), respectively. The effects of amine amount (from 10 to 70wt.%), CO2 concentration in the feed, sorption temperature and gas hourly space velocity on the CO2 capture performance have been investigated. The sorption capacity has been evaluated using the breakthrough method, with a fixed bed reactor equipped with on line gas chromatograph. The samples have been characterized by N2 adsorption-desorption, scanning electron microscopy and energy dispersive X-ray (SEM/EDX). A promising CO2 sorption capacity of 6.90 mmol/gsorbent has been obtained with 70wt.% of supported TEPA at 70°C under a stream containing 80vol% of CO2. Sorption tests, carried out with simulated biogas compositions (CH4/CO2 mixtures), have revealed an appreciable CO2 separation selectivity; stable performance was maintained for 20 adsorption-desorption cycles.

  1. Catalytic upgrading of butyric acid towards fine chemicals and biofuels

    PubMed Central

    Sjöblom, Magnus; Matsakas, Leonidas; Christakopoulos, Paul; Rova, Ulrika

    2016-01-01

    Fermentation-based production of butyric acid is robust and efficient. Modern catalytic technologies make it possible to convert butyric acid to important fine chemicals and biofuels. Here, current chemocatalytic and biocatalytic conversion methods are reviewed with a focus on upgrading butyric acid to 1-butanol or butyl-butyrate. Supported Ruthenium- and Platinum-based catalyst and lipase exhibit important activities which can pave the way for more sustainable process concepts for the production of green fuels and chemicals. PMID:26994015

  2. Microbial, Physical and Chemical Drivers of COS and 18O-CO2 Exchange in Soils

    NASA Astrophysics Data System (ADS)

    Meredith, L. K.; Boye, K.; Whelan, M.; Pang, E.; von Sperber, C.; Brueggemann, N.; Berry, J. A.; Welander, P. V.

    2015-12-01

    Carbonyl sulfide (COS) and the oxygen isotope composition (δ18O) of CO2 are potential tools for differentiating the contributions of photosynthesis and respiration to the balance of global carbon cycling. These processes are coupled at the leaf level via the enzyme carbonic anhydrase (CA), which hydrolyzes CO2 in the first biochemical step of the photosynthetic pathway (CO2 + H2O ⇌ HCO3- + H+) and correspondingly structural analogue COS (COS + H2O → CO2 + H2S). CA also accelerates the exchange of oxygen isotopes between CO2 and H2O leading to a distinct isotopic imprint [1]. The biogeochemical cycles of these tracers include significant, yet poorly characterized soil processes that challenge their utility for probing the carbon cycle. In soils, microbial CA also hydrolyze COS and accelerate O isotope exchange between CO2 and soil water. Soils have been observed to emit COS by undetermined processes. To account for these soil processes, measurements are needed to identify the key microbial, chemical, and physical factors. In this study, we survey COS and δ18O exchange in twenty different soils spanning a variety of biomes and soil properties. By comparing COS fluxes and δ18O-CO2 values emitted from moist soils we investigate whether the same types of CA catalyze these two processes. Additionally, we seek to identify the potential chemical drivers of COS emissions by measuring COS fluxes in dry soils. These data are compared with soil physical (bulk density, volumetric water content, texture), chemical (pH, elemental analysis, sulfate, sulfur K-edge XANES), and microbial measurements (biomass and phylogeny). Furthermore, we determine the abundance and diversity of CA-encoding genes to directly link CA with measured soil function. This work will define the best predictors for COS fluxes and δ18O-CO2 values from our suite of biogeochemical measurements. The suitability of identified predictor variables can be tested in follow-up studies and applied for modeling

  3. CO2 laser scribe of chemically strengthened glass with high surface compressive stress

    NASA Astrophysics Data System (ADS)

    Li, Xinghua; Vaddi, Butchi R.

    2011-03-01

    Chemically strengthened glass is finding increasing use in handheld, IT and TV cover glass applications. Chemically strengthened glass, particularly with high (>600MPa) compressive stress (CS) and deeper depth of layer (DOL), enable to retain higher strength after damage than non-strengthened glass when its surface is abraded. Corning Gorilla® Glass has particularly proven to be advantageous over competition in this attribute. However, due to high compressive stress (CS) and Central Tension (CT) cutting ion-exchanged glass is extremely difficult and often unmanageable where ever the applications require dicing the chemically strengthened mother glass into smaller parts. We at Corning have developed a CO2 laser scribe and break method (LSB) to separate a single chemically strengthened glass sheet into plurality of devices. Furthermore, CO2 laser scribe and break method enables debris-free separation of glass with high edge strength due to its mirror-like edge finish. We have investigated laser scribe and break of chemically strengthened glass with surface compressive stress greater than 600 MPa. In this paper we present the results of CO2 scribe and break method and underlying laser scribing mechanisms. We demonstrated cross-scribe repetitively on GEN 2 size chemically strengthened glass substrates. Specimens for edge strength measurements of different thickness and CS/DOL glass were prepared using the laser scribe and break technique. The specimens were tested using the standard 4-point bend method and the results are presented.

  4. Experimental and Quantum Chemical Approaches to Develop Highly Selective Nanocatalysts for CO2 -free Power Circulation.

    PubMed

    Yamauchi, Miho; Ozawa, Nobuki; Kubo, Momoji

    2016-10-01

    Renewable electricity must be utilized to usefully suppress the atmospheric CO2 concentration and slow the progression of global warming. We have thus proposed a new concept involving CO2 -free electric power circulation systems via highly selective electrochemical reactions of alcohol/carboxylic acid redox couples. Design concepts for nanocatalysts able to catalyze highly selective electrochemical reactions are provided from both experimental and quantum mechanical perspectives. © 2016 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Carbamate stabilities of sterically hindered amines from quantum chemical methods: relevance for CO2 capture.

    PubMed

    Gangarapu, Satesh; Marcelis, Antonius T M; Zuilhof, Han

    2013-12-02

    The influence of electronic and steric effects on the stabilities of carbamates formed from the reaction of CO2 with a wide range of alkanolamines was investigated by quantum chemical methods. For the calculations, B3LYP, M11-L, MP2, and spin-component-scaled MP2 (SCS-MP2) methods were used, coupled with SMD and SM8 solvation models. A reduction in carbamate stability leads to an increased CO2 absorption capacity of the amine and a reduction of the energy required for solvent regeneration. Important factors for the reduction of the carbamate stability were an increase in steric hindrance around the nitrogen atom, charge on the N atom and intramolecular hydrogen bond strength. The present study indicates that secondary ethanolamines with sterically hindering groups near the N atom show significant potential as candidates for industrial CO2-capture solvents.

  6. Frontiers, Opportunities, and Challenges in Biochemical and Chemical Catalysis of CO2

    SciTech Connect

    Appel, Aaron M.; Bercaw, John E.; Bocarsly, Andrew B.; Dobbek, Holger; DuBois, Daniel L.; Dupuis, Michel; Ferry, James G.; Fujita, Etsuko; Hille, Russ; Kenis, Paul; Kerfeld, Cheryl A.; Morris, Robert H.; Peden, Charles HF; Portis, Archie; Ragsdale, Steve; Rauchfuss, Thomas B.; Reek, Joost; Seefeldt, Lance C.; Thauer, Rudolf K.; Waldrop, Grover L.

    2013-08-14

    Our central premise is that catalytic scientists can learn by studying how these important metabolic processes occur in nature. Complementarily, biochemists can learn by studying how catalytic scientists view these same chemical transformations promoted by synthetic catalysts. From these studies, hypotheses can be developed and tested through manipulation of enzyme structure and by synthesizing simple molecular catalysts to incorporate different structural features of the enzymes. It is hoped that these studies will lead to new and useful concepts in catalyst design for fuel production and utilization. This paper describes the results of a workshop held to explore these concepts in regard to the development of new and more efficient catalytic processes for the conversion of CO2 to a variety of carbon-based fuels. The organization of this overview/review is as follows: 1) The first section briefly explores how interactions between the catalysis and biological communities have been fruitful in developing new catalysts for the reduction of protons to hydrogen, the simplest fuel generation reaction. 2) The second section assesses the state of the art in both biological and chemical reduction of CO2 by two electrons to form either carbon monoxide (CO) or formate (HCOO-). It also attempts to identify common principles between biological and synthetic catalysts and productive areas for future research. 3) The third section explores both biological and chemical processes that result in the reduction of CO2 beyond the level of CO and formate, again seeking to identify common principles and productive areas of future research. 4) The fourth section explores the formation of carbon-carbon bonds in biological and chemical systems in the same vein as the other sections. 5) A fifth section addresses the role of non-redox reactions of CO2 in biological systems and their role in carbon metabolism, with a parallel discussion of chemical systems. 6) In section 6, the topics of

  7. Bio-electrochemical synthesis of commodity chemicals by autotrophic acetogens utilizing CO2 for environmental remediation.

    PubMed

    Jabeen, Gugan; Farooq, Robina

    2016-09-01

    Bio-electrochemical synthesis (BES) is a technique in which electro-autotrophic bacteria such as Clostridium ljungdahlii utilize electric currents as an electron source from the cathode to reduce CO2 to extracellular, multicarbon, exquisite products through autotrophic conversion. The BES of volatile fatty acids and alcohols directly from CO2 is a sustainable alternative for non-renewable, petroleum-based polymer production. This conversion of CO2 implies reduction of greenhouse gas emissions. The synthesis of heptanoic acid, heptanol, hexanoic acid and hexanol, for the first time, by Clostridium ljungdahlii was a remarkable achievement of BES. In our study, these microorganisms were cultivated on the cathode of a bio-electrochemical cell at -400 mV by a DC power supply at 37 degree Centrigrade, pH 6.8, and was studied for both batch and continuous systems. Pre-enrichment of bio-cathode enhanced the electroactivity of cells and resulted in maximizing extracellular products in less time. The main aim of the research was to investigate the impact of low-cost substrate CO2, and the longer cathode recovery range was due to bacterial reduction of CO2 to multicarbon chemical commodities with electrons driven from the cathode. Reactor design was simplified for cost-effectiveness and to enhance energy efficiencies. The Columbic recovery of ethanoic acid, ethanol, ethyl butyrate, hexanoic acid, heptanoic acid and hexanol being in excess of 80 percent proved that BES was a remarkable technology.

  8. Microbial electrolysis desalination and chemical-production cell for CO2 sequestration.

    PubMed

    Zhu, Xiuping; Logan, Bruce E

    2014-05-01

    Mineral carbonation can be used for CO2 sequestration, but the reaction rate is slow. In order to accelerate mineral carbonation, acid generated in a microbial electrolysis desalination and chemical-production cell (MEDCC) was examined to dissolve natural minerals rich in magnesium/calcium silicates (serpentine), and the alkali generated by the same process was used to absorb CO2 and precipitate magnesium/calcium carbonates. The concentrations of Mg(2+) and Ca(2+) dissolved from serpentine increased 20 and 145 times by using the acid solution. Under optimal conditions, 24 mg of CO2 was absorbed into the alkaline solution and 13 mg of CO2 was precipitated as magnesium/calcium carbonates over a fed-batch cycle (24h). Additionally, the MEDCC removed 94% of the COD (initially 822 mg/L) and achieved 22% desalination (initially 35 g/L NaCl). These results demonstrate the viability of this process for effective CO2 sequestration using renewable organic matter and natural minerals.

  9. Stochastic Modeling of CO2 Migrations and Chemical Reactions in Deep Saline Formations

    NASA Astrophysics Data System (ADS)

    Ni, C.; Lee, I.; Lin, C.

    2013-12-01

    correlation lengths in a Gaussian covariance model are varied in the MCS and the uncertainty of the CO2 and other chemical concentrations are evaluated based on 144 random realizations. In this study a constant injection rate of100Mt/year supercritical CO2 is applied in the bottom of CF. The continuous injection time is 20 years and the uncertainty results are evaluated at 100 years. By comparing with the case without small-scale variability simulation results show that the CO2 plume sizes in the horizontal direction increase from tens of meters to hundreds of meters when the variances of small-scale variability are varied from 1.0 to 4.0. The changes of correlation lengths (i.e., from 100m, 200m, to 400m) show small contribution on the size increases of CO2 plumes. Other uncertainties of chemical concentrations show behaviors similar to the CO2 plume patterns.

  10. Chemical and Physical Reactions of Wellbore Cement under CO2 Storage Conditions: Effects of Cement Additives

    NASA Astrophysics Data System (ADS)

    Kutchko, B. G.; Strazisar, B. R.; Huerta, N.; Lowry, G. V.; Dzombak, D. A.; Thaulow, N.

    2008-12-01

    Sequestration of CO2 into geologic formations requires long-term storage and low leakage rates to be effective. Active and abandoned wells in candidate storage formations must be evaluated as potential leakage points. Wellbore integrity is an important part of an overall integrated assessment program being developed at NETL to assess potential risks at CO2 storage sites. Such a program is needed for ongoing policy and regulatory decisions for geologic carbon sequestration. The permeability and integrity of the cement in the well is a primary factor affecting its ability to prevent leakage. Cement must be able to maintain low permeability over lengthy exposure to reservoir conditions in a CO2 injection and storage scenario. Although it is known that cement may be altered by exposure to CO2, the results of ongoing research indicate that cement curing conditions, fluid properties, and cement additives play a significant role in the rate of alteration and reaction. The objective of this study is to improve understanding of the factors affecting wellbore cement integrity for large-scale geologic carbon sequestration projects. Due to the high frequency use of additives (pozzolan) in wellbore cement, it is also essential to understand the reaction of these cement-pozzolan systems upon exposure to CO2 under sequestration conditions (15.5 MPa and 50°C). Laboratory experiments were performed to determine the physical and chemical changes, as well as the rate of alteration of commonly used pozzolan-cement systems under simulated sequestration reservoir conditions, including both supercritical CO2 and CO2-saturated brine. The rate of alteration of the cement-pozzolan systems is considerably faster than with neat cement. However, the alteration of physical properties is much less significant with the pozzolanic blends. Permeability of a carbonated pozzolanic cement paste remains sufficiently small to block significant vertical migration of CO2 in a wellbore. All of the

  11. FMC Chemicals: Burner Management System Upgrade Improves Performance and Saves Energy at a Chemical Plant

    SciTech Connect

    Not Available

    2004-07-01

    FMC Chemicals Corporation increased the efficiency of two large coal-fired boilers at its soda ash mine in Green River, Wyoming, by upgrading the burner management system. The project yields annual energy savings of 250,000 MMBtu.

  12. Development and testing of a long-range airborne CO2 DIAL chemical detection system

    NASA Astrophysics Data System (ADS)

    Higdon, N. Scott; Senft, Daniel C.; Fox, Marsha J.; Hamilton, Carla M.; Kelly, Brian T.; Dowling, James A.; Pierrottet, Diego F.; Dean, David R.; Richter, Dale A.; Bousek, Ronald R.

    1998-11-01

    The Air Force Research Laboratory has developed and tested an airborne CO2 differential absorption lidar system for the remote detection of chemicals. The Laser Airborne Remote Sensing DIAL system uses topographic backscatter to provide a long-range measurement of the column-content absorption of chemical plumes in the path of the laser beam. A high-power CO2 laser, capable of operation on multiple isotopes, and a Mersenne telescope constitute the major transceiver components. In addition to the laser, telescope, and transceiver optics, several onboard diagnostic instruments were mounted on the flight bench to monitor and optimize the system performance during airborne operation. The flight bench, electronics racks, and data acquisition and experiment control stations were designed to be integrated onto the AFRL C-135E research aircraft, and to utilize the existing pointing and tracking system on the aircraft.

  13. Chemicals loading in acetylated bamboo assisted by supercritical CO2 based on phase equilibrium data

    NASA Astrophysics Data System (ADS)

    Silviana, Petermann, M.

    2015-12-01

    Indonesia has a large tropical forest. However, the deforestation still appears annually and vastly. This reason drives a use of bamboo as wood alternative. Recently, there are many modifications of bamboo in order to prolong the shelf life. Unfortunately, the processes need more chemicals and time. Based on wood modification, esterifying of bamboo was undertaken in present of a dense gas, i.e. supercritical CO2. Calculation of chemicals loading referred to ASTM D1413-99 by using the phase equilibrium data at optimum condition by a statistical design. The results showed that the acetylation of bamboo assisted by supercritical CO2 required 14.73 kg acetic anhydride/m3 of bamboo for a treatment of one hour.

  14. [Analysis of the chemical constituents of volatile oil from the Folium Rhododendri Daurici by supercritical CO2 extraction].

    PubMed

    Jiao, Shu-qing; Liu, Feng-hua

    2009-02-01

    To compare the chemical constituents of volatile oils from Folium Rhododendri Daurici between supercritical CO2 extraction (SCE-CO2) and steam distillation (SD). The chemical constituents of volatile oils obtained by two methods were analyzed by GC-MS. 52 compounds in the volatile oil extracted by SCE-CO2 and 48 compounds in the volatile oil extracted by SD were separated and identified separately. There were 45 same components. The chemical constituents obtained by SCE-CO2 and SD are approached.

  15. Chemical and anatomical changes in Liquidambar styraciflua L. xylem after long term exposure to elevated CO2.

    PubMed

    Kim, Keonhee; Labbé, Nicole; Warren, Jeffrey M; Elder, Thomas; Rials, Timothy G

    2015-03-01

    The anatomical and chemical characteristics of sweetgum were studied after 11 years of elevated CO2 (544 ppm, ambient at 391 ppm) exposure. Anatomically, branch xylem cells were larger for elevated CO2 trees, and the cell wall thickness was thinner. Chemically, elevated CO2 exposure did not impact the structural components of the stem wood, but non-structural components were significantly affected. Principal component analysis (PCA) was employed to detect differences between the CO2 treatments by considering numerous structural and chemical variables, as well as tree size, and data from previously published sources (i.e., root biomass, production and turnover). The PCA results indicated a clear separation between trees exposed to ambient and elevated CO2 conditions. Correlation loadings plots of the PCA revealed that stem structural components, ash, Ca, Mg, total phenolics, root biomass, production and turnover were the major responses that contribute to the separation between the elevated and ambient CO2 treated trees.

  16. Stream geochemistry, chemical weathering and CO 2 consumption potential of andesitic terrains, Dominica, Lesser Antilles

    NASA Astrophysics Data System (ADS)

    Goldsmith, Steven T.; Carey, Anne E.; Johnson, Brent M.; Welch, Susan A.; Lyons, W. Berry; McDowell, William H.; Pigott, Jeffrey S.

    2010-01-01

    Recent studies of chemical weathering of andesitic-dacitic material on high-standing islands (HSIs) have shown these terrains have some of the highest observed rates of chemical weathering and associated CO 2 consumption yet reported. However, the paucity of stream gauge data in many of these terrains has limited determination of chemical weathering product fluxes. In July 2006 and March 2008, stream water samples were collected and manual stream gauging was performed in watersheds throughout the volcanic island of Dominica in the Lesser Antilles. Distinct wet and dry season solute concentrations reveal the importance of seasonal variations on the weathering signal. A cluster analysis of the stream geochemical data shows the importance of parent material age on the overall delivery of solutes. Observed Ca:Na, HCO 3:Na and Mg:Na ratios suggest crystallinity of the parent material may also play an important role in determining weathering fluxes. From total dissolved solids concentrations and mean annual discharge calculations we calculate chemical weathering yields of (6-106 t km -2 a -1), which are similar to those previously determined for basalt terrains. Silicate fluxes (3.1-55.4 t km -2 a -1) and associated CO 2 consumption (190-1575 × 10 3 mol km -2 a -1) determined from our study are among the highest determined to date. The calculated chemical fluxes from our study confirm the weathering potential of andesitic-dacitic terrains and that additional studies of these terrains are warranted.

  17. Electrocatalytic upgrading of biomass pyrolysis oils to chemical and fuel

    NASA Astrophysics Data System (ADS)

    Lam, Chun Ho

    The present project's aim is to liquefy biomass through fast pyrolysis and then upgrade the resulting "bio-oil" to renewable fuels and chemicals by intensifying its energy content using electricity. This choice reflects three points: (a) Liquid hydrocarbons are and will long be the most practical fuels and chemical feedstocks because of their energy density (both mass and volume basis), their stability and relative ease of handling, and the well-established infrastructure for their processing, distribution and use; (b) In the U.S., the total carbon content of annually harvestable, non-food biomass is significantly less than that in a year's petroleum usage, so retention of plant-captured carbon is a priority; and (c) Modern technologies for conversion of sunlight into usable energy forms---specifically, electrical power---are already an order of magnitude more efficient than plants are at storing solar energy in chemical form. Biomass fast pyrolysis (BFP) generates flammable gases, char, and "bio-oil", a viscous, corrosive, and highly oxygenated liquid consisting of large amounts of acetic acid and water together with hundreds of other organic compounds. With essentially the same energy density as biomass and a tendency to polymerize, this material cannot practically be stored or transported long distances. It must be upgraded by dehydration, deoxygenation, and hydrogenation to make it both chemically and energetically compatible with modern vehicles and fuels. Thus, this project seeks to develop low cost, general, scalable, robust electrocatalytic methods for reduction of bio-oil into fuels and chemicals.

  18. A Single-Culture Bioprocess of Methanothermobacter thermautotrophicus to Upgrade Digester Biogas by CO2-to-CH4 Conversion with H2

    PubMed Central

    Martin, Matthew R.; Fornero, Jeffrey J.; Angenent, Largus T.

    2013-01-01

    We optimized and tested a postbioprocessing step with a single-culture archaeon to upgrade biogas (i.e., increase methane content) from anaerobic digesters via conversion of CO2 into CH4 by feeding H2 gas. We optimized a culture of the thermophilic methanogen Methanothermobacter thermautotrophicus using: (1) a synthetic H2/CO2 mixture; (2) the same mixture with pressurization; (3) a synthetic biogas with different CH4 contents and H2; and (4) an industrial, untreated biogas and H2. A laboratory culture with a robust growth (dry weight of 6.4–7.4 g/L; OD600 of 13.6–15.4), a volumetric methane production rate of 21 L/L culture-day, and a H2 conversion efficiency of 89% was moved to an industrial anaerobic digester facility, where it was restarted and fed untreated biogas with a methane content of ~70% at a rate such that CO2 was in excess of the stoichiometric requirements in relation to H2. Over an 8-day operating period, the dry weight of the culture initially decreased slightly before stabilizing at an elevated level of ~8 g/L to achieve a volumetric methane production rate of 21 L/L culture-day and a H2 conversion efficiency of 62%. While some microbial contamination of the culture was observed via microscopy, it did not affect the methane production rate of the culture. PMID:24194675

  19. Chemical Processes with Supercritical CO2 in Engineered Geologic Systems: Significance, Previous Study, and Path Forward (Invited)

    NASA Astrophysics Data System (ADS)

    Xu, T.; Pruess, K.

    2009-12-01

    Chemical reactions with dissolved CO2 in the aqueous phase have long been considered in fundamental geosciences and practical applications. Recently, studies on geologic carbon sequestration and enhanced geothermal systems using CO2 as heat transmission fluid have brought new interests in chemical reaction processes directly with supercritical CO2 (scCO2, or gas phase). In the vicinity of a CO2 injection well, the aqueous fluid initially present in a geological formation would be quickly removed by dissolution (evaporation) into the flowing gas stream and by immiscible displacement by the scCO2, creating a gas phase dominant zone. In this zone, the water evaporation could cause formation dry-out and precipitation of salt near the injection well, reducing formation porosity, permeability, and injectivity. The scCO2 may directly attack well construction materials such as cement. Over time, the gas phase will tend to migrate upwards towards the caprock because the density of the scCO2 is lower than that of the aqueous phase. In the upper portions of the reservoir, the scCO2 will directly react with caprock minerals and alter the hydrological properties and mechanical strength. On the other hand, the scCO2 phase will maintain the dissolution into the aqueous phase, lowering pH, inducing mineral dissolution, complexing with dissolved cations, increasing CO2 solubility, increasing the density of the aqueous phase, and promoting “convective mixing”. Chemical processes are quite different in the scCO2 dominant geologic systems. The absence of an aqueous phase poses unique questions, as little is presently known about the chemistry of non-aqueous systems. Additional issues arise from the reactivity of water that is dissolved in the ScCO2 phase. In this presentation, the author will discuss the importance, state of the studies performed, and future research directions.

  20. Synthesis inversion of atmospheric CO2 using the NIRE chemical transport model

    NASA Astrophysics Data System (ADS)

    Taguchi, Shoichi

    Seasonal variations of CO2 emissions from the land biota and oceans are retrieved by use of an inverse method. Concentrations of CO2, computed by an atmospheric chemical transport model (NIRE-CTM-93), are fitted to the observed CO2 concentrations in terms of annual mean concentrations between 1984 to 1985, one-year period components, half-year components, and a global trend averaged over the years 1979 to 1996. The emissions due to fossil fuel combustion, those from land biota consisting of thirteen land areas, and those from the ocean consisting of twelve oceanic areas, are considered. The problem is solved by a least squares method, using singular value decomposition. A prior estimate of the emissions due to fossil fuel combustion is used as a tight constraint. When the annual mean emission, the net flux from the land biota during the growing season, and the net flux from the ocean are loosely constrained to zero, the solution indicates that areas consist of two groups. That is, those areas with relatively reliable estimates and those without. No reliable estimates are obtained for Africa, tropical and South America, tropical Asia, the tropical and the South Atlantic Ocean, and the western tropical Pacific. A reasonable global budget is not obtained due to unreliable estimates. The amplitude of the seasonal variations over middle-latitude North America is found to be less than that of some tropical land areas.

  1. Efficient Ionic-Liquid-Promoted Chemical Fixation of CO2 into α-Alkylidene Cyclic Carbonates.

    PubMed

    Qiu, Jikuan; Zhao, Yuling; Li, Zhiyong; Wang, Huiyong; Fan, Maohong; Wang, Jianji

    2017-03-22

    The efficient conversion of CO2 into value-added chemicals under metal-free conditions is of significant importance from the viewpoint of sustainable chemistry. In this work, ionic liquids (ILs) with different properties were used to promote the reaction between CO2 and propargylic alcohol for the synthesis of α-alkylidene cyclic carbonates. The protic IL 1,8-diazabicyclo-[5.4.0]-7-undecenium 2-methylimidazolide ([DBUH][MIm]) was prepared by simple neutralization of the superbase with a weak proton donor and could efficiently promote the reactions in high yields. After the reactions, the IL was separated from the reaction mixtures by simply adding water, and then reused after drying without an observable decrease in the catalytic activity and selectivity. NMR spectroscopy and detailed density functional theory analysis were used to propose a reaction mechanism. Both the cation and anion of the IL played a key synergistic role in promoting the reaction. These findings may be useful for the rational design of novel metal-free and recyclable routes for the reaction between CO2 and propargylic alcohols. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. [Comparison of the chemical components of essential oil extracted by supercritical CO2 fluid and steam distillation from Pteris multifida].

    PubMed

    Chen, Feng; Chen, Huan; Li, Shu-Jie; Lin, Jing-Ming; Wang, Zhao-Yu

    2013-08-01

    To compare the chemical components of essential oil extracted by supercritical CO2 fluid extraction (SFE-CO2) and steam distillation extraction (SD) from Pteris multifida. The essential oil of Pteris multifida was extracted by SFE-CO2 and SD. The chemical components of essential oil were separated and analyzed by GC-MS. Their relative contents were determined by normalization of peak area. Twenty -seven compounds in the essential oil extracted by SFE-CO2 and 45 compounds in the essential oil extracted by SD were identified respectively. There were 11 common components. The chemical components of essential oil extracted by SFE-CO2 are different from that extracted by SD.

  3. Controlled noxious chemical stimulation: responses of rat trigeminal brainstem neurones to CO2 pulses applied to the nasal mucosa.

    PubMed

    Anton, F; Peppel, P; Euchner, I; Handwerker, H O

    1991-02-25

    The nasal mucosa of halothane-anesthetized rats was stimulated with defined CO2 pulses. Recordings were performed from single trigeminal brainstem neurons to characterize their responses to this controlled chemical irritation. All cells examined with this stimulus displayed graded discharges to increasing concentrations of CO2. Enhanced responses were obtained in a group of neurons when the duration of the interstimulus interval was increased. The application of chemical irritants, notably mustard oil or acetic acid induced vigorous ongoing discharges in all cells tested. The CO2 stimulation method described here thus provides an ideal model for the quantitative physiological and pharmacological examination of chemically induced nociception.

  4. Chemical and magnetic interface properties of tunnel junctionswith co2mnsi/co2fesi multilayer electrode showing large tunnelingmagnetoresistance

    SciTech Connect

    Schmalhorst, J.; Ebke, D.; Sacher, M.D.; Liu, N.; Thomas, A.; Reiss, G.; Hutten, A.; Arenholz, E.

    2007-01-01

    Transport, as well as chemical and magnetic interface properties of two kinds of magnetic tunnel junctions (MTJs) with Co{sub 2}FeSi electrode, Al-O barrier, and Co-Fe counter electrode, are investigated. For junctions with Co{sub 2}FeSi single-layer electrodes, a tunnel magnetoresistance of up to 52% is found after optimal annealing for an optimal Al thickness of 1.5 nm, whereas the room temperature bulk magnetization of the Co{sub 2}FeSi film reaches only 75% of the expected value. By using a [Co{sub 2}MnSi/Co{sub 2}FeSi]{sub x10} multilayer electrode, the magnetoresistance can be increased to 114%, corresponding to a large spin polarization of 0.74, and the full bulk magnetization is reached. For Al thickness smaller than 1 nm, the TMR of both kinds of MTJs decreases rapidly to zero. On the other hand, for 2- to 3-nm-thick Al, the TMR decreases only slowly. The Al thickness dependence of the TMR is directly correlated to the element-specific magnetic moments of Fe and Co at the Co{sub 2}FeSi/Al-O interface for all Al thickness. Especially, for optimal Al thickness and annealing, the interfacial Fe moment of the single-layer electrode is about 20% smaller than for the multilayer electrode, indicating smaller atomic disorder at the barrier interface for the latter MTJ.

  5. Porous Ionic Polymers as a Robust and Efficient Platform for Capture and Chemical Fixation of Atmospheric CO2.

    PubMed

    Sun, Qi; Jin, Yingyin; Aguila, Briana; Meng, Xiangju; Ma, Shengqian; Xiao, Feng-Shou

    2017-03-22

    Direct use of atmospheric CO2 as a C1 source to synthesize high-value chemicals through environmentally benign processes is of great interest, yet challenging. Porous heterogeneous catalysts that are capable of simultaneously capturing and converting CO2 are promising candidates for such applications. Herein, a family of organic ionic polymers with nanoporous structure, large surface area, strong affinity for CO2 , and very high density of catalytic active sites (halide ions) was synthesized through the free-radical polymerization of vinylfunctionalized quaternary phosphonium salts. The resultant porous ionic polymers (PIPs) exhibit excellent activities in the cycloaddition of epoxides with atmospheric CO2 , outperforming the corresponding soluble phosphonium salt analogues and ranking among the highest of known metal-free catalytic systems. The high CO2 uptake capacity of the PIPs facilitates the enrichment of CO2 molecules around the catalytic centers, thereby benefiting its conversion. We have demonstrated for the first time that atmospheric CO2 can be directly converted to cyclic carbonates at room temperature using a heterogeneous catalytic system under metal-solvent free conditions. Moreover, the catalysts proved to be robust and fully recyclable, demonstrating promising potential for practical utilization for the chemical fixation of CO2 . Our work thereby paves a way to the advance of PIPs as a new type of platform for capture and conversion of CO2 . © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Influence of Chemical, Mechanical, and Transport Processes on Wellbore Leakage from Geologic CO2 Storage Reservoirs.

    PubMed

    Carroll, Susan A; Iyer, Jaisree; Walsh, Stuart D C

    2017-08-15

    Wells are considered to be high-risk pathways for fluid leakage from geologic CO2 storage reservoirs, because breaches in this engineered system have the potential to connect the reservoir to groundwater resources and the atmosphere. Given these concerns, a few studies have assessed leakage risk by evaluating regulatory records, often self-reported, documenting leakage in gas fields. Leakage is thought to be governed largely by initial well-construction quality and the method of well abandonment. The geologic carbon storage community has raised further concerns because acidic fluids in the CO2 storage reservoir, alkaline cement meant to isolate the reservoir fluids from the overlying strata, and steel casings in wells are inherently reactive systems. This is of particular concern for storage of CO2 in depleted oil and gas reservoirs with numerous legacy wells engineered to variable standards. Research suggests that leakage risks are not as great as initially perceived because chemical and mechanical alteration of cement has the capacity to seal damaged zones. Our work centers on defining the coupled chemical and mechanical processes governing flow in damaged zones in wells. We have developed process-based models, constrained by experiments, to better understand and forecast leakage risk. Leakage pathways can be sealed by precipitation of carbonate minerals in the fractures and deformation of the reacted cement. High reactivity of cement hydroxides releases excess calcium that can precipitate as carbonate solids in the fracture network under low brine flow rates. If the flow is fast, then the brine remains undersaturated with respect to the solubility of calcium carbonate minerals, and zones depleted in calcium hydroxides, enriched in calcium carbonate precipitates, and made of amorphous silicates leached of original cement minerals are formed. Under confining pressure, the reacted cement is compressed, which reduces permeability and lowers leakage risks. The

  7. Upgraded biogas from municipal solid waste for natural gas substitution and CO2 reduction--a case study of Austria, Italy, and Spain.

    PubMed

    Starr, Katherine; Villalba, Gara; Gabarrell, Xavier

    2015-04-01

    Biogas is rich in methane and can be further purified through biogas upgrading technologies, presenting a viable alternative to natural gas. Landfills and anaerobic digestors treating municipal solid waste are a large source of such biogas. They therefore offer an attractive opportunity to tap into this potential source of natural gas while at the same time minimizing the global warming impact resulting from methane emissions in waste management schemes (WMS) and fossil fuel consumption reduction. This study looks at the current municipal solid waste flows of Spain, Italy, and Austria over one year (2009), in order to determine how much biogas is generated. Then it examines how much natural gas could be substituted by using four different biogas upgrading technologies. Based on current waste generation rates, exploratory but realistic WMS were created for each country in order to maximize biogas production and potential for natural gas substitution. It was found that the potential substitution of natural gas by biogas resulting from the current WMS seems rather insignificant: 0.2% for Austria, 0.6% for Italy and 0.3% for Spain. However, if the WMS is redesigned to maximize biogas production, these figures can increase to 0.7% for Austria, 1% for Italy and 2% for Spain. Furthermore, the potential CO2 reduction as a consequence of capturing the biogas and replacing fossil fuel can result in up to a 93% reduction of the annual national waste greenhouse gas emissions of Spain and Italy. Copyright © 2015 Elsevier Ltd. All rights reserved.

  8. Colour and chemical changes of the lime wood surface due to CO2 laser thermal modification

    NASA Astrophysics Data System (ADS)

    Kubovský, Ivan; Kačík, František

    2014-12-01

    We studied colour and main wood components changes of lime wood caused by CO2 laser beam irradiation. The dry surface of lime wood (Tilia vulgaris L.) was irradiated with the CO2 laser beam (wavelength of 10.6 μm) at different exposures (expressed as the irradiation dose). Colour changes were monitored by the spectrophotometer, chemical changes were observed by the ATR-FTIR spectroscopy and carbohydrates were analysed by the HPLC method. With the growth of the irradiation dose (from 8.1 to 28.7 J cm-2) lightness (ΔL*) decrease and increase of the total colour difference (ΔE*) were observed. Higher values of the input energy lead to accelerating the mutual reaction of the functional groups resulting in the subsequent condensation of lignin. The total decrease in saccharides at the highest irradiation dose reaches 27.39% of the initial amount of saccharides in the reference sample. We have observed degradation and loss of hemicelluloses.

  9. PdZn catalysts for CO2 hydrogenation to methanol using chemical vapour impregnation (CVI).

    PubMed

    Bahruji, H; Bowker, M; Jones, W; Hayward, J; Ruiz Esquius, J; Morgan, D J; Hutchings, G J

    2017-02-09

    The formation of PdZn bimetallic alloys on ZnO, TiO2 and Al2O3 supports was investigated, together with the effect of alloy formation on the CO2 hydrogenation reaction. The chemical vapour impregnation (CVI) method produced PdZn nanoparticles with diameters of 3-6 nm. X-ray photoelectron spectroscopy and X-ray diffraction revealed the changes in the structure of the PdZn alloy that help stabilise formate intermediates during methanol synthesis. PdZn supported on TiO2 exhibits high methanol productivity of 1730 mmol kgcat(-1) h(-1) that is associated with the high dispersion of the supported PdZn alloy.

  10. Supercritical CO2 extract of Cinnamomum zeylanicum: chemical characterization and antityrosinase activity.

    PubMed

    Marongiu, Bruno; Piras, Alessandra; Porcedda, Silvia; Tuveri, Enrica; Sanjust, Enrico; Meli, Massimo; Sollai, Francesca; Zucca, Paolo; Rescigno, Antonio

    2007-11-28

    The volatile oil of the bark of Cinnamomum zeylanicum was extracted by means of supercritical CO2 fluid extraction in different conditions of pressure and temperature. Its chemical composition was characterized by GC-MS analysis. Nineteen compounds, which in the supercritical extract represented >95% of the oil, were identified. (E)-Cinnamaldehyde (77.1%), (E)-beta-caryophyllene (6.0%), alpha-terpineol (4.4%), and eugenol (3.0%) were found to be the major constituents. The SFE oil of cinnamon was screened for its biological activity about the formation of melanin in vitro. The extract showed antityrosinase activity and was able to reduce the formation of insoluble flakes of melanin from tyrosine. The oil also delayed the browning effect in apple homogenate. (E)-Cinnamaldehyde and eugenol were found to be mainly responsible of this inhibition effect.

  11. Solar-to-chemical and solar-to-fuel production from CO2 by metabolically engineered microorganisms.

    PubMed

    Woo, Han Min

    2017-01-11

    Recent development of carbon capture utilization (CCU) for reduction of greenhouse gas emission are reviewed. In the case of CO2 utilization, I describe development of solar-to-chemical and solar-to-fuel technology that refers to the use of solar energy to convert CO2 to desired chemicals and fuels. Photoautotrophic cyanobacterial platforms have been extensively developed on this principle, producing a diverse range of alcohols, organic acids, and isoprenoids directly from CO2. Recent breakthroughs in the metabolic engineering of cyanobacteria were reviewed. In addition, adoption of the light harvesting mechanisms from nature, photovoltaics-derived water splitting technologies have recently been integrated with microbial biotechnology to produce desired chemicals. Studies on the integration of electrode material with next-generation microbes are showcased for alternative solar-to-chemical and solar-to-fuel platforms.

  12. Chemical and anatomical changes in Liquidambar styraciflua L. xylem after long term exposure to elevated CO2

    DOE PAGES

    Kim, Keonhee; Labbé, Nicole; Warren, Jeffrey M.; ...

    2015-01-17

    The anatomical and chemical characteristics of sweetgum were studied after 11 years of elevated CO2 (544 ppm, ambient at 391 ppm) exposure. Anatomically, branch xylem cells were larger for elevated CO2 trees, and the cell wall thickness was thinner. Chemically, elevated CO2 exposure did not impact the structural components of the stem wood, but non-structural components were significantly affected. Principal component analysis (PCA) was employed to detect differences between the CO2 treatments by considering numerous structural and chemical variables, as well as tree size, and data from previously published sources (for example, root biomass, production and turnover). The PCA resultsmore » indicated a clear separation between trees exposed to ambient and elevated CO2 conditions. Lastly, correlation loadings plots of the PCA revealed that stem structural components, ash, Ca, Mg, total phenolics, root biomass, production and turnover were the major responses that contribute to the separation between the elevated and ambient CO2 treated trees.« less

  13. Chemical absorption and CO2 biofixation via the cultivation of Spirulina in semicontinuous mode with nutrient recycle.

    PubMed

    da Rosa, Gabriel Martins; Moraes, Luiza; Cardias, Bruna Barcelos; de Souza, Michele da Rosa Andrade Zimmermann; Costa, Jorge Alberto Vieira

    2015-09-01

    The chemical absorption of carbon dioxide (CO2) is a technique used for the mitigation of the greenhouse effect. However, this process consumes high amounts of energy to regenerate the absorbent and to separate the CO2. CO2 removal by microalgae can be obtained via the photosynthesis process. The objective of this study was to investigate the cultivation and the macromolecules production by Spirulina sp. LEB 18 with the addition of monoethanolamine (MEA) and CO2. In the cultivation with MEA, were obtained higher results of specific growth rate, biomass productivity, CO2 biofixation, CO2 use efficiency, and lower generation time. Besides this, the carbohydrate concentration obtained at the end of this assay was approximately 96.0% higher than the control assay. Therefore, Spirulina can be produced using medium recycle and the addition of MEA, thereby promoting the reduction of CO2 emissions and showing potential for areas that require higher concentrations of carbohydrates, such as in bioethanol production. Copyright © 2015 Elsevier Ltd. All rights reserved.

  14. Analysis of anthropogenic CO2 signal in ICARTT using a regional chemical transport model and observed tracers

    NASA Astrophysics Data System (ADS)

    Campbell, J. E.; Carmichael, G. R.; Tang, Y.; Chai, T.; Vay, S. A.; Choi, Y.-H.; Sachse, G. W.; Singh, H. B.; Schnoor, J. L.; Woo, J.; Vukovich, J. M.; Streets, D. G.; Huey, L. G.; Stanier, C. O.

    2007-04-01

    Atmospheric CO2 inversion studies infer surface sources and sinks from observations and models. These studies usually require determination of the fossil fuel component of the observation, which can be estimated using anthropogenic tracers such as CO. The objective of this study is to demonstrate a new CO tracer method that accounts for overlapping forest fire and photochemical CO influences, and to quantify several aspects of the uncertainty in the CO tracer technique. Photochemistry model results and observations from the International Consortium for Atmospheric Research on Transport and Transformation experiment are used to quantify changes in the fossil fuel CO2 prediction from the CO tracer method with and without the inclusion of CO from biomass burning and photochemistry. Although the chemical sources and sinks tend to offset each other, there are regions where the chemical reactions change fossil fuel CO2 predictions by up to +/-4 ppm. Including biomass burning lowers fossil fuel CO2 by an average of 12 ppm in plumes heavily influenced by long-range transport of forest fire CO. An alternate fossil fuel CO2 calculation is done in a power plant plume using SO2 as a tracer, giving a change in 20 ppm from the CO method, indicative of uncertainty in the assumed CO:CO2 ratio.

  15. Effect of chemical environment and rock composition on fracture mechanics properties of reservoir lithologies in context of CO2 sequestration

    NASA Astrophysics Data System (ADS)

    Major, J. R.; Eichhubl, P.; Callahan, O. A.

    2015-12-01

    The coupled chemical and mechanical response of reservoir and seal rocks to injection of CO2 have major implications on the short and long term security of sequestered carbon. Many current numerical models evaluating behavior of reservoirs and seals during and after CO2 injection in the subsurface consider chemistry and mechanics separately and use only simple mechanical stability criteria while ignoring time-dependent failure parameters. CO2 injection irreversibly alters the subsurface chemical environment which can then affect geomechanical properties on a range of time scales by altering rock mineralogy and cements through dissolution, remobilization, and precipitation. It has also been documented that geomechanical parameters such as fracture toughness (KIC) and subcritical index (SCI) are sensitive to chemical environment. Double torsion fracture mechanics testing of reservoir lithologies under controlled environmental conditions relevant to CO2 sequestration show that chemical environment can measurably affect KIC and SCI. This coupled chemical-mechanical behavior is also influenced by rock composition, grains, amount and types of cement, and fabric. Fracture mechanics testing of the Aztec Sandstone, a largely silica-cemented, subarkose sandstone demonstrate it is less sensitive to chemical environment than Entrada Sandstone, a silty, clay-rich sandstone. The presence of de-ionized water lowers KIC by approximately 20% and SCI 30% in the Aztec Sandstone relative to tests performed in air, whereas the Entrada Sandstone shows reductions on the order of 70% and 90%, respectively. These results indicate that rock composition influences the chemical-mechanical response to deformation, and that the relative chemical reactivity of target reservoirs should be recognized in context of CO2 sequestration. In general, inert grains and cements such as quartz will be less sensitive to the changing subsurface environment than carbonates and clays.

  16. Metallosalen-Based Ionic Porous Polymers as Bifunctional Catalysts for the Conversion of CO2 into Valuable Chemicals.

    PubMed

    Luo, Rongchang; Chen, Yaju; He, Qian; Lin, Xiaowei; Xu, Qihang; He, Xiaohui; Zhang, Wuying; Zhou, Xiantai; Ji, Hongbing

    2016-12-31

    A series of new metallosalen-based ionic porous organic polymers (POPs) were synthesized for the first time using a simple unique strategy based on the free-radical copolymerization reaction. Various techniques were used to characterize the physicochemical properties of these catalysts. These well-designed materials endowed high surface area, hierarchical porous structures, and enhanced CO2 /N2 adsorptive selectivity. Moreover, these POPs having both metal centers (Lewis acid) and ionic units (nucleophile) could serve as bifunctional catalysts in the catalytic conversion of CO2 into high value-added chemicals without any additional co-catalyst under mild and solvent-free conditions, for example, CO2 /epoxides cycloaddition and Nformylation of amines from CO2 and hydrosilanes. The results demonstrated that the irregular porous structure was very favorable for the diffusion of substrates and products, and the microporous structural property resulted in the enrichment of CO2 near the catalytic centers in the CO2 -involved transformations. Additionally, the superhydrophobic property could not only enhance the chemoselectivity of products but also promote the stability and recyclability of catalysts.

  17. Calculating chemical equilibria in the heparin-Co2+ ion-glycine system

    NASA Astrophysics Data System (ADS)

    Feofanova, M. A.; Frantseva, Yu. V.; Zhuravlev, E. V.; Ryasensky, S. S.; Baranova, N. V.

    2013-08-01

    Results from investigating interactions in the heparin-Co2+ ion-glycine system are presented. The stoichiometry of cobalt complexes with heparin and glycine compositions CoOHHtpGly4- and CoHepGly3- is established.

  18. Chemical, physical, and biological controls on the spatial heterogeneity of annual soil CO2 and CH4 fluxes

    NASA Astrophysics Data System (ADS)

    Warner, D. L.; Inamdar, S. P.; Vargas, R.

    2016-12-01

    Soils play a major role in global CO2 and CH4 fluxes. However, the magnitudes of these fluxes vary widely in space and time due to the inherent heterogeneity of the underlying chemical, physical, and biological environmental controlling factors of these fluxes. Understanding the relationships between these controlling factors and the resulting CO2 and CH4 fluxes is critical for identifying potential climate change feedbacks in soils. We examined an array of chemical (organic matter content and quality), physical (soil texture, water content, and bulk density), and biological (fungal, bacterial, and methanogen/troph functional gene ratios) controlling factors on soil CO2 and CH4 fluxes over the course of one year in a topographically complex forested catchment. Cumulative annual CO2 and CH4 fluxes ranged from 18.0 to 79.3 mol CO2 m-2 y-1 and -42 to 15 mmol CH4 m-2 y-1 across 20 sites within the 12 ha study area. Annual fluxes of both gases were significantly different across valley-bottom wetlands, transition zones, and uplands. Additionally, both CO2 efflux and CH4 uptake were negatively correlated to bulk density, and were significantly related to optical characteristics of pore water and water-extractable SOM. Soil water content was closely related to fluxes of both gases and many of the other controlling factors. This study provides insights into the many influential controlling factors on soil CO2 and CH4 fluxes, highlighting the complex interactions of topography, hydrology, and the carbon cycle in forest ecosystems.

  19. Effects of Steam and CO2 in the Fluidizing Gas when Using Bituminous Coal in Chemical-Looping Combustion

    NASA Astrophysics Data System (ADS)

    Leion, H.; Lyngfelt, A.; Mattisson, T.

    Chemical-looping combustion (CLC) is a combustion technology where an oxygen carrier is used to transfer oxygen from the combustion air to the fuel in order to avoid direct contact between air and fuel. Thus, the CO2 is inherently separated from the flue gases with a potential for considerably lower energy penalty and cost compared to other techniques for CO2 separation. The oxygen carrier is circulated between two reactors, a fuel and an air reactor, where the flue gas from the air reactor contains oxygen depleted air and the flue gas from the fuel reactor contains mainly CO2 and H2O. The water can easily be condensed and the remaining CO2 can be transported for underground storage. Most of the prior work with CLC has focused on using natural gas and syngas as fuel and oxygen carrying material normally produced from pure chemicals. However, recent work on adapting the CLC process for solid fuels with ores and natural minerals as oxygen carrier shows promising results. This paper will present results from reactivity investigations in a laboratory fluidized-bed reactor system using previously investigated natural mineral ilmenite as oxygen carrier and a bituminous Colombian coal as fuel. Experiments were conducted at a temperature of 970°C with N2, steam, and/or CO2 in the fluidizing gas. Synergy effects between steam and CO2 on fuel conversion was noted. The results show that the fuel conversion was a roughly a factor 5 faster with steam as compared to CO2 in the fluidizing gas.

  20. The Idaho Chemical Processing Plant Product Denitrator Upgrade

    SciTech Connect

    N /A

    1982-05-01

    The upgrade and redesign of a fluidized-bed denitrator for production of uranium trioxide from uranyl nitrate solution is discussed. The success of the project in improving process efficiency and personnel safety is also addressed based on subsequent operation.

  1. Development of a Method for Measuring Carbon Balance in Chemical Sequestration of CO2

    SciTech Connect

    Cheng, Zhongxian; Pan, Wei-Ping; Riley, John T.

    2006-09-09

    Anthropogenic CO2 released from fossil fuel combustion is a primary greenhouse gas which contributes to “global warming.” It is estimated that stationary power generation contributes over one-third of total CO2 emissions. Reducing CO2 in the atmosphere can be accomplished either by decreasing the rate at which CO2 is emitted into the atmosphere or by increasing the rate at which it is removed from it. Extensive research has been conducted on determining a fast and inexpensive method to sequester carbon dioxide. These methods can be classified into two categories, CO2 fixation by natural sink process for CO2, or direct CO2 sequestration by artificial processes. In direct sequestration, CO2 produced from sources such as coal-fired power plants, would be captured from the exhausted gases. CO2 from a combustion exhaust gas is absorbed with an aqueous ammonia solution through scrubbing. The captured CO2 is then used to synthesize ammonium bicarbonate (ABC or NH4HCO3), an economical source of nitrogen fertilizer. In this work, we studied the carbon distribution after fertilizer is synthesized from CO2. The synthesized fertilizer in laboratory is used as a “CO2 carrier” to “transport” CO2 from the atmosphere to crops. After biological assimilation and metabolism in crops treated with ABC, a considerable amount of the carbon source is absorbed by the plants with increased biomass production. The majority of the unused carbon source percolates into the soil as carbonates, such as calcium carbonate (CaCO3) and magnesium carbonate (MgCO3). These carbonates are environmentally benign. As insoluble salts, they are found in normal rocks and can be stored safely and permanently in soil. This investigation mainly focuses on the carbon distribution after the synthesized fertilizer is applied to soil. Quantitative examination of carbon distribution in an ecosystem is a challenging task since the carbon in the soil may come from various sources. Therefore synthesized 14C

  2. Chemical-mechanical coupling observed for depleted oil reservoirs subjected to long-term CO2-exposure - A case study of the Werkendam natural CO2 analogue field

    NASA Astrophysics Data System (ADS)

    Hangx, Suzanne; Bakker, Elisenda; Bertier, Pieter; Nover, Georg; Busch, Andreas

    2015-10-01

    Geological storage of CO2 is one of the most promising technologies to rapidly reduce anthropogenic emissions of carbon dioxide. In order to ensure storage integrity, it is important to understand the effect of long-term CO2/brine/rock interactions on the mechanical behaviour of a storage complex. As most of these reactions are too slow to reproduce on laboratory timescales, we studied a natural CO2 analogue reservoir (the Röt Fringe Sandstone, Werkendam field, the Netherlands; 125-135 Ma of CO2-exposure) and its unreacted counterpart. We focused on CO2-induced mineralogical and porosity-permeability changes, and their effect on mechanical behaviour of both intact rock and simulated fault gouge. Overall, CO2-exposure did not lead to drastic mineralogical changes. The CO2-exposed material shows a stronger dependence of permeability on porosity, which is attributed to differences in diagenesis (closed-system diagenesis and hydrocarbon emplacement) taking place before CO2 charging. The limited extent of reaction was in part the result of bitumen coatings protecting specific mineral phases from reaction. In local, mm-sized zones displaying significant anhydrite cement dissolution, enhanced porosity was observed. For most of the reservoir the long-term mechanical behaviour after CO2-exposure could be described by the behaviour of the unreacted sandstone, while these more 'porous' zones had a lower rock strength. In addition, CO2-exposure did not affect the fault friction behaviour, and slip is expected to result in stable sliding. Simple stress path calculations predict that reservoir failure due to depletion and injection is unlikely, even for the 'porous' zones, nor will fault reactivation occur for realistic injection scenarios.

  3. Robust C–C bonded porous networks with chemically designed functionalities for improved CO2 capture from flue gas

    PubMed Central

    Thirion, Damien; Lee, Joo S; Özdemir, Ercan

    2016-01-01

    Effective carbon dioxide (CO2) capture requires solid, porous sorbents with chemically and thermally stable frameworks. Herein, we report two new carbon–carbon bonded porous networks that were synthesized through metal-free Knoevenagel nitrile–aldol condensation, namely the covalent organic polymer, COP-156 and 157. COP-156, due to high specific surface area (650 m2/g) and easily interchangeable nitrile groups, was modified post-synthetically into free amine- or amidoxime-containing networks. The modified COP-156-amine showed fast and increased CO2 uptake under simulated moist flue gas conditions compared to the starting network and usual industrial CO2 solvents, reaching up to 7.8 wt % uptake at 40 °C. PMID:28144294

  4. Robust C-C bonded porous networks with chemically designed functionalities for improved CO2 capture from flue gas.

    PubMed

    Thirion, Damien; Lee, Joo S; Özdemir, Ercan; Yavuz, Cafer T

    2016-01-01

    Effective carbon dioxide (CO2) capture requires solid, porous sorbents with chemically and thermally stable frameworks. Herein, we report two new carbon-carbon bonded porous networks that were synthesized through metal-free Knoevenagel nitrile-aldol condensation, namely the covalent organic polymer, COP-156 and 157. COP-156, due to high specific surface area (650 m(2)/g) and easily interchangeable nitrile groups, was modified post-synthetically into free amine- or amidoxime-containing networks. The modified COP-156-amine showed fast and increased CO2 uptake under simulated moist flue gas conditions compared to the starting network and usual industrial CO2 solvents, reaching up to 7.8 wt % uptake at 40 °C.

  5. Quantum Chemical Study of CH3 + O2 Combustion Reaction System: Catalytic Effects of Additional CO2 Molecule.

    PubMed

    Masunov, Artëm E; Wait, Elizabeth; Vasu, Subith S

    2017-08-03

    The supercritical carbon dioxide diluent is used to control the temperature and to increase the efficiency in oxycombustion fossil fuel energy technology. It may affect the rates of combustion by altering mechanisms of chemical reactions, compared to the ones at low CO2 concentrations. Here, we investigate potential energy surfaces of the four elementary reactions in the CH3 + O2 reactive system in the presence of one CO2 molecule. In the case of reaction CH3 + O2 → CH2O + OH (R1 channel), van der Waals (vdW) complex formation stabilizes the transition state and reduces the activation barrier by ∼2.2 kcal/mol. Alternatively, covalently bonded CO2 may form a six-membered ring transition state and reduce the activation barrier by ∼0.6 kcal/mol. In case of reaction CH3 + O2 → CH3O + O (R2 channel), covalent participation of CO2 lowers the barrier for the rate limiting step by 3.9 kcal/mol. This is expected to accelerate the R2 process, important for the branching step of the radical chain reaction mechanism. For the reaction CH3 + O2 → CHO + H2O (R3 channel) with covalent participation of CO2, the activation barrier is lowered by 0.5 kcal/mol. The reaction CH2O + OH → CHO + H2O (R4 channel) involves hydrogen abstraction from formaldehyde by OH radical. Its barrier is reduced from 7.1 to 0.8 kcal/mol by formation of vdW complex with spectator CO2. These new findings are expected to improve the kinetic reaction mechanism describing combustion processes in supercritical CO2 medium.

  6. Using the Relationship between Vehicle Fuel Consumption and CO2 Emissions To Illustrate Chemical Principles

    NASA Astrophysics Data System (ADS)

    Oliver-Hoyo, Maria T.; Pinto, Gabriel

    2008-02-01

    This instructional resource utilizes consumer product information by which students compare theoretical stoichiometric calculations to CO 2 car emissions and fuel consumption data. Representing graphically the emission of CO 2 versus consumption of fuel provides a tangible way of connecting concepts studied in chemistry classes to everyday life. Considerable simplification of an otherwise complex chemistry problem provides comparable theoretical and actual data. Practice with unit conversion and graphing enhance this activity promoting skills used by professionals to perform emission measurements. This activity may be used to bring awareness of car emissions issues such as the environmental impact of CO 2 emissions and the differences of hybrid engines or gasoline versus diesel engines. Scientific literacy can be approached by incorporating exercises such as this one into chemistry classroom activities. Students have expressed keen interest in this type of "tangible" chemistry where a concrete example of everyday life puts textbook chemistry in context.

  7. Mechanistic studies of pyridinium electrochemistry: alternative chemical pathways in the presence of CO2.

    PubMed

    Peroff, A G; Weitz, E; Van Duyne, R P

    2016-01-21

    Protonated heterocyclic amines, such as pyridinium, have been utilized as catalysts in the electrocatalytic reduction of carbon dioxide. While these represent a new and exciting class of electrocatalysts, the details of the mechanism and faradaic processes occurring in solution are unclear. We report a series of cyclic voltammetry experiments involving Pt, Ag, Au, and Cu electrodes, under both aqueous and nonaqueous conditions, directed towards gaining an improved mechanistic understanding of pyridinium electrochemistry. Surface-enhanced Raman (SER) spectroelectrochemistry was also performed on Cu film-over-nanosphere electrodes in order to identify adsorbed species. It was found that the reduction potential of pyridinium (-0.58 V vs. SCE) and its electrochemical reversibility are unique features of platinum electrodes. In contrast, the reduction potentials on Ag, Au, and Cu electrodes are ∼400 mV more negative than Pt in both the presence and the absence of CO2. SER spectroelectrochemistry of pyridinium solutions shows no evidence for a pyridinium radical or a pyridinium ion. Increased cathodic current in the presence of CO2 is only detected at scan rates less than 10 mV s(-1) in aqueous solutions. The addition of CO2 resulted in a shift in the potential for the hydrogen evolution reaction. Pyridinium electrochemistry was observed under nonaqueous conditions; however no increase in cathodic current was observed when CO2 was added to the solution. Based on this set of results it is concluded that the reduction potential of pyridinium is surface dependent, CO2 acts as a pseudo-reserve of H(+), and pyridinium and CO2 create an alternative mechanism for hydrogen evolution.

  8. Microbial Reverse-Electrodialysis Electrolysis and Chemical-Production Cell for H2 Production and CO2 Sequestration

    PubMed Central

    2014-01-01

    Natural mineral carbonation can be accelerated using acid and alkali solutions to enhance atmospheric CO2 sequestration, but the production of these solutions needs to be carbon-neutral. A microbial reverse-electrodialysis electrolysis and chemical-production cell (MRECC) was developed to produce these solutions and H2 gas using only renewable energy sources (organic matter and salinity gradient). Using acetate (0.82 g/L) as a fuel for microorganisms to generate electricity in the anode chamber (liquid volume of 28 mL), 0.45 mmol of acid and 1.09 mmol of alkali were produced at production efficiencies of 35% and 86%, respectively, along with 10 mL of H2 gas. Serpentine dissolution was enhanced 17–87-fold using the acid solution, with approximately 9 mL of CO2 absorbed and 4 mg of CO2 fixed as magnesium or calcium carbonates. The operational costs, based on mineral digging and grinding, and water pumping, were estimated to be only $25/metric ton of CO2 fixed as insoluble carbonates. Considering the additional economic benefits of H2 generation and possible wastewater treatment, this method may be a cost-effective and environmentally friendly method for CO2 sequestration. PMID:24741666

  9. High temperature chemical kinetic study of the H2-CO-CO2-NO reaction system

    NASA Technical Reports Server (NTRS)

    Jachimowski, C. J.

    1975-01-01

    An experimental study of the kinetics of the H2-CO-CO2-NO reaction system was made behind incident shock waves at temperatures of 2460 and 2950 K. The overall rate of the reaction was measured by monitoring radiation from the CO + O yields CO2 + h upoilon reaction. Correlation of these data with a detailed reaction mechanism showed that the high-temperature rate of the reaction N + OH yields NO + H can be described by the low-temperature (320 K) rate coefficient. Catalytic dissociation of molecular hydrogen was an important reaction under the tests conditions.

  10. A Review of Hazardous Chemical Species Associated with CO2 Capturefrom Coal-Fired Power Plants and Their Potential Fate in CO2 GeologicStorage

    SciTech Connect

    Apps, J.A.

    2006-02-23

    Conventional coal-burning power plants are major contributors of excess CO2 to the atmospheric inventory. Because such plants are stationary, they are particularly amenable to CO2 capture and disposal by deep injection into confined geologic formations. However, the energy penalty for CO2 separation and compression is steep, and could lead to a 30-40 percent reduction in useable power output. Integrated gas combined cycle (IGCC) plants are thermodynamically more efficient, i.e.,produce less CO2 for a given power output, and are more suitable for CO2 capture. Therefore, if CO2 capture and deep subsurface disposal were to be considered seriously, the preferred approach would be to build replacement IGCC plants with integrated CO2 capture, rather than retrofit existing conventional plants. Coal contains minor quantities of sulfur and nitrogen compounds, which are of concern, as their release into the atmosphere leads to the formation of urban ozone and acid rain, the destruction of stratospheric ozone, and global warming. Coal also contains many trace elements that are potentially hazardous to human health and the environment. During CO2 separation and capture, these constituents could inadvertently contaminate the separated CO2 and be co-injected. The concentrations and speciation of the co-injected contaminants would differ markedly, depending on whether CO2 is captured during the operation of a conventional or an IGCC plant, and the specific nature of the plant design and CO2 separation technology. However, regardless of plant design or separation procedures, most of the hazardous constituents effectively partition into the solid waste residue. This would lead to an approximately two order of magnitude reduction in contaminant concentration compared with that present in the coal. Potential exceptions are Hg in conventional plants, and Hg and possibly Cd, Mo and Pb in IGCC plants. CO2 capture and injection disposal could afford an opportunity to deliberately capture

  11. Dual roles of CO2*- for degrading synthetic organic chemicals in the photo/ferrioxalate system.

    PubMed

    Jeong, Joonseon; Yoon, Jeyong

    2004-09-01

    In this study, the relative importance of the dual reaction pathways of CO2*- in the photo/ferrioxalate system, where it acts both as a reductant for reducing the ferric ion and as an agent for the formation of H(2)O(2), was investigated as a function of the concentrations of ferrioxalate and oxygen. We studied the two competitive reactions of CO2*- in the photo/ferrioxalate system, which depend on the relative concentrations of ferrioxalate to oxygen, with the degradation of 2,4-dichlorophenoxyacetic acid (2,4-D), which was used as a target pollutant. At high concentrations of ferrioxalate, almost all of the CO2*- reacted with ferrioxalate to reduce Fe(III) to Fe(II), whereas at low concentrations of ferrioxalate, a majority of the CO2*- contributed to the formation of H(2)O(2), as a result of its reaction with oxygen, which allows the Fenton reaction to occur without any external supply of H(2)O(2).

  12. Chemical ordering and large tunnel magnetoresistance in Co2FeAl/MgAl2O4/Co2FeAl(001) junctions

    NASA Astrophysics Data System (ADS)

    Scheike, Thomas; Sukegawa, Hiroaki; Inomata, Koichiro; Ohkubo, Tadakatsu; Hono, Kazuhiro; Mitani, Seiji

    2016-05-01

    Epitaxial magnetic tunnel junctions (MTJs) with a Co2FeAl/CoFe (0.5 nm)/MgAl2O4/Co2FeAl(001) structure were fabricated by magnetron sputtering. High-temperature in situ annealing led to a high degree of B2-order in the Co2FeAl layers and cation order of the MgAl2O4 barrier. Large tunnel magnetoresistance (TMR) of up to 342% was obtained at room temperature (616% at 4 K), in contrast to the TMR ratio ( ≲ 160%) suppressed by the band-folding effect in Fe/cation-ordered MgAl2O4/Fe MTJs. The present study reveals that the high degree of B2-order and the resulting high spin polarization in the Co2FeAl electrodes enable us to bypass the band-folding problem in spinel barriers.

  13. Fate of injected CO2 in the Wilcox Group, Louisiana, Gulf Coast Basin: Chemical and isotopic tracers of microbial-brine-rock-CO2 interactions

    USGS Publications Warehouse

    Shelton, Jenna L.; McIntosh, Jennifer C.; Warwick, Peter D.; Lee Zhi Yi, Amelia

    2016-01-01

    The “2800’ sandstone” of the Olla oil field is an oil and gas-producing reservoir in a coal-bearing interval of the Paleocene–Eocene Wilcox Group in north-central Louisiana, USA. In the 1980s, this producing unit was flooded with CO2 in an enhanced oil recovery (EOR) project, leaving ∼30% of the injected CO2 in the 2800’ sandstone post-injection. This study utilizes isotopic and geochemical tracers from co-produced natural gas, oil and brine to determine the fate of the injected CO2, including the possibility of enhanced microbial conversion of CO2 to CH4 via methanogenesis. Stable carbon isotopes of CO2, CH4 and DIC, together with mol% CO2 show that 4 out of 17 wells sampled in the 2800’ sandstone are still producing injected CO2. The dominant fate of the injected CO2appears to be dissolution in formation fluids and gas-phase trapping. There is some isotopic and geochemical evidence for enhanced microbial methanogenesis in 2 samples; however, the CO2 spread unevenly throughout the reservoir, and thus cannot explain the elevated indicators for methanogenesis observed across the entire field. Vertical migration out of the target 2800’ sandstone reservoir is also apparent in 3 samples located stratigraphically above the target sand. Reservoirs comparable to the 2800’ sandstone, located along a 90-km transect, were also sampled to investigate regional trends in gas composition, brine chemistry and microbial activity. Microbial methane, likely sourced from biodegradation of organic substrates within the formation, was found in all oil fields sampled, while indicators of methanogenesis (e.g. high alkalinity, δ13C-CO2 and δ13C-DIC values) and oxidation of propane were greatest in the Olla Field, likely due to its more ideal environmental conditions (i.e. suitable range of pH, temperature, salinity, sulfate and iron concentrations).

  14. Effects of salinity and short-term elevated atmospheric CO2 on the chemical equilibrium between CO2 fixation and photosynthetic electron transport of Stevia rebaudiana Bertoni.

    PubMed

    Hussin, Sayed; Geissler, Nicole; El-Far, Mervat M M; Koyro, Hans-Werner

    2017-09-01

    The effect of water salinity on plant growth and photosynthetic traits of Stevia rebaudiana was investigated to determine its level and mechanisms of salinity tolerance. It was also attempted to assess how short-term elevated CO2 concentration would influence the boundaries and mechanisms of its photosynthetic capacity. The plants were grown in gravel/hydroponic system under controlled greenhouse conditions and irrigated with four different salinity levels (0, 25, 50 and 100 mol m(-3)NaCl). Low salinity did not significantly alter the plant fresh weight, which was substantially decreased by 67% at high salinity treatment. Salinity tolerance threshold was reached at 50 mol m(-3) NaCl while C50 was between 50 and 100 mol m(-3) NaCl, indicating that S. rebaudiana is a moderate salt tolerant species. Salt-induced growth reduction was apparently linked to a significant decline of about 47% in the photosynthetic rates (Anet) at high salinity treatment, leading consequently to a disequilibrium between CO2-assimilation and electron transport rates (indicated by enhanced ETRmax/Agross ratio). Elevated atmospheric CO2 enhanced CO2 assimilation rates by 65% and 80% for control and high-salt-stressed plants respectively, likely due to significant increases in intercellular CO2 concentration (indicated by enhanced Ci/Ca). The priority for Stevia under elevated atmospheric CO2 was not to save water but to maximize photosynthesis so that the PWUE was progressively improved and the threat of oxidative stress was diminished (decline in ETRmax/Agross). The results imply that elevated CO2 level could ameliorate some of the detrimental effects of salinity, conferring higher tolerance and survival of S. rebaudiana, a highlydesired feature with the forthcoming era of global changes. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

  15. Chemical composition and growing kinetics of titanium nitrided layers under CO2 laser irradiation

    NASA Astrophysics Data System (ADS)

    Laurens, Patricia; L'Enfant, Herve; Dubois, Thierry; Saint Catherine, Marie C.

    1997-08-01

    The growth and morphology of nitrided layers formed during the solid phase nitriding of pure titanium by CO2 laser were investigated. In the case of a laser treatment carried out under isothermal conditions, it was shown that CO2 photons irradiation of the substrate does not produce any specific assisted nitride growth: nitriding kinetics, nitride composition and structure were similar to those obtained after nitriding using a classical heating system. From the nitriding kinetics, nitrogen diffusion coefficients were determined using an analytical solution of Fick's equation. This allows to plot the evolution of the nitrogen concentration with respect to depth and to compare calculated profiles to those determined experimentally by Nuclear Reaction Microanalysis.

  16. Chemical weathering and long-term CO2 consumption in the Ayeyarwady and Mekong river basins in the Himalayas

    NASA Astrophysics Data System (ADS)

    Manaka, Takuya; Otani, Souya; Inamura, Akihiko; Suzuki, Atsushi; Aung, Thura; Roachanakanan, Raywadee; Ishiwa, Takeshige; Kawahata, Hodaka

    2015-06-01

    The role of terrestrial river systems in the global carbon cycle on a long timescale has been a subject of interest, especially in the context of past climate changes such as the global cooling in the Cenozoic. The discharges of water and carbon into the ocean from the Himalayan watersheds are among the highest in the world. However, there are few reliable geochemical data from the Ayeyarwady River. This study focused on reevaluating chemical weathering in the Himalayan watersheds based on samples taken from the Ayeyarwady, Mekong, and Chao Phraya Rivers and on chemical analysis of the composition of dissolved substances in these rivers. Comparisons of water quality showed that, unlike in previous studies, the total alkalinity budgets of the Ayeyarwady are dominated by carbonate rather than silicate weathering. Long-term CO2 consumption by silicate weathering in the Ayeyarwady is estimated to be only 63-145 × 109 mol yr-1, which is only 10% of the previous estimate. Our results also suggest that the total Himalayan watersheds account for only about 10% of the total global CO2 consumption by silicate weathering. Although we need further studies, chemical weathering and associated CO2 uptake in the Himalayas likely played a lesser role in long-term global cooling in the past than previously appreciated.

  17. The effect of increased atmospheric temperature and CO2 concentration during crop growth on the chemical composition and in vitro rumen fermentation characteristics of wheat straw.

    PubMed

    He, Xiangyu; Wu, Yanping; Cai, Min; Mu, Chunlong; Luo, Weihong; Cheng, Yanfen; Zhu, Weiyun

    2015-01-01

    This experiment was conducted to investigate the effects of increased atmospheric temperature and CO2 concentration during crop growth on the chemical composition and in vitro rumen fermentation characteristics of wheat straw. The field experiment was carried out from November 2012 to June 2013 at Changshu (31°32'93″N, 120°41'88″E) agro-ecological experimental station. A total of three treatments were set. The concentration of CO2 was increased to 500 μmol/mol in the first treatment (CO2 group). The temperature was increased by 2 °C in the second treatment (TEM group) and the concentration of CO2 and temperature were both increased in the third treatment (CO2 + TEM group). The mean temperature and concentration of CO2 in control group were 10.5 °C and 413 μmol/mol. At harvesting, the wheat straws were collected and analyzed for chemical composition and in vitro digestibility. Results showed that dry matter was significantly increased in all three treatments. Ether extracts and neutral detergent fiber were significantly increased in TEM and CO2 + TEM groups. Crude protein was significantly decreased in CO2 + TEM group. In vitro digestibility analysis of wheat straw revealed that gas production was significantly decreased in CO2 and CO2 + TEM groups. Methane production was significantly decreased in TEM and CO2 + TEM groups. Ammonia nitrogen and microbial crude protein were significantly decreased in all three treatments. Total volatile fatty acids were significantly decreased in CO2 and CO2 + TEM groups. In conclusion, the chemical composition of the wheat straw was affected by temperature and CO2 and the in vitro digestibility of wheat straw was reduced, especially in the combined treatment of temperature and CO2.

  18. A Lumped, Macroscopic Approach to Modeling Soil Moisture, CO2 Transport, and Chemical Weathering in the Critical Zone

    NASA Astrophysics Data System (ADS)

    Porporato, A. M.; Parolari, A.

    2015-12-01

    Ecohydrological processes in the root zone act as a dynamic interface between the atmosphere and the deeper soil layers, modulating the conditions that drive chemical weathering along the soil profile. Among these processes, soil moisture dynamics respond to intermittent rainfall pulses and to runoff and evapotranspiration losses. In addition, carbon dioxide (CO2) and its associated acidity are introduced into the soil moisture via root and microbial respiration. The coupling of soil moisture and CO2 dynamics in the root zone acts as an important controller of the critical zone development through the chemical weathering and water chemistry exported through runoff and percolation. Due to spatial and temporal variability and non-linearity, modeling these coupled root zone soil moisture and CO2 dynamics presents a number of challenges. In this talk, a lumped, macroscopic approach to modeling soil moisture, CO2 transport, and chemical weathering in the critical zone is introduced. The model considers a homogeneous soil column, therefore simplifying known spatial heterogeneities, and focuses on temporal variability resulting from non-linear processes and stochastic rainfall forcing. First, at short time-scales, the deterministic temporal evolution of soil moisture, dissolved inorganic carbon, pH, and alkalinity is analyzed using a dynamical system approach. Second, at longer inter-annual time-scales where rainfall stochasticity becomes an important driver of the system behavior, the system is analyzed probabilistically and its average behavior described using a novel macroscopic approach. This averaging of the nonlinear stochastic dynamics results in a closure problem that is addressed through a first-order approximation of non-linear fluxes, including the correlation between soil moisture and solutes. The model provides a method to assess how changes in external forcing or system properties propagate into and alter critical zone structure and function, and to isolate

  19. Subcritical crack growth in a chemically reactive environment-implications for caprock integrity for CO2 storage

    NASA Astrophysics Data System (ADS)

    Fan, Z.; Eichhubl, P.; Callahan, O. A.; Major, J. R.; Chen, X.

    2015-12-01

    Seal integrity of cap-rock is a critical constraint on the long term performance of CO2 containment site. During fluid migration, the coupled geochemical reaction of minerals and geomechanical deformation of rock matrix may affect the seal integrity. The potential leakage of injected CO2 from cap-rock through preexisting fractures/faults represents a major concern associated with geological storage of CO2. To address the fundamental question of CO2 leakage through subcritical growth of fractures driven by chemically reactive fluid across caprocks, we build a Dugdale cohesive model. Ahead of the physical crack tip, a narrow band of cohesive zone is assumed to exist with the upper and lower cohesive surfaces held by the cohesive traction. In the vicinity of the crack tip, minerals dissolve due to the acidic environment and migrate from the physical crack tip into the cohesive zone causing damage of rock matrix in the form of a reduction of cohesive traction.Focusing on the dissolution of calcite and following the stress corrosion theory, we assume the degradation of cohesive traction is linearly proportional to the concentration of Ca2+whose evolution follows the reactive diffusion equation. Using a critical crack opening displacement criterion, the subcritical propagation behavior of crack due to stress corrosion is captured and the rate-limiting effects including the chemical reactions to produce the Ca2+ and the transport of minerals along the newly generated fracture cohesive zone are incorporated. Subcritical crack growth rate under different chemical environment conditions is examined and compared with the experimental fracture mechanics testing.

  20. Biosynthesis of platform chemical 3-hydroxypropionic acid (3-HP) directly from CO2 in cyanobacterium Synechocystis sp. PCC 6803.

    PubMed

    Wang, Yunpeng; Sun, Tao; Gao, Xingyan; Shi, Mengliang; Wu, Lina; Chen, Lei; Zhang, Weiwen

    2016-03-01

    3-hydroxypropionic acid (3-HP) is an important platform chemical with a wide range of applications. So far large-scale production of 3-HP has been mainly through petroleum-based chemical processes, whose sustainability and environmental issues have attracted widespread attention. With the ability to fix CO2 directly, cyanobacteria have been engineered as an autotrophic microbial cell factory to produce fuels and chemicals. In this study, we constructed the biosynthetic pathway of 3-HP in cyanobacterium Synechocystis sp. PCC 6803, and then optimized the system through the following approaches: i) increasing expression of malonyl-CoA reductase (MCR) gene using different promoters and cultivation conditions; ii) enhancing supply of the precursor malonyl-CoA by overexpressing acetyl-CoA carboxylase and biotinilase; iii) improving NADPH supply by overexpressing the NAD(P) transhydrogenase gene; iv) directing more carbon flux into 3-HP by inactivating the competing pathways of PHA and acetate biosynthesis. Together, the efforts led to a production of 837.18 mg L(-1) (348.8 mg/g dry cell weight) 3-HP directly from CO2 in Synechocystis after 6 days cultivation, demonstrating the feasibility photosynthetic production of 3-HP directly from sunlight and CO2 in cyanobacteria. In addition, the results showed that overexpression of the ribulose-1, 5-bisphosphate carboxylase/oxygenase (Rubisco) gene from Anabaena sp. PCC 7120 and Synechococcus sp. PCC 7942 led to no increase of 3-HP production, suggesting CO2 fixation may not be a rate-limiting step for 3-HP biosynthesis in Synechocystis.

  1. CHEMICAL FIXATION OF CO2 IN COAL COMBUSTION PRODUCTS AND RECYCLING THROUGH BIOSYSTEMS

    SciTech Connect

    C. Henry Copeland; Paul Pier; Samantha Whitehead; Paul Enlow; Richard Strickland; David Behel

    2003-12-15

    This Annual Technical Progress Report presents the principle results in enhanced growth of algae using coal combustion products as a catalyst to increase bicarbonate levels in solution. A co-current reactor is present that increases the gas phase to bicarbonate transfer rate by a factor of five to nine. The bicarbonate concentration at a given pH is approximately double that obtained using a control column of similar construction. Algae growth experiments were performed under laboratory conditions to obtain baseline production rates and to perfect experimental methods. The final product of this initial phase in algae production is presented. Algal growth can be limited by several factors, including the level of bicarbonate available for photosynthesis, the pH of the growth solution, nutrient levels, and the size of the cell population, which determines the available space for additional growth. In order to supply additional CO2 to increase photosynthesis and algal biomass production, fly ash reactor has been demonstrated to increase the available CO2 in solution above the limits that are achievable with dissolved gas alone. The amount of dissolved CO2 can be used to control pH for optimum growth. Periodic harvesting of algae can be used to maintain algae in the exponential, rapid growth phase. An 800 liter scale up demonstrated that larger scale production is possible. The larger experiment demonstrated that indirect addition of CO2 is feasible and produces significantly less stress on the algal system. With better harvesting methods, nutrient management, and carbon dioxide management, an annual biomass harvest of about 9,000 metric tons per square kilometer (36 MT per acre) appears to be feasible. To sequester carbon, the algal biomass needs to be placed in a permanent location. If drying is undesirable, the biomass will eventually begin to aerobically decompose. It was demonstrated that algal biomass is a suitable feed to an anaerobic digester to produce methane

  2. Crystal engineering of an nbo topology metal-organic framework for chemical fixation of CO2 under ambient conditions.

    PubMed

    Gao, Wen-Yang; Chen, Yao; Niu, Youhong; Williams, Kia; Cash, Lindsay; Perez, Pastor J; Wojtas, Lukasz; Cai, Jianfeng; Chen, Yu-Sheng; Ma, Shengqian

    2014-03-03

    Crystal engineering of the nbo metal-organic framework (MOF) platform MOF-505 with a custom-designed azamacrocycle ligand (1,4,7,10-tetrazazcyclododecane-N,N',N'',N'''-tetra-p-methylbenzoic acid) leads to a high density of well-oriented Lewis active sites within the cuboctahedral cage in MMCF-2, [Cu2(Cu-tactmb)(H2O)3(NO3)2]. This MOF demonstrates high catalytic activity for the chemical fixation of CO2 into cyclic carbonates at room temperature under 1 atm pressure.

  3. Real-time measurements of chemical and isotope composition of atmospheric and volcanic CO2 at Mt. Etna (Italy)

    NASA Astrophysics Data System (ADS)

    Rizzo, Andrea L.; Jost, Hans-Jürg; Caracausi, Antonio; Paonita, Antonio; Liotta, Marcello; Martelli, Mauro

    2014-05-01

    We present unprecedented data of real-time measurements of chemical and isotope (δ13C) composition of CO2 in air and in fumarolic-plume gases collected at Mt. Etna volcano. Two campaigns of measurements were performed on 11 July and on 5-6 September 2013, by using a Delta Ray tunable diode laser. With the assumption of a two components mixing, a simple linear regression was applied to the data in order to obtain the volcanogenic δ13C. Data acquired along the route Catania-Etna, while car was moving, showed an excess of 13C-depleted CO2 when passing through inhabited centers due to atmospheric pollution produced by the cars exhaust. Fumaroles of Torre del Filosofo (2,900 m a.s.l.) displayed a δ13C between -3.2±0.03o and -3.7±0.05o comparable to IRMS measurements of discrete samples collected in the same date and in previous investigations. Diluted plume gases were collected at more than 1 km from the craters and showed δ13C=-2.2±0.2o accordingly with collected crater fumaroles. Considering the huge amount of data that may be acquired in a very short time by Delta Ray, we demonstrate that the addition to the atmospheric CO2 content of ~100 ppm of CO2 from an unknown source is enough to allow a mathematical calculation of the end-member with an uncertainty generally < 0.15‰This is feasible with the assumption of a binary mixing. We thus infer that the application performed at Mt. Etna may represent an historical step forward for the scientific community in volcanic surveillance.

  4. [Comparison of Chemical Components of Essential Oil from Ocimum basilicum var. pilosum Extracted by Supercritical CO2 Fluid and Steam Distillation].

    PubMed

    Wang, Zhao-yu; Zheng, Jia-huan; Shi, Sheng-ying; Luo, Zhi-xiong; Ni, Shun-yu; Lin, Jing-ming

    2015-11-01

    To compare the chemical components of essential oil prepared by steam distillation extraction (SD) and supercritical CO2 fluid extraction (SFE-CO2) from Ocimum basilicum var. pilosum whole plant. The essential oil of Ocimum basilicum var. pilosum were extracted by SD and SFE-CO2. The chemical components of essential oil were separated and analyzed by gas chromatography-mass spectrometry( GC-MS). Their relative contents were determined by normalization of peak area. 40 and 42 compounds were detected in the essential oil prepared by SD and SFE-CO2 respectively. 25 compounds were common. Thereare significant differences of the chemical components between the Ocimum basilicum var. pilosum essential oil prepared by SD and thatby SFE-CO2. Different methods showed different extraction efficiency with a special compound. It might be a good idea to unite several methods in the modern traditional Chinese medicine industry.

  5. Towards understanding the variability in biospheric CO2 fluxes: using FTIR spectrometry and a chemical transport model to investigate the sources and sinks of carbonyl sulfide and its link to CO2

    NASA Astrophysics Data System (ADS)

    Wang, Yuting; Deutscher, Nicholas M.; Palm, Mathias; Warneke, Thorsten; Notholt, Justus; Baker, Ian; Berry, Joe; Suntharalingam, Parvadha; Jones, Nicholas; Mahieu, Emmanuel; Lejeune, Bernard; Hannigan, James; Conway, Stephanie; Mendonca, Joseph; Strong, Kimberly; Campbell, J. Elliott; Wolf, Adam; Kremser, Stefanie

    2016-02-01

    Understanding carbon dioxide (CO2) biospheric processes is of great importance because the terrestrial exchange drives the seasonal and interannual variability of CO2 in the atmosphere. Atmospheric inversions based on CO2 concentration measurements alone can only determine net biosphere fluxes, but not differentiate between photosynthesis (uptake) and respiration (production). Carbonyl sulfide (OCS) could provide an important additional constraint: it is also taken up by plants during photosynthesis but not emitted during respiration, and therefore is a potential means to differentiate between these processes. Solar absorption Fourier Transform InfraRed (FTIR) spectrometry allows for the retrievals of the atmospheric concentrations of both CO2 and OCS from measured solar absorption spectra. Here, we investigate co-located and quasi-simultaneous FTIR measurements of OCS and CO2 performed at five selected sites located in the Northern Hemisphere. These measurements are compared to simulations of OCS and CO2 using a chemical transport model (GEOS-Chem). The coupled biospheric fluxes of OCS and CO2 from the simple biosphere model (SiB) are used in the study. The CO2 simulation with SiB fluxes agrees with the measurements well, while the OCS simulation reproduced a weaker drawdown than FTIR measurements at selected sites, and a smaller latitudinal gradient in the Northern Hemisphere during growing season when comparing with HIPPO (HIAPER Pole-to-Pole Observations) data spanning both hemispheres. An offset in the timing of the seasonal cycle minimum between SiB simulation and measurements is also seen. Using OCS as a photosynthesis proxy can help to understand how the biospheric processes are reproduced in models and to further understand the carbon cycle in the real world.

  6. On the value of CO2 cleaning operations: An engineering and chemical analysis

    SciTech Connect

    Williams, L. L.; Durkee, J.B.

    2004-01-01

    This study examines the chemical and engineering reasons why cleaning and particle-removal applications involving pressurized liquid and supercritical CO{sub 2} have been successful, and not. It is possible to predict which applications involving CO{sub 2} cleaning are likely to be successful, and which are not. The two key issues, which apply to use of any solvent for cleaning work, are: (1) How well the Hansen Solubility Parameters of the solvent match those of the soil - either chemical or polymer; and (2) How well the physical properties of the solvent augment the removal methods intended to liberate soil and particles from the substrate to be cleaned.

  7. Control of Convective Dissolution by Chemical Reactions: General Classification and Application to CO2 Dissolution in Reactive Aqueous Solutions

    NASA Astrophysics Data System (ADS)

    Loodts, V.; Thomas, C.; Rongy, L.; De Wit, A.

    2014-09-01

    In partially miscible two-layer systems within a gravity field, buoyancy-driven convective motions can appear when one phase dissolves with a finite solubility into the other one. We investigate the influence of chemical reactions on such convective dissolution by a linear stability analysis of a reaction-diffusion-convection model. We show theoretically that a chemical reaction can either enhance or decrease the onset time of the convection, depending on the type of density profile building up in time in the reactive solution. We classify the stabilizing and destabilizing scenarios in a parameter space spanned by the solutal Rayleigh numbers. As an example, we experimentally demonstrate the possibility to enhance the convective dissolution of gaseous CO2 in aqueous solutions by a classical acid-base reaction.

  8. Chemical reaction CO+OH • → CO2+H• autocatalyzed by carbon dioxide: Quantum chemical study of the potential energy surfaces

    DOE PAGES

    Masunov, Artem E.; Wait, Elizabeth; Vasu, Subith S.

    2016-06-28

    The supercritical carbon dioxide medium, used to increase efficiency in oxy combustion fossil energy technology, may drastically alter both rates and mechanisms of chemical reactions. Here we investigate potential energy surface of the second most important combustion reaction with quantum chemistry methods. Two types of effects are reported: formation of the covalent intermediates and formation of van der Waals complexes by spectator CO2 molecule. While spectator molecule alter the activation barrier only slightly, the covalent bonding opens a new reaction pathway. The mechanism includes sequential covalent binding of CO2 to OH radical and CO molecule, hydrogen transfer from oxygen tomore » carbon atoms, and CH bond dissociation. This reduces the activation barrier by 11 kcal/mol at the rate-determining step and is expected to accelerate the reaction rate. The finding of predicted catalytic effect is expected to play an important role not only in combustion but also in a broad array of chemical processes taking place in supercritical CO2 medium. Furthermore, tt may open a new venue for controlling reaction rates for chemical manufacturing.« less

  9. Chemical Reaction CO+OH(•) → CO2+H(•) Autocatalyzed by Carbon Dioxide: Quantum Chemical Study of the Potential Energy Surfaces.

    PubMed

    Masunov, Artëm E; Wait, Elizabeth; Vasu, Subith S

    2016-08-04

    The supercritical carbon dioxide medium, used to increase efficiency in oxy combustion fossil energy technology, may drastically alter both rates and mechanisms of chemical reactions. Here we investigate potential energy surface of the second most important combustion reaction with quantum chemistry methods. Two types of effects are reported: formation of the covalent intermediates and formation of van der Waals complexes by spectator CO2 molecule. While spectator molecule alter the activation barrier only slightly, the covalent bonding opens a new reaction pathway. The mechanism includes sequential covalent binding of CO2 to OH radical and CO molecule, hydrogen transfer from oxygen to carbon atoms, and CH bond dissociation. This reduces the activation barrier by 11 kcal/mol at the rate-determining step and is expected to accelerate the reaction rate. The finding of predicted catalytic effect is expected to play an important role not only in combustion but also in a broad array of chemical processes taking place in supercritical CO2 medium. It may open a new venue for controlling reaction rates for chemical manufacturing.

  10. Anion-Exchange Membrane Fuel Cells with Improved CO2 Tolerance: Impact of Chemically Induced Bicarbonate Ion Consumption.

    PubMed

    Katayama, Yu; Yamauchi, Kosuke; Hayashi, Kohei; Okanishi, Takeou; Muroyama, Hiroki; Matsui, Toshiaki; Kikkawa, Yuuki; Negishi, Takayuki; Watanabe, Shin; Isomura, Takenori; Eguchi, Koichi

    2017-08-30

    Over the last few decades, because of the significant development of anion exchange membranes, increasing efforts have been devoted the realization of anion exchange membrane fuel cells (AEMFCs) that operate with the supply of hydrogen generated on-site. In this paper, ammonia was selected as a hydrogen source, following which the effect of conceivable impurities, unreacted NH3 and atmospheric CO2, on the performance of AEMFCs was established. As expected, we show that these impurities worsen the performance of AEMFCs significantly. Furthermore, with the help of in situ attenuated total reflection infrared (ATR-IR) spectroscopy, it was revealed that the degradation of the cell performance was primarily due to the inhibition of the hydrogen oxidation reaction (HOR). This is attributed to the active site occupation by CO-related adspecies derived from (bi)carbonate adspecies. Interestingly, this degradation in the HOR activity is suppressed in the presence of both NH3 and HCO3(-) because of the bicarbonate ion consumption reaction induced by the existence of NH3. Further analysis using in situ ATR-IR and electrochemical methods revealed that the poisonous CO-related adspecies were completely removed under NH3-HCO3(-) conditions, accompanied by the improvement in HOR activity. Finally, a fuel cell test was conducted by using the practical AEMFC with the supply of NH3-contained H2 gas to the anode and ambient air to the cathode. The result confirmed the validity of this positive effect of NH3-HCO3(-) coexistence on CO2-tolerence of AEMFCs. The cell performance achieved nearly 95% of that without any impurity in the fuels. These results clearly show the impact of the chemically induced bicarbonate ion consumption reaction on the realization of highly CO2-tolerent AEMFCs.

  11. OPERATIONAL EXPERIENCE: UPGRADED MPC AND A SYSTEMS FOR THE RADIOCHEMICAL PLANT OF THE SIBERIAN CHEMICAL COMBINE

    SciTech Connect

    RODRIGUEZ,C.GOLOSKOKOV,I.FISHBONE,L.GOODEY,K.LOOMIS,M.CRAIN,B.JR.LARSEN,R.

    2003-07-18

    The success of reducing the risk of nuclear proliferation through physical protection and material control/accounting systems depends upon the development of an effective design that includes consideration of the objectives of the systems and the resources available to implement the design. Included among the objectives of the design are facility characterization, definition of threat, and identification of targets. When considering resources, the designer must consider funds available, rapid low-cost elements, technology elements, human resources, and the availability of resources to sustain operation of the end system. The Siberian Chemical Combine (SCC) is a multi-function nuclear facility located in the Tomsk region of Siberia, Russia. Beginning in 1996, SCC joined with the United States Department of Energy (US/DOE) Material Protection, Control, and Accounting (MPC&A) Program to develop and implement MPC&A upgrades for the Radiochemical, Chemical Metallurgical, Conversion, Uranium Enrichment, and Reactor Plants of the SCC. At the Radiochemical Plant the MPC&A design and implementation process has been largely completed for the Plutonium Storage Facility and related areas of the Radiochemical Plant. Design and implementation of upgrades for the Radiochemical Plant include rapid physical protection upgrades such as bricking up of doors and windows, and installation of security-hardened doors. Rapid material control and accounting upgrades include installation of modern balances and bar code equipment. Comprehensive MPC&A upgrades include the installation of access controls to sensitive areas of the Plant, alarm communication and display (AC&D) systems to detect and annunciate alarm conditions, closed circuit (CCTV) systems to assess alarm conditions, central and secondary alarm station upgrades that enable security forces to assess and respond to alarm conditions, material control and accounting upgrades that include upgraded physical inventory procedures, and

  12. Spatial variations in chemical weathering and CO 2 consumption in Nepalese High Himalayan catchments during the monsoon season

    NASA Astrophysics Data System (ADS)

    Wolff-Boenisch, Domenik; Gabet, Emmanuel J.; Burbank, Douglas W.; Langner, Heiko; Putkonen, Jaakko

    2009-06-01

    The major ion chemistry of the Marsyandi basin and six of its tributaries in the Nepalese Himalaya have been investigated during the monsoon months of 2002. Weekly water samples taken at 10 river monitoring stations in the Annapurna watershed over the course of 4 months provide chemical weathering data for the region at an unprecedented temporal and spatial resolution. The river chemistry of all but one basin is heavily dominated by carbonate weathering which, compared to silicate weathering, contributes 80 to 97% of the total solute load. This prevalence is due to a combination of (a) intrinsically faster dissolution kinetics of carbonates, (b) relatively high runoff and (c) glacial meltwater and low temperatures at high altitudes resulting in enhanced carbonate solubilities. Monitoring stations with headwaters in the Tethyan Sedimentary Series (TSS) are particularly carbonate-rich and slightly supersaturated with respect to calcite through half of the monsoon season. Silicate weathering in the TSS is driven largely by sulfuric acid and therefore does not contribute significantly to the drawdown of atmospheric CO 2. With respect to the tributaries in the Greater Himalayan Sequence (GHS), carbonate weathering is practically as predominant as for the TSS, in spite of the largely felsic lithology of the GHS. Relative to the TSS, the primary proton source in the GHS has shifted, with at least 80% of the protons derived from carbonic acid. Averaged over the whole field area, the CO 2 fluxes, based on silicate-derived Ca and Mg, are considerably lower than the global average. Assuming that this study area is representative of the entire range, we conclude that in situ weathering of the High Himalayas does not represent a significant sink of atmospheric carbon dioxide, despite the presence of a watershed south of the GHS that is characterized by a four times higher CO 2 consumption rate than the global average. Silicate weathering rates of all basins appear to be climate

  13. Long-term operation of microbial electrosynthesis cell reducing CO2 to multi-carbon chemicals with a mixed culture avoiding methanogenesis.

    PubMed

    Bajracharya, Suman; Yuliasni, Rustiana; Vanbroekhoven, Karolien; Buisman, Cees J N; Strik, David P B T B; Pant, Deepak

    2017-02-01

    In microbial electrosynthesis (MES), CO2 can be reduced preferably to multi-carbon chemicals by a biocathode-based process which uses electrochemically active bacteria as catalysts. A mixed anaerobic consortium from biological origin typically produces methane from CO2 reduction which circumvents production of multi-carbon compounds. This study aimed to develop a stable and robust CO2 reducing biocathode from a mixed culture inoculum avoiding the methane generation. An effective approach was demonstrated based on (i) an enrichment procedure involving inoculum pre-treatment and several culture transfers in H2:CO2 media, (ii) a transfer from heterotrophic to autotrophic growth and (iii) a sequential batch operation. Biomass growth and gradual acclimation to CO2 electro-reduction accomplished a maximum acetate production rate of 400mgLcatholyte(-1)d(-1) at -1V (vs. Ag/AgCl). Methane was never detected in more than 300days of operation. Accumulation of acetate up to 7-10gL(-1) was repeatedly attained by supplying (80:20) CO2:N2 mixture at -0.9 to -1V (vs. Ag/AgCl). In addition, ethanol and butyrate were also produced from CO2 reduction. Thus, a robust CO2 reducing biocathode can be developed from a mixed culture avoiding methane generation by adopting the specific culture enrichment and operation procedures without the direct addition of chemical inhibitor.

  14. The contribution of changes in P release and CO2 consumption by chemical weathering to the historical trend in land carbon uptake

    NASA Astrophysics Data System (ADS)

    Goll, D. S.; Moosdorf, N.; Brovkin, V.; Hartmann, J.

    2013-12-01

    The atmospheric carbon dioxide (CO2) concentration has increased to a level unprecedented in the last 2 million years, and the concentration is projected to increase further with a rate unseen in geological past. The increase in CO2 cause a rise in surface temperatures and changes in the hydrological cycle through the redistribution of rainfall patterns. All of these changes will impact the weathering of rocks, which in turn affect atmospheric CO2 concentrations via two different pathways. On the one hand, CO2 is consumed by the dissolution reaction of the exposed minerals. And on the other hand, biological CO2 fixation is affected due to changes in phosphorus release from minerals, as biological activity is constrained by phosphorus availability at large scales. The traditional view is that both effects are negligible on a centennial time scale, but recent work on catchment scale challenge this view in favor of a potential high sensitivity of weathering to ongoing climate and land use changes. To globally quantify the contribution of CO2 fixation associated with weathering on the historical trend in terrestrial CO2 uptake, we applied a model of chemical weathering and phosphorus release under climate reconstructions from four Earth System Models. The simulations indicate that changes in weathering could have contributed considerably to the trend in terrestrial CO2 uptake since the pre-industrial revolution, with warming being the main driver of change. The increase in biological CO2 fixation is of comparable magnitude as the increase in CO2 consumption by chemical weathering. Our simulations support the previous findings on catchment scale that weathering can change significantly on a centennial time scale. This finding has implications for 21st century climate projections, which ignore changes in weathering, as well as for long-term airborne fraction of CO2 emissions, whose calculation usually neglects changes in phosphorus availability.

  15. The contribution of changes in P release and CO2 consumption by chemical weathering to the historical trend in land carbon uptake

    NASA Astrophysics Data System (ADS)

    Goodale, C. L.; Fredriksen, G.; McCalley, C. K.; Sparks, J. P.; Thomas, S. A.

    2011-12-01

    The atmospheric carbon dioxide (CO2) concentration has increased to a level unprecedented in the last 2 million years, and the concentration is projected to increase further with a rate unseen in geological past. The increase in CO2 cause a rise in surface temperatures and changes in the hydrological cycle through the redistribution of rainfall patterns. All of these changes will impact the weathering of rocks, which in turn affect atmospheric CO2 concentrations via two different pathways. On the one hand, CO2 is consumed by the dissolution reaction of the exposed minerals. And on the other hand, biological CO2 fixation is affected due to changes in phosphorus release from minerals, as biological activity is constrained by phosphorus availability at large scales. The traditional view is that both effects are negligible on a centennial time scale, but recent work on catchment scale challenge this view in favor of a potential high sensitivity of weathering to ongoing climate and land use changes. To globally quantify the contribution of CO2 fixation associated with weathering on the historical trend in terrestrial CO2 uptake, we applied a model of chemical weathering and phosphorus release under climate reconstructions from four Earth System Models. The simulations indicate that changes in weathering could have contributed considerably to the trend in terrestrial CO2 uptake since the pre-industrial revolution, with warming being the main driver of change. The increase in biological CO2 fixation is of comparable magnitude as the increase in CO2 consumption by chemical weathering. Our simulations support the previous findings on catchment scale that weathering can change significantly on a centennial time scale. This finding has implications for 21st century climate projections, which ignore changes in weathering, as well as for long-term airborne fraction of CO2 emissions, whose calculation usually neglects changes in phosphorus availability.

  16. Malaria Parasite Metabolic Pathways (MPMP) Upgraded with Targeted Chemical Compounds.

    PubMed

    Ginsburg, Hagai; Abdel-Haleem, Alyaa M

    2016-01-01

    Malaria Parasite Metabolic Pathways (MPMP) is the website for the functional genomics of intraerythrocytic Plasmodium falciparum. All the published information about targeted chemical compounds has now been added. Users can find the drug target and publication details linked to a drug database for further information about the medicinal properties of each compound.

  17. Copper-manganese mixed oxides: CO2-selectivity, stable, and cyclic performance for chemical looping combustion of methane.

    PubMed

    Mungse, Pallavi; Saravanan, Govindachetty; Uchiyama, Tomoki; Nishibori, Maiko; Teraoka, Yasutake; Rayalu, Sadhana; Labhsetwar, Nitin

    2014-09-28

    Chemical looping combustion (CLC) is a key technology for oxy-fuel combustion with inherent separation of CO2 from a flue gas, in which oxygen is derived from a solid oxygen carrier. Multi-cycle CLC performance and the product selectivity towards CO2 formation were achieved using mixed oxide of Cu and Mn (CuMn2O4) (Fd3[combining macron]m, a = b = c = 0.83 nm) as an oxygen carrier. CuMn2O4 was prepared by the co-precipitation method followed by annealing at 900 °C using copper(II) nitrate trihydrate and manganese(II) nitrate tetrahydrate as metal precursors. CuMn2O4 showed oxygen-desorption as well as reducibility at elevated temperatures under CLC conditions. The lattice of CuMn2O4 was altered significantly at higher temperature, however, it was reinstated virtually upon cooling in the presence of air. CuMn2O4 was reduced to CuMnO2, Mn3O4, and Cu2O phases at the intermediate stages, which were further reduced to metallic Cu and MnO upon the removal of reactive oxygen from their lattice. CuMn2O4 showed a remarkable activity towards methane combustion reaction at 750 °C. The reduced phase of CuMn2O4 containing Cu and MnO was readily reinstated when treated with air or oxygen at 750 °C, confirming efficient regeneration of the oxygen carrier. Neither methane combustion efficiency nor oxygen carrying capacity was altered with the increase of CLC cycles at any tested time. The average oxygen carrying capacity of CuMn2O4 was estimated to be 114 mg g(-1), which was not altered significantly with the repeated CLC cycles. Pure CO2 but no CO, which is one of the possible toxic by-products, was formed solely upon methane combustion reaction of CuMn2O4. CuMn2O4 shows potential as a practical CLC material both in terms of multi-cycle performance and product selectivity towards CO2 formation.

  18. Production of chemicals from C1 gases (CO, CO2) by Clostridium carboxidivorans.

    PubMed

    Fernández-Naveira, Ánxela; Abubackar, Haris Nalakath; Veiga, María C; Kennes, Christian

    2017-03-01

    Bioprocesses in conventional second generation biorefineries are mainly based on the fermentation of sugars obtained from lignocellulosic biomass or agro-industrial wastes. An alternative to this process consists in gasifying those same feedstocks or even other carbon-containing materials to obtain syngas which can also be fermented by some anaerobic bacteria to produce chemicals or fuels. Carbon monoxide, carbon dioxide and hydrogen, which are the main components of syngas, are also found in some industrial waste gases, among others in steel industries. Clostridium carboxidivorans is able to metabolise such gases to produce ethanol and higher alcohols, i.e. butanol and hexanol, following the Wood-Ljungdahl pathway. This does simultaneously allow the removal of volatile pollutants involved in climate change. The bioconversion is a two step process in which organic acids (acetate, butyrate, hexanoate) are produced first, followed by the accumulation of alcohols; although partial overlap in time of acids and alcohols production may sometimes take place as well. Several parameters, among others pH, temperature, or gas-feed flow rates in bioreactors, affect the bioconversion process. Besides, the accumulation of high concentrations of alcohols in the fermentation broth inhibits the growth and metabolic activity of C. carboxidivorans.

  19. Direct PEM fuel cell using "organic chemical hydrides" with zero-CO2 emission and low-crossover.

    PubMed

    Kariya, Nobuko; Fukuoka, Atsushi; Ichikawa, Masaru

    2006-04-14

    A series of "organic chemical hydrides" such as cyclohexane, methylcyclohexane, cyclohexene, 2-propanol, and cyclohexanol were applied to the direct PEM fuel cell. High performances of the PEM fuel cell were achieved by using cyclohexane (OCV = 920 mV, PD(max) = 15 mW cm(-2)) and 2-propanol (OCV = 790 mV, PD(max) = 78 mW cm(-2)) as fuels without CO(2) emissions. The rates of fuel crossover for cyclohexane, 2-propanol, and methanol were estimated, and the rates of fuel permeation of cyclohexane and 2-propanol were lower than that of methanol. Water electrolysis and electro-reductive hydrogenation of acetone mediated by PEM were carried out and formation of 2-propanol in cathode side was observed. This system is the first example of a "rechargeable" direct fuel cell.

  20. Novel process and catalytic materials for converting CO2 and H2 containing mixtures to liquid fuels and chemicals.

    PubMed

    Meiri, Nora; Dinburg, Yakov; Amoyal, Meital; Koukouliev, Viatcheslav; Nehemya, Roxana Vidruk; Landau, Miron V; Herskowitz, Moti

    2015-01-01

    Carbon dioxide and water are renewable and the most abundant feedstocks for the production of chemicals and fungible fuels. However, the current technologies for production of hydrogen from water are not competitive. Therefore, reacting carbon dioxide with hydrogen is not economically viable in the near future. Other alternatives include natural gas, biogas or biomass for the production of carbon dioxide, hydrogen and carbon monoxide mixtures that react to yield chemicals and fungible fuels. The latter process requires a high performance catalyst that enhances the reverse water-gas-shift (RWGS) reaction and Fischer-Tropsch synthesis (FTS) to higher hydrocarbons combined with an optimal reactor system. Important aspects of a novel catalyst, based on a Fe spinel and three-reactor system developed for this purpose published in our recent paper and patent, were investigated in this study. Potassium was found to be a key promoter that improves the reaction rates of the RWGS and FTS and increases the selectivity of higher hydrocarbons while producing mostly olefins. It changed the texture of the catalyst, stabilized the Fe-Al-O spinel, thus preventing decomposition into Fe3O4 and Al2O3. Potassium also increased the content of Fe5C2 while shifting Fe in the oxide and carbide phases to a more reduced state. In addition, it increased the relative exposure of carbide iron on the catalysts surface, the CO2 adsorption and the adsorption strength. A detailed kinetic model of the RWGS, FTS and methanation reactions was developed for the Fe spinel catalyst based on extensive experimental data measured over a range of operating conditions. Significant oligomerization activity of the catalyst was found. Testing the pelletized catalyst with CO2, CO and H2 mixtures over a range of operating conditions demonstrated its high productivity to higher hydrocarbons. The composition of the liquid (C5+) was found to be a function of the potassium content and the composition of the feedstock.

  1. Highly Efficient Oxygen-Storage Material with Intrinsic Coke Resistance for Chemical Looping Combustion-Based CO2 Capture.

    PubMed

    Imtiaz, Qasim; Kurlov, Alexey; Rupp, Jennifer Lilia Marguerite; Müller, Christoph Rüdiger

    2015-06-22

    Chemical looping combustion (CLC) and chemical looping with oxygen uncoupling (CLOU) are emerging thermochemical CO2 capture cycles that allow the capture of CO2 with a small energy penalty. Here, the development of suitable oxygen carrier materials is a key aspect to transfer these promising concepts to practical installations. CuO is an attractive material for CLC and CLOU because of its high oxygen-storage capacity (20 wt %), fast reaction kinetics, and high equilibrium partial pressure of oxygen at typical operating temperatures (850-1000 °C). However, despite its promising characteristics, its low Tammann temperature requires the development of new strategies to phase-stabilize CuO-based oxygen carriers. In this work, we report a strategy based on stabilization by co-precipitated ceria (CeO2-x ), which allowed us to increase the oxygen capacity, coke resistance, and redox stability of CuO-based oxygen carriers substantially. The performance of the new oxygen carriers was evaluated in detail and compared to the current state-of-the-art materials, that is, Al2 O3 -stabilized CuO with similar CuO loadings. We also demonstrate that the higher intrinsic oxygen uptake, release, and mobility in CeO2-x -stabilized CuO leads to a three times higher carbon deposition resistance compared to that of Al2 O3 -stabilized CuO. Moreover, we report a high cyclic stability without phase intermixing for CeO2-x -supported CuO. This was accompanied by a lower reduction temperature compared to state-of-the-art Al2 O3 -supported CuO. As a result of its high resistance towards carbon deposition and fast oxygen uncoupling kinetics, CeO2-x -stabilized CuO is identified as a very promising material for CLC- and CLOU-based CO2 capture architectures. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. The effect of nitrogen doping on mercury oxidation/chemical adsorption on the CuCo2O4(110) surface: a molecular-level description.

    PubMed

    Mei, Zhijian; Fan, Maohong; Zhang, Ruiqing; Shen, Zhemin; Wang, Wenhua

    2014-07-14

    Based on density functional theory (DFT) calculations, the detailed mercury oxidation/chemical adsorption mechanisms on the N-doped CuCo2O4(110) surface are studied. The DFT calculations show that Ow (bonded with one Cu(2+) ion and one Co(3+) ion) is far more active than Os (bonded with three Co(3+) ions) and the mercury oxidation/chemical adsorption activation energy (Ea) on the virgin CuCo2O4(110) surface involving Ow is 0.85 eV. The physically adsorbed mercury overcomes the Ea and enters the energy well that plays an important role in mercury oxidation/chemical adsorption. Nitrogen doping can greatly increase the activity of Ow and decrease the activity of Os at the same time, which greatly affect the mercury oxidation/chemical adsorption abilities on the CuCo2O4(110) surface, and the Ea variation of mercury oxidation/chemical adsorption is as follows: 0.85 eV (virgin CuCo2O4(110)) → 0.76 eV (one N-doped CuCo2O4(110)) → 0.69 eV (two N-doped CuCo2O4(110)) → 0.48 eV (three N-doped CuCo2O4(110)). In addition, N-doping can decrease the adsorption energy of mercury and mercuric oxide. The effect of N-doping on the bonding mechanism of mercury adsorption on the CuCo2O4(110) surface is analyzed by the local density of state (LDOS) and the natural bonding orbital (NBO). The calculation results correspond well to the experimental data.

  3. Flow paths and chemical reactivity of CO2 in carbonates using Mercury-Intrusion Capillary Pressure data and dimensionless numbers

    NASA Astrophysics Data System (ADS)

    Vialle, S.; Dvorkin, J. P.; Mavko, G. M.

    2012-12-01

    Experiments performed earlier by Vialle and Vanorio (2011) [1] have showed that the injection of CO2-rich water (pH=3.2) in various calcite limestones lead to heterogeneous dissolution of the pore structure, inducing secondary porosity and changing the rock stiffness. The presence of oil in the pore space affects the magnitude of these changes by lowering the reactive surface area. We present here a semi-quantitative analysis at the mesoscale to investigate how different initial pore microgeometries and heterogeneities in pore microgeometry affect the fluid-rock interactions. In particular, we aim at quantitatively explaining (1) why, in clean samples, higher-porosity micrite with rounded grains appears to be more affected by dissolution than tight micrite and spar cement and (2) why, for the same number of pore volumes of fluid injected, the magnitude of the changes in porosity (and subsequently elastic properties) differs among the studied rock samples. Rock microgeometry is studied by classical rock-physics methods, He-pycnometry and Mercury-Intrusion Capillary Pressure (MICP) tests, as well as by Scanning Electron Microscopy (SEM) imaging. Experiments were performed on subsamples (~0.5cm3) extracted from core plugs (~12cm3): two Fontainebleau sandstones, to serve as benchmarks, and two calcite carbonates from two different geological formations. In order to relate pore microgeometry to flow paths and chemical reactivity of CO2 in carbonate rocks, we chose to work at a scale that lies between the pore scale and the core scale. The method consists of physically subdividing the core plugs under examination into subsets based on the pore-throat sizes; these subsets correspond to three types of microstructure: "macropores", "microporous rounded micrite", and "spar cement"/"tight micrite". The dimensionless Péclet (Pe) and Damkhöler (Da) numbers, defined as the ratio between the advection rate and the diffusion rate, and as the ratio between the reaction rate and

  4. Towards understanding the variability in biospheric CO2 fluxes: using FTIR spectrometry and a chemical transport model to investigate the sources and sinks of carbonyl sulfide and its link to CO2

    NASA Astrophysics Data System (ADS)

    Wang, Y.; Deutscher, N. M.; Palm, M.; Warneke, T.; Notholt, J.; Baker, I.; Berry, J.; Suntharalingam, P.; Jones, N.; Mahieu, E.; Lejeune, B.; Campbell, J. E.; Wolf, A.; Kremser, S.

    2015-09-01

    Understanding carbon dioxide (CO2) biospheric processes is of great importance because the terrestrial exchange drives the seasonal and inter-annual variability of CO2 in the atmosphere. Atmospheric inversions based on CO2 concentration measurements alone can only determine net biosphere fluxes, but not differentiate between photosynthesis (uptake) and respiration (production). Carbonyl sulfide (OCS) could provide an important additional constraint: it is also taken up by plants during photosynthesis but not emitted during respiration, and therefore is a potential mean to differentiate between these processes. Solar absorption Fourier Transform InfraRed (FTIR) spectrometry allows for the retrievals of the atmospheric concentrations of both CO2 and OCS from measured solar absorption spectra. Here, we investigate co-located and quasi-simultaneous FTIR measurements of OCS and CO2 performed at three selected sites located in the Northern Hemisphere. These measurements are compared to simulations of OCS and CO2 using a chemical transport model (GEOS-Chem). The OCS simulations are driven by different land biospheric fluxes to reproduce the seasonality of the measurements. Increasing the plant uptake of Kettle et al. (2002a) by a factor of three resulted in the best comparison with FTIR measurements. However, there are still discrepancies in the latitudinal distribution when comparing with HIPPO (HIAPER Pole-to-Pole Observations) data spanning both hemispheres. The coupled biospheric fluxes of OCS and CO2 from the simple biosphere model (SiB) are used in the study and compared to measurements. The CO2 simulation with SiB fluxes agrees with the measurements well, while the OCS simulation reproduced a weaker drawdown than FTIR measurements at selected sites, and a smaller latitudinal gradient in the Northern Hemisphere during growing season. An offset in the timing of the seasonal cycle minimum between SiB simulation and measurements is also seen. Using OCS as a

  5. Etchant solutions for the removal of Cu(0) in a supercritical CO2-based "dry" chemical mechanical planarization process for device fabrication.

    PubMed

    Bessel, Carol A; Denison, Ginger M; DeSimone, Joseph M; DeYoung, James; Gross, Stephen; Schauer, Cynthia K; Visintin, Pamela M

    2003-04-30

    The microelectronics industry is focused on increasing chip complexity, improving the density of electron carriers, and decreasing the dimensions of the interconnects into the sub-0.25 mum regime while maintaining high aspect ratios. Water-based chemical mechanical planarization or polishing (CMP) faces several technical and environmental challenges. Condensed CO2 has significant potential for replacing current CMP solvents as a "dry" etching medium because of its unique properties. In working toward a condensed CO2-based CMP process, we have successfully investigated the oxidation and chelation of solid copper metal in liquid and supercritical CO2 using ethyl peroxydicarbonate and a beta-diketone chelating agent.

  6. Mass Conservation in a Chemical Transport Model and its Effect on CO2 and SF6 Simulations

    NASA Technical Reports Server (NTRS)

    Zhu, Z.; Weaver, C.; Kawa, S. R.; Douglass, A. R.; Bhartia, P. K. (Technical Monitor)

    2002-01-01

    Chemical transport models (CTMs) must conserve mass to be useful for applications involving assessment of the effect of various pollutants on the troposphere and stratosphere. Furthermore, calculations of the evolution of constituents such as SF6 are used to evaluate overall model transport, and interpretation of such simulations is clouded if mass conservation is not assured. For realistic simulations or predictions, it is crucial that constituents are not produced or lost by transport or other processes in the CTMs. Analysis of CO2 and SF6 experiments using a CTM shows that problems with mass conservation can seriously degrade the simulations. Failure to conserve mass results from inconsistency of the surface pressure tendency and the divergence of horizontal mass flux when the model is forced by assimilated meteorological data. We have developed an effective method to eliminate the inconsistency by modifying the divergent part of the wind field. The changes in the wind fields are quite small but the impact on mass conservation is large. Parameterizations of physical processes such as convection or turbulent transport can also affect mass conservation. The lack of conservation is small but accumulates when integrations are lengthy such as required for SF6. This lack of conservation is found using winds from either a GCM or from an assimilation system. A simple adjustment removes much of the inaccuracy in the convective parameterization. A CO2 simulation using assimilated winds from the most recent version of the Goddard Earth Observing System Data Assimilation System will be used to illustrate the impact of these transport improvements.

  7. Mass Conservation in a Chemical Transport Model and its Effect on CO2 and SF6 Simulations

    NASA Technical Reports Server (NTRS)

    Zhu, Z.; Weaver, C.; Kawa, S. R.; Douglass, A. R.; Bhartia, P. K. (Technical Monitor)

    2002-01-01

    Chemical transport models (CTMs) must conserve mass to be useful for applications involving assessment of the effect of various pollutants on the troposphere and stratosphere. Furthermore, calculations of the evolution of constituents such as SF6 are used to evaluate overall model transport, and interpretation of such simulations is clouded if mass conservation is not assured. For realistic simulations or predictions, it is crucial that constituents are not produced or lost by transport or other processes in the CTMs. Analysis of CO2 and SF6 experiments using a CTM shows that problems with mass conservation can seriously degrade the simulations. Failure to conserve mass results from inconsistency of the surface pressure tendency and the divergence of horizontal mass flux when the model is forced by assimilated meteorological data. We have developed an effective method to eliminate the inconsistency by modifying the divergent part of the wind field. The changes in the wind fields are quite small but the impact on mass conservation is large. Parameterizations of physical processes such as convection or turbulent transport can also affect mass conservation. The lack of conservation is small but accumulates when integrations are lengthy such as required for SF6. This lack of conservation is found using winds from either a GCM or from an assimilation system. A simple adjustment removes much of the inaccuracy in the convective parameterization. A CO2 simulation using assimilated winds from the most recent version of the Goddard Earth Observing System Data Assimilation System will be used to illustrate the impact of these transport improvements.

  8. Understanding the CO Dissociation in [Fe(CN)2(CO)2(dithiolate)](2-) Complexes with Quantum Chemical Topology Tools.

    PubMed

    Lebon, Alexandre; Orain, Pierre-Yves; Memboeuf, Antony

    2017-09-07

    The active site of the [NiFe]-hydrogenase contains a pentacoordinated iron atom; therefore, a vacant coordination site is available for substrate binding. Nonetheless, most organometallic models of the [NiFe]-hydrogenase failed to reproduce this key feature of the active site. In order to rationalize such behavior, quantum chemical calculations were carried out on a series of [Fe(CN)2(CO)n(dithiolate)](2-) n = 1,2 complexes, where dithiolate denotes the ligands (CF3)2C2S2(2-), (CO2Me)2C2S2(2-), Ph2C2S2(2-), C6Cl2H2S2(2-), C6H4S2(2-), C2H4S2(2-), and C3H6S2(2-). Structural and energetic features are discussed, and a topological analysis based on two scalar fields, the one-electron density and the electron localization function (ELF), has been attempted to describe the nature of the metal-ligand bonds. The present approach contributes to better understand the ability of noninnocent dithiolene to strongly labilize one CO whereas innocent dithiolate cannot. The methodology developed throughout the paper could be useful in the field of the CO-releasing molecules.

  9. CO2 enhanced chemical vapor deposition growth of few-layer graphene over NiO(x).

    PubMed

    Son, In Hyuk; Song, Hyun Jae; Kwon, Soonchul; Bachmatiuk, Alicja; Lee, Seung Jae; Benayad, Anass; Park, Jong Hwan; Choi, Jae-Young; Chang, Hyuk; Rümmeli, Mark H

    2014-09-23

    The use of mild oxidants in chemical vapor deposition (CVD) reactions has proven enormously useful. This was also true for the CVD growth of carbon nanotubes. As yet though, the use of mild oxidants in the CVD of graphene has remained unexplored. Here we explore the use of CO2 as a mild oxidant during the growth of graphene over Ni with CH4 as the feedstock. Both our experimental and theoretical findings provide in-depth insight into the growth mechanisms and point to the mild oxidants playing multiple roles. Mild oxidants lead to the formation of a suboxide in the Ni, which suppresses the bulk diffusion of C species suggesting a surface growth mechanism. Moreover, the formation of a suboxide leads to enhanced catalytic activity at the substrate surface, which allows reduced synthesis temperatures, even as low as 700 °C. Even at these low temperatures, the quality of the graphene is exceedingly high as indicated by a negligible D mode in the Raman spectra. These findings suggest the use of mild oxidants in the CVD fabrication as a whole could have a positive impact.

  10. Chemical and morphological changes during olivine carbonation for CO2 storage in the presence of NaCl and NaHCO3.

    PubMed

    Gadikota, Greeshma; Matter, Juerg; Kelemen, Peter; Park, Ah-Hhyung Alissa

    2014-03-14

    The increasing concentrations of CO2 in the atmosphere are attributed to the rising consumption of fossil fuels for energy generation around the world. One of the most stable and environmentally benign methods of reducing atmospheric CO2 is by storing it as thermodynamically stable carbonate minerals. Olivine ((Mg,Fe)2SiO4) is an abundant mineral that reacts with CO2 to form Mg-carbonate. The carbonation of olivine can be enhanced by injecting solutions containing CO2 at high partial pressure into olivine-rich formations at high temperatures, or by performing ex situ mineral carbonation in a reactor system with temperature and pressure control. In this study, the effects of NaHCO3 and NaCl, whose roles in enhanced mineral carbonation have been debated, were investigated in detail along with the effects of temperature, CO2 partial pressure and reaction time for determining the extent of olivine carbonation and its associated chemical and morphological changes. At high temperature and high CO2 pressure conditions, more than 70% olivine carbonation was achieved in 3 hours in the presence of 0.64 M NaHCO3. In contrast, NaCl did not significantly affect olivine carbonation. As olivine was dissolved and carbonated, its pore volume, surface area and particle size were significantly changed and these changes influenced subsequent reactivity of olivine. Thus, for both long-term simulation of olivine carbonation in geologic formations and the ex situ reactor design, the morphological changes of olivine during its reaction with CO2 should be carefully considered in order to accurately estimate the CO2 storage capacity and understand the mechanisms for CO2 trapping by olivine.

  11. [Analyze on chemical compositions of Dalbergia odorifera essential oils extracted by CO2-supercritical-fluid-extraction and steam distillation extraction].

    PubMed

    Song, Wei-Feng; Liao, Mei-Jin; Luo, Shu-Yuan

    2011-11-01

    To analyze the chemical compositions of Dalbergia odorifera essential oils extacted by CO2-supercritical-fluid-extraction (SFE-CO2) and steam distillation extraction (SD). The essential oils of Dalbergia odorifera were extracted by steam distillation extraction and SFE-CO2. The chemical components were separated and analyzed by gas chromatography-mass spectrometry. 12 compounds were identified in SFE sample. The major components from essential oils were 2-propenoic acid-3(4-methoxyphenyl)-ethyl ester (14.53%), nerolidol (14.95%), ageratochromene (1.33%). 9 compounds were identified in SD sample. The major components from essential oils were nerolidol (26.61%), cedrol (1.65%). The SFE method is better than the SD method in reliability stability and reproducibility, and suitable for essential oils extraction of Dalbergia odorifera.

  12. Using Carbonyl Sulfide Column Measurements and a Chemical Transport Model to Investigate Variability in Biospheric CO2 Fluxes

    NASA Astrophysics Data System (ADS)

    Wang, Y.; Palm, M.; Deutscher, N. M.; Warneke, T.; Notholt, J.; Baker, I. T.; Berry, J. A.; Suntharalingam, P.; Campbell, J. E.; Wolf, A.

    2014-12-01

    Understanding the CO2 processes on land is of great importance, because the terrestrial exchange drives the seasonal and interannual variability of CO2 in the atmosphere. Atmospheric inversions based on CO2 concentration measurements alone can only determine net biosphere fluxes, but not differentiate between photosynthesis (uptake) and respiration (production). Carbonyl sulfide (OCS) could provide an important additional constraint: it is also taken up by plants during photosynthesis but not emitted during respiration, and therefore is a potential means to differentiate between these processes. Solar absorption Fourier Transform InfraRed (FTIR) spectrometry allows for the retrieval of the atmospheric concentrations of both CO2 and OCS. Here, we investigate co-located and nearly simultaneous measurements of OCS and CO2 measured at 3 sites via FTIR spectrometers. These northern-hemispheric sites span a wide range of latitudes and all have multiple year time-series. The sites include Ny-Alesund (79°N), Bremen (53°N) and Paramaribo (6°N). We compare these measurements to simulations of OCS and CO2 using the GEOS-Chem model. The simulations are driven by different land biospheric fluxes of OCS and CO2 to match the seasonality of the measurements. The simple biosphere model (SiB-COS) are used in the study because it simultaneously calculates the biospheric fluxes of both OCS and CO2. The CO2 simulation with SiB fluxes agrees with the measurements better than a simulation using CASA. Comparison of the OCS simulations with different fluxes indicates that the latitudinal distribution of the OCS fluxes within SiB needs to be adjusted.

  13. Using Carbonyl Sulfide column measurements and a Chemical Transport Model to investigate variability in biospheric CO2 fluxes

    NASA Astrophysics Data System (ADS)

    Wang, Yuting; Petri, Christof; Palm, Mathias; Warneke, Thorsten; Baker, Ian; Berry, Joe; Suntharalingam, Parvadha; Campbell, Elliott; Wolf, Adam; Deutscher, Nick; Notholt, Justus

    2015-04-01

    Understanding the CO2 processes on land is of great importance, because the terrestrial exchange drives the seasonal and interannual variability of CO2 in the atmosphere. Atmospheric inversions based on CO2 concentration measurements alone can only determine net biosphere fluxes, but not differentiate between photosynthesis (uptake) and respiration (production). Carbonyl sulfide (OCS) could provide an important additional constraint: it is also taken up by plants during photosynthesis but not emitted during respiration, and therefore is a potential means to differentiate between these processes. Solar absorption Fourier Transform InfraRed (FTIR) spectrometry allows for the retrieval of the atmospheric concentrations of both CO2 and OCS. Here, we investigate co-located and nearly simultaneous measurements of OCS and CO2 measured at 3 sites via FTIR spectrometers. These northern-hemispheric sites span a wide range of latitudes and all have multiple year time-series. The sites include Ny-Alesund (79°N), Bremen (53°N) and Paramaribo (6°N). We compare these measurements to simulations of OCS and CO2 using the GEOS-Chem model. The simulations are driven by different land biospheric fluxes of OCS and CO2 to match the seasonality of the measurements. The simple biosphere model (SiB-COS) are used in the study because it simultaneously calculates the biospheric fluxes of both OCS and CO2. The CO2 simulation with SiB fluxes agrees with the measurements better than a simulation using CASA. Comparison of the OCS simulations with different fluxes indicates that the latitudinal distribution of the OCS fluxes within SiB needs to be adjusted.

  14. Potential impacts on groundwater resources of deep CO2 storage: natural analogues for assessing potential chemical effects

    NASA Astrophysics Data System (ADS)

    Lions, J.; Gale, I.; May, F.; Nygaard, E.; Ruetters, H.; Beaubien, S.; Sohrabi, M.; Hatzignatiou, D. G.; CO2GeoNet Members involved in the present study Team

    2011-12-01

    Carbon dioxide Capture and Storage (CCS) is considered as one of the promising options for reducing atmospheric emissions of CO2 related to human activities. One of the main concerns associated with the geological storage of CO2 is that the CO2 may leak from the intended storage formation, migrate to the near-surface environment and, eventually, escape from the ground. This is a concern because such leakage may affect aquifers overlying the storage site and containing freshwater that may be used for drinking, industry and agriculture. The IEA Greenhouse Gas R&D Programme (IEAGHG) recently commissioned the CO2GeoNet Association to undertake a review of published and unpublished literature on this topic with the aim of summarizing 'state of the art' knowledge and identifying knowledge gaps and research priorities in this field. Work carried out by various CO2GeoNet members was also used in this study. This study identifies possible areas of conflict by combining available datasets to map the global and regional superposition of deep saline formations (DSF) suitable for CO2 storage and overlying fresh groundwater resources. A scenario classification is developed for the various geological settings where conflict could occur. The study proposes two approaches to address the potential impact mechanisms of CO2 storage projects on the hydrodynamics and chemistry of shallow groundwater. The first classifies and synthesizes changes of water quality observed in natural/industrial analogues and in laboratory experiments. The second reviews hydrodynamic and geochemical models, including coupled multiphase flow and reactive transport. Various models are discussed in terms of their advantages and limitations, with conclusions on possible impacts on groundwater resources. Possible mitigation options to stop or control CO2 leakage are assessed. The effect of CO2 pressure in the host DSF and the potential effects on shallow aquifers are also examined. The study provides a review of

  15. Study of Superbase-Based Deep Eutectic Solvents as the Catalyst in the Chemical Fixation of CO2 into Cyclic Carbonates under Mild Conditions

    PubMed Central

    García-Argüelles, Sara; Iglesias, Marta; Del Monte, Francisco

    2017-01-01

    Superbases have shown high performance as catalysts in the chemical fixation of CO2 to epoxides. The proposed reaction mechanism typically assumes the formation of a superbase, the CO2 adduct as the intermediate, most likely because of the well-known affinity between superbases and CO2, i.e., superbases have actually proven quite effective for CO2 absorption. In this latter use, concerns about the chemical stability upon successive absorption-desorption cycles also merits attention when using superbases as catalysts. In this work, 1H NMR spectroscopy was used to get further insights about (1) whether a superbase, the CO2 adduct, is formed as an intermediate and (2) the chemical stability of the catalyst after reaction. For this purpose, we proposed as a model system the chemical fixation of CO2 to epichlorohydrin (EP) using a deep eutectic solvent (DES) composed of a superbase, e.g., 2,3,4,6,7,8-hexahydro-1H-pyrimido[1,2-a]pyrimidine (TBD) or 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine (DBU), as a hydrogen acceptor and an alcohol as a hydrogen bond donor, e.g., benzyl alcohol (BA), ethylene glycol (EG), and methyldiethanolamine (MDEA), as the catalyst. The resulting carbonate was obtained with yields above 90% and selectivities approaching 100% after only two hours of reaction in pseudo-mild reaction conditions, e.g., 1.2 bars and 100 °C, and after 20 h if the reaction conditions of choice were even milder, e.g., 1.2 bars and 50 °C. These results were in agreement with previous works using bifunctional catalytic systems composed of a superbase and a hydrogen bond donor (HBD) also reporting good yields and selectivities, thus confirming the suitability of our choice to perform this study. PMID:28773128

  16. Theoretical study of the influence of chemical reactions and physical parameters on the convective dissolution of CO2 in aqueous solutions

    NASA Astrophysics Data System (ADS)

    Loodts, Vanessa; Rongy, Laurence; De Wit, Anne

    2014-05-01

    Subsurface carbon sequestration has emerged as a promising solution to the problem of increasing atmospheric carbon dioxide (CO2) levels. How does the efficiency of such a sequestration process depend on the physical and chemical characteristics of the storage site? This question is emblematic of the need to better understand the dynamics of CO2 in subsurface formations, and in particular, the properties of the convective dissolution of CO2 in the salt water of aquifers. This dissolution is known to improve the safety of the sequestration by reducing the risks of leaks of CO2 to the atmosphere. Buoyancy-driven convection makes this dissolution faster by transporting dissolved CO2 further away from the interface. Indeed, upon injection, the less dense CO2 phase rises above the aqueous layer where it starts to dissolve. The dissolved CO2 increases the density of the aqueous solution, thereby creating a layer of denser CO2-rich solution above less dense solution. This unstable density gradient in the gravity field is at the origin of convection. In this framework, we theoretically investigate the effect of CO2 pressure, salt concentration, temperature, and chemical reactions on the dissolution-driven convection of CO2 in aqueous solutions. On the basis of a linear stability analysis, we assess the stability of the time-dependent density profiles developing when CO2 dissolves in an aqueous layer below it. We predict that increasing CO2 pressure destabilizes the system with regard to buoyancy-driven convection, because it increases the density gradient at the origin of the instability. By contrast, increasing salt concentration or temperature stabilizes the system via effects on CO2 solubility, solutal expansion coefficient, diffusion coefficient and on the viscosity and density of the solution. We also show that a reaction of CO2 with chemical species dissolved in the aqueous solution can either enhance or decrease the amplitude of the convective dissolution compared

  17. Recycling of CO2: Probing the Chemical State of the Ni(111) Surface during the Methanation Reaction with Ambient-Pressure X-Ray Photoelectron Spectroscopy.

    PubMed

    Heine, Christian; Lechner, Barbara A J; Bluhm, Hendrik; Salmeron, Miquel

    2016-10-12

    Using ambient-pressure X-ray photoelectron spectroscopy (AP-XPS), we studied the adsorption and reactions of CO2 and CO2 + H2 on the Ni(111) surface to identify the surface chemical state and the nature of the adsorbed species during the methanation reaction. In 200 mTorr CO2, we found that NiO is formed from CO2 dissociation into CO and atomic oxygen. Additionally, carbonate (CO3(2-)) is present on the surface from further reaction of CO2 with NiO. The addition of H2 into the reaction environment leads to reduction of NiO and the disappearance of CO3(2-). At temperatures >160 °C, CO adsorbed on hollow sites, and atomic carbon and OH species are present on the surface. We conclude that the methanation reaction proceeds via dissociation of CO2, followed by reduction of CO to atomic carbon and its hydrogenation to methane.

  18. A microporous Cu-MOF with optimized open metal sites and pore spaces for high gas storage and active chemical fixation of CO2.

    PubMed

    Gao, Chao-Ying; Tian, Hong-Rui; Ai, Jing; Li, Lei-Jiao; Dang, Song; Lan, Ya-Qian; Sun, Zhong-Ming

    2016-09-25

    A microporous Cu-MOF with optimized open metal sites and pore space was constructed based on a designed bent ligand; it exhibits high-capacity multiple gas storage under atmospheric pressure and efficient catalytic activity for chemical fixation of CO2 under mild conditions.

  19. Application of Chemical Doping and Architectural Design Principles To Fabricate Nanowire Co2Ni3ZnO8 Arrays for Aqueous Asymmetric Supercapacitors.

    PubMed

    Liu, Qi; Yang, Bin; Liu, Jingyuan; Yuan, Yi; Zhang, Hongsen; Liu, Lianhe; Wang, Jun; Li, Rumin

    2016-08-10

    Electrode materials derived from transition metal oxides have a serious problem of low electron transfer rate, which restricts their practical application. However, chemically doped graphene transforms the chemical bonding configuration to enhance electron transfer rate and, therefore, facilitates the successful fabrication of Co2Ni3ZnO8 nanowire arrays. In addition, the Co2Ni3ZnO8 electrode materials, considered as Ni and Zn ions doped into Co3O4, have a high electron transfer rate and electrochemical response capability, because the doping increases the degree of crystal defect and reaction of Co/Ni ions with the electrolyte. Hence, the Co2Ni3ZnO8 electrode exhibits a high rate property and excellent electrochemical cycle stability, as determined by electrochemical analysis of the relationship between specific capacitance, IR drop, Coulomb efficiency, and different current densities. From the results of a three-electrode system of electrochemical measurement, the Co2Ni3ZnO8 electrode demonstrates a specific capacitance of 1115 F g(-1) and retains 89.9% capacitance after 2000 cycles at a current density of 4 A g(-1). The energy density of the asymmetric supercapacitor (AC//Co2Ni3ZnO8) is 54.04 W h kg(-1) at the power density of 3200 W kg(-1).

  20. Chemical evolution of dissolved inorganic carbon species flowing in thin water films and its implications for (rapid) degassing of CO2 during speleothem growth

    NASA Astrophysics Data System (ADS)

    Hansen, Maximilian; Dreybrodt, Wolfgang; Scholz, Denis

    2013-04-01

    Rapid degassing of CO2 from a thin film of drip water on the surface of stalagmites is often considered to have a large effect on both speleothem growth and stable isotope values and is offered as an explanation for higher δ13C and δ18O values than expected under conditions of stable isotope equilibrium. However, the time constant for degassing of CO2 from the solution only depends on film thickness and the coefficient of molecular diffusion for CO2. Thus, for thin films, the time for degassing of CO2 is much shorter than the time for subsequent equilibration of the dissolved carbon species and precipitation of CaCO3. In this context, degassing of CO2 is always fast. Here we present three experiments that enable the determination of the time constants for degassing of CO2, τdeg, subsequent equilibration to a new pCO2, τeq, and precipitation of CaCO3, τpr, in a thin film of an H2O-CO2-CaCO3 solution flowing on a calcite surface. The experiments are performed under cave-analogue conditions. At a temperature of 20 °C and for a film thickness of δ ≈ 0.01 cm, τdeg ≈ 2 s. τeq ≈ 13 s and, thus, one order of magnitude larger. Finally, τpr ≈ 400 s for δ ≈ 0.01 cm, again one order of magnitude larger. The experimentally determined values for τdeg, τeqτpr are in good agreement with the theoretical predictions. Our results confirm that the chemical evolution of the drip water proceeds in three subsequent major steps. During the first step of degassing of CO2, pH and Ca2+ concentration remain almost constant. During equilibration to the lower pCO2 of the solution, pH increases to about 8 whereas the Ca2+ concentration still remains constant. Finally, during precipitation of calcite, pCO2 remains at its low level and pH decreases slightly. These results suggest that the drip rate may have an important influence on the stable isotope signals recorded in speleothems. Stalagmites growing beneath drip sites with stable, intermediate drip rates (i.e., in the

  1. Coal Direct Chemical Looping Retrofit to Pulverized Coal Power Plants for In-Situ CO2 Capture

    SciTech Connect

    Zeng, Liang; Li, Fanxing; Kim, Ray; Bayham, Samuel; McGiveron, Omar; Tong, Andrew; Connell, Daniel; Luo, Siwei; Sridhar, Deepak; Wang, Fei; Sun, Zhenchao; Fan, Liang-Shih

    2013-09-30

    A novel Coal Direct Chemical Looping (CDCL) system is proposed to effectively capture CO2 from existing PC power plants. The work during the past three years has led to an oxygen carrier particle with satisfactory performance. Moreover, successful laboratory, bench scale, and integrated demonstrations have been performed. The proposed project further advanced the novel CDCL technology to sub-pilot scale (25 kWth). To be more specific, the following objectives attained in the proposed project are: 1. to further improve the oxygen carrying capacity as well as the sulfur/ash tolerance of the current (working) particle; 2. to demonstrate continuous CDCL operations in an integrated mode with > 99% coal (bituminous, subbituminous, and lignite) conversion as well as the production of high temperature exhaust gas stream that is suitable for steam generation in existing PC boilers; 3. to identify, via demonstrations, the fate of sulfur and NOx; 4. to conduct thorough techno-economic analysis that validates the technical and economical attractiveness of the CDCL system. The objectives outlined above were achieved through collaborative efforts among all the participants. CONSOL Energy Inc. performed the techno-economic analysis of the CDCL process. Shell/CRI was able to perform feasibility and economic studies on the large scale particle synthesis and provide composite particles for the sub-pilot scale testing. The experience of B&W (with boilers) and Air Products (with handling gases) assisted the retrofit system design as well as the demonstration unit operations. The experience gained from the sub-pilot scale demonstration of the Syngas Chemical Looping (SCL) process at OSU was able to ensure the successful handling of the solids. Phase 1 focused on studies to improve the current particle to better suit the CDCL operations. The optimum operating conditions for the reducer reactor such as the temperature, char gasification enhancer type, and flow rate were identified. The

  2. New candidate for biofuel feedstock beyond terrestrial biomass for thermo-chemical process (pyrolysis/gasification) enhanced by carbon dioxide (CO2).

    PubMed

    Kwon, Eilhann E; Jeon, Young Jae; Yi, Haakrho

    2012-11-01

    The enhanced thermo-chemical process (i.e., pyrolysis/gasification) of various macroalgae using carbon dioxide (CO(2)) as a reaction medium was mainly investigated. The enhanced thermo-chemical process was achieved by expediting the thermal cracking of volatile chemical species derived from the thermal degradation of the macroalgae. This process enables the modification of the end products from the thermo-chemical process and significant reduction of the amount of condensable hydrocarbons (i.e., tar, ∼50%), thereby directly increasing the efficiency of the gasification process.

  3. [Optimize the extraction process with supercritical CO2 fluid from lotus leaves by the uniform design and analysis on the chemical constituents by GC-MS].

    PubMed

    Yin, Hui-jing; Qian, Yi-fan; Pu, Cun-hai

    2007-04-01

    To study the optimum parameters of the supercritical CO, fluid extraction of lotus leaves and chemical constituents of extractive matters. Supercritical CO2 fluid extraction condition was selected by uniform design. The extraction pressure, extraction temperature, extraction time were three factors in the experiment. GC-MS was applied for analyzing the extraction. The optimum condition were obtained: the extraction pressure was 26 Mpa, the extraction temperature was 40 degrees C, the extracion time was 90 minutes. The major constituent was 1H-Pyrrole-2-carboxaldehyde, 1-ethyl-in extractive matters. Uniform design can optimize the CO2 Supercritical Fluid Extraction process quickly and accuratly with satisfactory results.

  4. Chemical structures of coal lithotypes before and after CO2 adsorption as investigated by advanced solid-state 13C nuclear magnetic resonance spectroscopy

    USGS Publications Warehouse

    Cao, X.; Mastalerz, Maria; Chappell, M.A.; Miller, L.F.; Li, Y.; Mao, J.

    2011-01-01

    Four lithotypes (vitrain, bright clarain, clarain, and fusain) of a high volatile bituminous Springfield Coal from the Illinois Basin were characterized using advanced solid-state 13C nuclear magnetic resonance (NMR) spectroscopy. The NMR techniques included quantitative direct polarization/magic angle spinning (DP/MAS), cross polarization/total sideband suppression (CP/TOSS), dipolar dephasing, CHn selection, and recoupled C-H long-range dipolar dephasing techniques. The lithotypes that experienced high-pressure CO2 adsorption isotherm analysis were also analyzed to determine possible changes in coal structure as a result of CO2 saturation at high pressure and subsequent evacuation. The main carbon functionalities present in original vitrain, bright clarain, clarain and fusain were aromatic carbons (65.9%-86.1%), nonpolar alkyl groups (9.0%-28.9%), and aromatic C-O carbons (4.1%-9.5%). Among these lithotypes, aromaticity increased in the order of clarain, bright clarain, vitrain, and fusain, whereas the fraction of alkyl carbons decreased in the same order. Fusain was distinct from other three lithotypes in respect to its highest aromatic composition (86.1%) and remarkably small fraction of alkyl carbons (11.0%). The aromatic cluster size in fusain was larger than that in bright clarain. The lithotypes studied responded differently to high pressure CO2 saturation. After exposure to high pressure CO2, vitrain and fusain showed a decrease in aromaticity but an increase in the fraction of alkyl carbons, whereas bright clarain and clarain displayed an increase in aromaticity but a decrease in the fraction of alkyl carbons. Aromatic fused-rings were larger for bright clarain but smaller for fusain in the post-CO2 adsorption samples compared to the original lithotypes. These observations suggested chemical CO2-coal interactions at high pressure and the selectivity of lithotypes in response to CO2 adsorption. ?? 2011 Elsevier B.V.

  5. Climate Extreme Effects on the Chemical Composition of Temperate Grassland Species under Ambient and Elevated CO2: A Comparison of Fructan and Non-Fructan Accumulators

    PubMed Central

    Zinta, Gaurav; Van den Ende, Wim; Janssens, Ivan A.; Asard, Han

    2014-01-01

    Elevated CO2 concentrations and extreme climate events, are two increasing components of the ongoing global climatic change factors, may alter plant chemical composition and thereby their economic and ecological characteristics, e.g. nutritional quality and decomposition rates. To investigate the impact of climate extremes on tissue quality, four temperate grassland species: the fructan accumulating grasses Lolium perenne, Poa pratensis, and the nitrogen (N) fixing legumes Medicago lupulina and Lotus corniculatus were subjected to water deficit at elevated temperature (+3°C), under ambient CO2 (392 ppm) and elevated CO2 (620 ppm). As a general observation, the effects of the climate extreme were larger and more ubiquitous in combination with elevated CO2. The imposed climate extreme increased non-structural carbohydrate and phenolics in all species, whereas it increased lignin in legumes and decreased tannins in grasses. However, there was no significant effect of climate extreme on structural carbohydrates, proteins, lipids and mineral contents and stoichiometric ratios. In combination with elevated CO2, climate extreme elicited larger increases in fructan and sucrose content in the grasses without affecting the total carbohydrate content, while it significantly increased total carbohydrates in legumes. The accumulation of carbohydrates in legumes was accompanied by higher activity of sucrose phosphate synthase, sucrose synthase and ADP-Glc pyrophosphorylase. In the legumes, elevated CO2 in combination with climate extreme reduced protein, phosphorus (P) and magnesium (Mg) contents and the total element:N ratio and it increased phenol, lignin, tannin, carbon (C), nitrogen (N) contents and C:N, C:P and N:P ratios. On the other hand, the tissue composition of the fructan accumulating grasses was not affected at this level, in line with recent views that fructans contribute to cellular homeostasis under stress. It is speculated that quality losses will be less

  6. Effect of A-Site Cation Ordering on Chemical Stability, Oxygen Stoichiometry and Electrical Conductivity in Layered LaBaCo2O5+δ Double Perovskite

    PubMed Central

    Bernuy-Lopez, Carlos; Høydalsvik, Kristin; Einarsrud, Mari-Ann; Grande, Tor

    2016-01-01

    The effect of the A-site cation ordering on the chemical stability, oxygen stoichiometry and electrical conductivity in layered LaBaCo2O5+δ double perovskite was studied as a function of temperature and partial pressure of oxygen. Tetragonal A-site cation ordered layered LaBaCo2O5+δ double perovskite was obtained by annealing cubic A-site cation disordered La0.5Ba0.5CoO3-δ perovskite at 1100 °C in N2. High temperature X-ray diffraction between room temperature (RT) and 800 °C revealed that LaBaCo2O5+δ remains tetragonal during heating in oxidizing atmosphere, but goes through two phase transitions in N2 and between 450 °C and 675 °C from tetragonal P4/mmm to orthorhombic Pmmm and back to P4/mmm due to oxygen vacancy ordering followed by disordering of the oxygen vacancies. An anisotropic chemical and thermal expansion of LaBaCo2O5+δ was demonstrated. La0.5Ba0.5CoO3-δ remained cubic at the studied temperature irrespective of partial pressure of oxygen. LaBaCo2O5+δ is metastable with respect to La0.5Ba0.5CoO3-δ at oxidizing conditions inferred from the thermal evolution of the oxygen deficiency and oxidation state of Co in the two materials. The oxidation state of Co is higher in La0.5Ba0.5CoO3-δ resulting in a higher electrical conductivity relative to LaBaCo2O5+δ. The conductivity in both materials was reduced with decreasing partial pressure of oxygen pointing to a p-type semiconducting behavior. PMID:28773279

  7. An integrated system combining chemical looping hydrogen generation process and solid oxide fuel cell/gas turbine cycle for power production with CO2 capture

    NASA Astrophysics Data System (ADS)

    Chen, Shiyi; Xue, Zhipeng; Wang, Dong; Xiang, Wenguo

    2012-10-01

    In this paper, the solid oxide fuel cell/gas turbine (SOFC/GT) cycle is integrated with coal gasification and chemical looping hydrogen generation (CLHG) for electric power production with CO2 capture. The CLHG-SOFC/GT plant is configurated and the schematic process is modeled using Aspen Plus® software. Syngas, produced by coal gasification, is converted to hydrogen with CO2 separation through a three-reactors CLHG process. Hydrogen is then fueled to SOFC for power generation. The unreacted hydrogen from SOFC burns in a combustor and drives gas turbine. The heat of the gas turbine exhaust stream is recovered in HRSG for steam bottoming cycle. At a system pressure of 20 bar and a cell temperature of 900 °C, the CLHG-SOFC/GT plant has a net power efficiency of 43.53% with no CO2 emissions. The hybrid power plant performance is attractive because of high energy conversion efficiency and zero-CO2-emission. Key parameters that influence the system performance are also discussed, including system operating pressure, cell temperature, fuel utilization factor, steam reactor temperature, CO2 expander exhaust pressure and inlet gas preheating.

  8. LHCb VELO upgrade

    NASA Astrophysics Data System (ADS)

    Hennessy, Karol

    2017-02-01

    The upgrade of the LHCb experiment, scheduled for LHC Run-III, scheduled to start in 2021, will transform the experiment to a trigger-less system reading out the full detector at 40 MHz event rate. All data reduction algorithms will be executed in a high-level software farm enabling the detector to run at luminosities of 2×1033 cm-2 s-1. The Vertex Locator (VELO) is the silicon vertex detector surrounding the interaction region. The current detector will be replaced with a hybrid pixel system equipped with electronics capable of reading out at 40 MHz. The upgraded VELO will provide fast pattern recognition and track reconstruction to the software trigger. The silicon pixel sensors have 55×55 μm2 pitch, and are read out by the VeloPix ASIC, from the Timepix/Medipix family. The hottest region will have pixel hit rates of 900 Mhits/s yielding a total data rate of more than 3 Tbit/s for the upgraded VELO. The detector modules are located in a separate vacuum, separated from the beam vacuum by a thin custom made foil. The foil will be manufactured through milling and possibly thinned further by chemical etching. The material budget will be minimised by the use of evaporative CO2 coolant circulating in microchannels within 400 μm thick silicon substrates. The current status of the VELO upgrade is described and latest results from operation of irradiated sensor assemblies are presented.

  9. DIC dynamics in stream water of volcanic settings: climatic and lithology impact on the CO2 chemical weathering (Lesser Antilles, Reunion, French Massif Central and Iceland)

    NASA Astrophysics Data System (ADS)

    Rive, K.; Agrinier, P.; Gaillardet, J.

    2006-12-01

    The chemical weathering of the volcanic rocks plays a key role in the regulation of atmospheric CO2. Indeed, CO2 is one of the main proton suppliers (e.g. Louvat, 1997; Dessert et al., 2003) via the acid-base system of the dissolved inorganic carbon (DIC = H2CO3 + HCO3- + CO32-). Consequently, riverine DIC fluxes can help to constrain chemical erosion fluxes. However the behavior of DIC in rivers must be first understood because it can be affected by many geochemical processes (e.g. CO2 degassing, carbonate precipitation/dissolution, photosynthesis, organic matter decay). In order to investigate these processes, we have used the δ13C of the DIC. Four volcanic sites have been studied. They have different climates (tropical, temperate and sub-polar), different lithologies and different histories of formation: basaltic-andesitic islands (subduction arc of the Lesser Antilles: Guadeloupe, Dominica and Martinique) and basaltic islands (Reunion hot spot and Iceland hot spot-MOR system). The main differences between these sites are 1) the thickness of soils, and 2) the type and the abundance of vegetation (both are controlled by climatic factors: the mean annual temperature and the mean annual rainfall) and 3) the absence of sedimentary carbonate rocks. The common points among these sites are the high relieves and the magmatic CO2 degassing which controls the DIC of the hydrothermal springs. In such active volcanism settings, magmatic CO2 contribution is seen only in few streams, generally located close to the volcano heights and in the proximity of the hydrothermal springs. These streams show high δ13CDIC, generally around -3 ‰, and high DIC. The rivers in all sampling sites show an endmember with a δ13CDIC of about -15 ‰, characteristic of the organic matter. Therefore, like in large rivers(e.g. Aucour et al., 1999 or Telmer and Veizer, 1999), organic matters are the main sources of DIC in these streams, even on sites with few vegetation (limited to grasslands or

  10. One-Step Reforming of CO2 and CH4 into High-Value Liquid Chemicals and Fuels at Room Temperature by Plasma-Driven Catalysis.

    PubMed

    Wang, Li; Yi, Yanhui; Wu, Chunfei; Guo, Hongchen; Tu, Xin

    2017-08-25

    The conversion of CO2 with CH4 into liquid fuels and chemicals in a single-step catalytic process that bypasses the production of syngas remains a challenge. In this study, liquid fuels and chemicals (e.g., acetic acid, methanol, ethanol, and formaldehyde) were synthesized in a one-step process from CO2 and CH4 at room temperature (30 °C) and atmospheric pressure for the first time by using a novel plasma reactor with a water electrode. The total selectivity to oxygenates was approximately 50-60 %, with acetic acid being the major component at 40.2 % selectivity, the highest value reported for acetic acid thus far. Interestingly, the direct plasma synthesis of acetic acid from CH4 and CO2 is an ideal reaction with 100 % atom economy, but it is almost impossible by thermal catalysis owing to the significant thermodynamic barrier. The combination of plasma and catalyst in this process shows great potential for manipulating the distribution of liquid chemical products in a given process. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. A Bifunctional Europium-Organic Framework with Chemical Fixation of CO2 and Luminescent Detection of Al(3).

    PubMed

    Xu, Hang; Zhai, Bin; Cao, Chun-Shuai; Zhao, Bin

    2016-10-03

    A novel three-dimensional lanthanide-organic framework {[Eu(BTB)(phen)]·4.5DMF·2H2O}n (1) has been synthesized. Structural characterization suggests that framework 1 possesses one-dimensional channels with potential pore volume, and the large channels in the framework can capture CO2. Interestingly, investigations on the cycloaddition reaction of CO2 and epoxides reveal that compound 1 can be considered as an efficient catalyst for CO2 fixation with epoxides under 1 atm pressure. Importantly, 1 can be reused at least five times without any obvious loss in catalytic activity. Furthermore, the luminescent explorations of 1 reveal that 1 can act as a recyclable sensor of Al(3+), and the corresponding detection limit can reach 5 × 10(-8) M (1.35 ppb), which is obviously lower than the United States Environmental Protection Agency's recommended level of Al(3+) in drinking water (200 ppb). These results show that 1 has a level of sensitivity higher than that of other reported MOF-based sensors of Al(3+).

  12. Photoelectrocatalytic reduction of CO2 into chemicals using Pt-modified reduced graphene oxide combined with Pt-modified TiO2 nanotubes.

    PubMed

    Cheng, Jun; Zhang, Meng; Wu, Gai; Wang, Xin; Zhou, Junhu; Cen, Kefa

    2014-06-17

    The photoelectrocatalytic (PEC) reduction of CO2 into high-value chemicals is beneficial in alleviating global warming and advancing a low-carbon economy. In this work, Pt-modified reduced graphene oxide (Pt-RGO) and Pt-modified TiO2 nanotubes (Pt-TNT) were combined as cathode and photoanode catalysts, respectively, to form a PEC reactor for converting CO2 into valuable chemicals. XRD, XPS, TEM, AFM, and SEM were employed to characterize the microstructures of the Pt-RGO and Pt-TNT catalysts. Reduction products, such as C2H5OH and CH3COOH, were obtained from CO2 under band gap illumination and biased voltage. A combined liquid product generation rate (CH3OH, C2H5OH, HCOOH, and CH3COOH) of approximately 600 nmol/(h·cm(2)) was observed. Carbon atom conversion rate reached 1,130 nmol/(h·cm(2)), which were much higher than those achieved using Pt-modified carbon nanotubes and platinum carbon as cathode catalysts.

  13. CO2-neutral fuels

    NASA Astrophysics Data System (ADS)

    Goede, A. P. H.

    2015-08-01

    The need for storage of renewable energy (RE) generated by photovoltaic, concentrated solar and wind arises from the fact that supply and demand are ill-matched both geographically and temporarily. This already causes problems of overcapacity and grid congestion in countries where the fraction of RE exceeds the 20% level. A system approach is needed, which focusses not only on the energy source, but includes conversion, storage, transport, distribution, use and, last but not least, the recycling of waste. Furthermore, there is a need for more flexibility in the energy system, rather than relying on electrification, integration with other energy systems, for example the gas network, would yield a system less vulnerable to failure and better adapted to requirements. For example, long-term large-scale storage of electrical energy is limited by capacity, yet needed to cover weekly to seasonal demand. This limitation can be overcome by coupling the electricity net to the gas system, considering the fact that the Dutch gas network alone has a storage capacity of 552 TWh, sufficient to cover the entire EU energy demand for over a month. This lecture explores energy storage in chemicals bonds. The focus is on chemicals other than hydrogen, taking advantage of the higher volumetric energy density of hydrocarbons, in this case methane, which has an approximate 3.5 times higher volumetric energy density. More importantly, it allows the ready use of existing gas infrastructure for energy storage, transport and distribution. Intermittent wind electricity generated is converted into synthetic methane, the Power to Gas (P2G) scheme, by splitting feedstock CO2 and H2O into synthesis gas, a mixture of CO and H2. Syngas plays a central role in the synthesis of a range of hydrocarbon products, including methane, diesel and dimethyl ether. The splitting is accomplished by innovative means; plasmolysis and high-temperature solid oxygen electrolysis. A CO2-neutral fuel cycle is

  14. Major ion chemistry in the headwaters of the Yamuna river system:. Chemical weathering, its temperature dependence and CO 2 consumption in the Himalaya

    NASA Astrophysics Data System (ADS)

    Dalai, T. K.; Krishnaswami, S.; Sarin, M. M.

    2002-10-01

    The Yamuna river and its tributaries in the Himalaya constitute the Yamuna River System (YRS). The YRS basin has a drainage area and discharge comparable in magnitude to those of the Bhagirathi and the Alaknanda rivers, which merge to form the Ganga at the foothills of the Himalaya. A detailed geochemical study of the YRS was carried out to determine: (i) the relative significance of silicate, carbonate and evaporite weathering in contributing to its major ion composition; (ii) CO 2 consumption via silicate weathering; and (iii) the factors regulating chemical weathering of silicates in the basin. The results show that the YRS waters are mildly alkaline, with a wide range of TDS, ˜32 to ˜620 mg l-1. In these waters, the abundances of Ca, Mg and alkalinity, which account for most of TDS, are derived mainly from carbonates. Many of the tributaries in the lower reaches of the Yamuna basin are supersaturated with calcite. In addition to carbonic acid, sulphuric acid generated by oxidation of pyrites also seems to be supplying protons for chemical weathering. Silicate weathering in YRS basin contributes, on average, ˜25% (molar basis) of total cations on a basin wide scale. Silicate weathering, however, does not seem to be intense in the basin as evident from low Si/(Na*+K) in the waters, ˜1.2 and low values of chemical index of alteration (CIA) in bed sediments, ˜60. CO 2 drawdown resulting from silicate weathering in the YRS basin in the Himalaya during monsoon ranges between (4 to 7) × 10 5 moles km -2 y -1. This is higher than that estimated for the Ganga at Rishikesh for the same season. The CO 2 consumption rates in the Yamuna and the Ganga basins in the Himalaya are higher than the global average value, suggesting enhanced CO 2 drawdown in the southern slopes of the Himalaya. The impact of this enhanced drawdown on the global CO 2 budget may not be pronounced, as the drainage area of the YRS and the Ganga in the Himalaya is small. The CO 2 drawdown by

  15. Spring carbonate chemistry dynamics of surface waters in the northern East China Sea: Water mixing, biological uptake of CO2, and chemical buffering capacity

    NASA Astrophysics Data System (ADS)

    Zhai, Wei-Dong; Chen, Jian-Fang; Jin, Hai-Yan; Li, Hong-Liang; Liu, Jin-Wen; He, Xian-Qiang; Bai, Yan

    2014-09-01

    We investigated sea surface total alkalinity (TAlk), dissolved inorganic carbon (DIC), dissolved oxygen (DO), and satellite-derived chlorophyll-a in the connection between the Yellow Sea and the East China Sea (ECS) during April to early May 2007. In spring, Changjiang dilution water (CDW), ECS offshore water, and together with Yellow Sea water (YSW) occupied the northern ECS. Using 16 day composite satellite-derived chlorophyll-a images, several algal blooms were identified in the CDW and ECS offshore water. Correspondingly, biological DIC drawdown of 73 ± 20 μmol kg-1, oversaturated DO of 10-110 μmol O2 kg-1, and low fugacity of CO2 of 181-304 μatm were revealed in these two waters. YSW also showed CO2 uptake in spring, due to the very low temperature. However, its intrusion virtually counteracted CO2 uptake in the northern ECS. In the CDW and the ECS offshore water, Revelle factor was 9.3-11.7 and 8.9-10.6, respectively, while relatively high Revelle factor values of 11.4-13.0 were revealed in YSW. In the ECS offshore water, the observed relationship between DIC drawdown and oversaturated DO departed from the Redfield ratio, indicating an effect of chemical buffering capacity on the carbonate system during air-sea reequilibration. Given the fact that the chemical buffering capacity slows down the air-sea reequilibration of CO2, the early spring DIC drawdown may have durative effects on the sea surface carbonate system until early summer. Although our study is subject to limited temporal and spatial coverage of sampling, these insights are fundamental to understanding sea surface carbonate chemistry dynamics in this important ocean margin.

  16. Towards Ideal NOx and CO2 Emission Control Technology for Bio-Oils Combustion Energy System Using a Plasma-Chemical Hybrid Process

    NASA Astrophysics Data System (ADS)

    Okubo, M.; Fujishima, H.; Yamato, Y.; Kuroki, T.; Tanaka, A.; Otsuka, K.

    2013-03-01

    A pilot-scale low-emission boiler system consisting of a bio-fuel boiler and plasma-chemical hybrid NOx removal system is investigated. This system can achieve carbon neutrality because the bio-fuel boiler uses waste vegetable oil as one of the fuels. The plasma-chemical hybrid NOx removal system has two processes: NO oxidation by ozone produced from plasma ozonizers and NO2 removal using a Na2SO3 chemical scrubber. Test demonstrations of the system are carried out for mixed oils (mixture of A-heavy oil and waste vegetable oil). Stable combustion is achieved for the mixed oil (20 - 50% waste vegetable oil). Properties of flue gas—e.g., O2, CO2 and NOx—when firing mixed oils are nearly the same as those when firing heavy oil for an average flue gas flow rate of 1000 Nm3/h. NOx concentrations at the boiler outlet are 90 - 95 ppm. Furthermore, during a 300-min continuous operation when firing 20% mixed oil, NOx removal efficiency of more than 90% (less than 10 ppm NOx emission) is confirmed. In addition, the CO2 reduction when heavy oil is replaced with waste vegetable oil is estimated. The system comparison is described between the plasma-chemical hybrid NOx removal and the conventional technology.

  17. Water geochemistry of the Qiantangjiang River, East China: Chemical weathering and CO2 consumption in a basin affected by severe acid deposition

    NASA Astrophysics Data System (ADS)

    Liu, Wenjing; Shi, Chao; Xu, Zhifang; Zhao, Tong; Jiang, Hao; Liang, Chongshan; Zhang, Xuan; Zhou, Li; Yu, Chong

    2016-09-01

    The chemical composition of the Qiantangjiang River, the largest river in Zhejiang province in eastern China, was measured to understand the chemical weathering of rocks and the associated CO2 consumption and anthropogenic influences within a silicate-dominated river basin. The average total dissolved solids (TDS, 113 mg l-1) and total cation concentration (TZ+, 1357 μeq l-1) of the river waters are comparable with those of global major rivers. Ca2+ and HCO3- followed by Na2+ and SO42-, dominate the ionic composition of the river water. There are four major reservoirs (carbonates, silicates, atmospheric and anthropogenic inputs) contributing to the total dissolved load of the investigated rivers. The dissolved loads of the rivers are dominated by both carbonate and silicate weathering, which together account for about 76.3% of the total cationic load origin. The cationic chemical weathering rates of silicate and carbonate for the Qiantangjiang basin are estimated to be approximately 4.9 ton km-2 a-1 and 13.9 ton km-2 a-1, respectively. The calculated CO2 consumption rates with the assumption that all the protons involved in the weathering reaction are provided by carbonic acid are 369 × 103 mol km-2 a-1 and 273 × 103 mol km-2 a-1 by carbonate and silicate weathering, respectively. As one of the most severe impacted area by acid rain in China, H2SO4 from acid precipitation is also an important proton donor in weathering reactions. When H2SO4 is considered, the CO2 consumption rates for the river basin are estimated at 286 × 103 mol km-2 a-1 for carbonate weathering and 211 × 103 mol km-2 a-1 for silicate weathering, respectively. The results highlight that the drawdown effect of CO2 consumption by carbonate and silicate weathering can be largely overestimated if the role of sulfuric acid is ignored, especially in the area heavily impacted by acid deposition like Qiantangjiang basin. The actual CO2 consumption rates (after sulfuric acid weathering effect

  18. Final Report: Development of a Chemical Model to Predict the Interactions between Supercritical CO2, Fluid and Rock in EGS Reservoirs

    SciTech Connect

    McPherson, Brian J.; Pan, Feng

    2014-09-24

    This report summarizes development of a coupled-process reservoir model for simulating enhanced geothermal systems (EGS) that utilize supercritical carbon dioxide as a working fluid. Specifically, the project team developed an advanced chemical kinetic model for evaluating important processes in EGS reservoirs, such as mineral precipitation and dissolution at elevated temperature and pressure, and for evaluating potential impacts on EGS surface facilities by related chemical processes. We assembled a new database for better-calibrated simulation of water/brine/ rock/CO2 interactions in EGS reservoirs. This database utilizes existing kinetic and other chemical data, and we updated those data to reflect corrections for elevated temperature and pressure conditions of EGS reservoirs.

  19. Particulate Formation from a Copper Oxide-Based Oxygen Carrier in Chemical Looping Combustion for CO2 Capture

    EPA Science Inventory

    Attrition behavior and particle loss of a copper oxide-based oxygen carrier from a methane chemical looping combustion (CLC) process was investigated in a fluidized bed reactor. The aerodynamic diameters of most elutriated particulates, after passing through a horizontal settling...

  20. Particulate Formation from a Copper Oxide-Based Oxygen Carrier in Chemical Looping Combustion for CO2 Capture

    EPA Science Inventory

    Attrition behavior and particle loss of a copper oxide-based oxygen carrier from a methane chemical looping combustion (CLC) process was investigated in a fluidized bed reactor. The aerodynamic diameters of most elutriated particulates, after passing through a horizontal settling...

  1. CARBON COATED (CARBONOUS) CATALYST IN EBULLATED BED REACTOR FOR PRODUCTION OF OXYGENATED CHEMICALS FROM SYNGAS/CO2

    SciTech Connect

    Peizheng Zhou

    2000-11-17

    There are a number of exothermic chemical reactions which might benefit from the temperature control and freedom from catalyst fouling provided by the ebullated bed reactor technology. A particularly promising area is production of oxygenated chemicals, such as alcohols and ethers, from synthesis gas, which can be economically produced from coal or biomass. The ebullated bed operation requires that the small-diameter ({approx} 1/32 inch) catalyst particles have enough mechanical strength to avoid loss by attrition. However, all of the State Of The Art (SOTA) catalysts and advanced catalysts for the purpose are low in mechanical strength. The patented carbon-coated catalyst technology developed in our laboratory converts catalyst particles with low mechanical strength to strong catalysts suitable for ebullated bed application. This R&D program is concerned with the modification on the mechanical strength of the SOTA and advanced catalysts so that the ebullated bed technology can be utilized to produce valuable oxygenated chemicals from syngas/CO{sub 2} efficiently and economically. The objective of this R&D program is to study the technical and economic feasibility of selective production of high-value oxygenated chemicals from synthesis gas and CO{sub 2} mixed feed in an ebullated bed reactor using carbon-coated catalyst particles.

  2. CARBON COATED (CARBONOUS) CATALYST IN EBULLATED BED REACTOR FOR PRODUCTION OF OXYGENATED CHEMICALS FROM SYNGAS/CO2

    SciTech Connect

    Peizheng Zhou

    2001-10-26

    There are a number of exothermic chemical reactions which might benefit from the temperature control and freedom from catalyst fouling provided by the ebullated bed reactor technology. A particularly promising area is production of oxygenated chemicals, such as alcohols and ethers, from synthesis gas, which can be economically produced from coal or biomass. The ebullated bed operation requires that the small-diameter ({approx}1/32 inch) catalyst particles have enough mechanical strength to avoid loss by attrition. However, all of the State Of The Art (SOTA) catalysts and advanced catalysts for the purpose are low in mechanical strength. The patented carbon-coated catalyst technology developed in our laboratory converts catalyst particles with low mechanical strength to strong catalysts suitable for ebullated bed application. This R&D program is concerned with the modification on the mechanical strength of the SOTA and advanced catalysts so that the ebullated bed technology can be utilized to produce valuable oxygenated chemicals from syngas/CO{sub 2} efficiently and economically. The objective of this R&D program is to study the technical and economic feasibility of selective production of high-value oxygenated chemicals from synthesis gas and CO{sub 2} mixed feed in an ebullated bed reactor using carbon-coated catalyst particles.

  3. Catalysis for biomass and CO2 use through solar energy: opening new scenarios for a sustainable and low-carbon chemical production.

    PubMed

    Lanzafame, Paola; Centi, Gabriele; Perathoner, Siglinda

    2014-11-21

    The use of biomass, bio-waste and CO2 derived raw materials, the latter synthesized using H2 produced using renewable energy sources, opens new scenarios to develop a sustainable and low carbon chemical production, particularly in regions such as Europe lacking in other resources. This tutorial review discusses first this new scenario with the aim to point out, between the different possible options, those more relevant to enable this new future scenario for the chemical production, commenting in particular the different drivers (economic, technological and strategic, environmental and sustainability and socio-political) which guide the selection. The case of the use of non-fossil fuel based raw materials for the sustainable production of light olefins is discussed in more detail, but the production of other olefins and polyolefins, of drop-in intermediates and other platform molecules are also analysed. The final part discusses the role of catalysis in establishing this new scenario, summarizing the development of catalysts with respect to industrial targets, for (i) the production of light olefins by catalytic dehydration of ethanol and by CO2 conversion via FTO process, (ii) the catalytic synthesis of butadiene from ethanol, butanol and butanediols, and (iii) the catalytic synthesis of HMF and its conversion to 2,5-FDCA, adipic acid, caprolactam and 1,6-hexanediol.

  4. CARBON COATED (CARBONOUS) CATALYST IN EBULLATED BED REACTOR FOR PRODUCTION OF OXYGENATED CHEMICALS FROM SYNGAS/CO2

    SciTech Connect

    Peizheng Zhou

    2002-12-30

    This report summarizes the work completed under DOE's Support of Advanced Fuel Research program, Contract No. DE-FG26-99FT40681. The contract period was October 2000 through September 2002. This R&D program investigated the modification of the mechanical strength of catalyst extrudates using Hydrocarbon Technologies, Inc. (HTI) carbon-coated catalyst technology so that the ebullated bed technology can be utilized to produce valuable oxygenated chemicals from syngas/CO{sub 2} efficiently and economically. Exothermic chemical reactions benefit from the temperature control and freedom from catalyst fouling provided by the ebullated bed reactor technology. The carbon-coated extrudates prepared using these procedures had sufficient attrition resistance and surface area for use in ebullated bed operation. The low cost of carbon coating makes the carbon-coated catalysts highly competitive in the market of catalyst extrudates.

  5. Numerical investigation of biogas diffusion flames characteristics under several operation conditions in counter-flow configuration with an emphasis on thermal and chemical effects of CO2 in the fuel mixture

    NASA Astrophysics Data System (ADS)

    Mameri, A.; Tabet, F.; Hadef, A.

    2017-08-01

    This study addresses the influence of several operating conditions (composition and ambient pressure) on biogas diffusion flame structure and NO emissions with particular attention on thermal and chemical effect of CO2. The biogas flame is modeled by a counter flow diffusion flame and analyzed in mixture fraction space using flamelet approach. The GRI Mech-3.0 mechanism that involves 53 species and 325 reactions is adopted for the oxidation chemistry. It has been observed that flame properties are very sensitive to biogas composition and pressure. CO2 addition decreases flame temperature by both thermal and chemical effects. Added CO2 may participate in chemical reaction due to thermal dissociation (chemical effect). Excessively supplied CO2 plays the role of pure diluent (thermal effect). The ambient pressure rise increases temperature and reduces flame thickness, radiation losses and dissociation amount. At high pressure, recombination reactions coupled with chain carrier radicals reduction, diminishes NO mass fraction.

  6. Numerical investigation of biogas diffusion flames characteristics under several operation conditions in counter-flow configuration with an emphasis on thermal and chemical effects of CO2 in the fuel mixture

    NASA Astrophysics Data System (ADS)

    Mameri, A.; Tabet, F.; Hadef, A.

    2017-03-01

    This study addresses the influence of several operating conditions (composition and ambient pressure) on biogas diffusion flame structure and NO emissions with particular attention on thermal and chemical effect of CO2. The biogas flame is modeled by a counter flow diffusion flame and analyzed in mixture fraction space using flamelet approach. The GRI Mech-3.0 mechanism that involves 53 species and 325 reactions is adopted for the oxidation chemistry. It has been observed that flame properties are very sensitive to biogas composition and pressure. CO2 addition decreases flame temperature by both thermal and chemical effects. Added CO2 may participate in chemical reaction due to thermal dissociation (chemical effect). Excessively supplied CO2 plays the role of pure diluent (thermal effect). The ambient pressure rise increases temperature and reduces flame thickness, radiation losses and dissociation amount. At high pressure, recombination reactions coupled with chain carrier radicals reduction, diminishes NO mass fraction.

  7. Hydrochemical and Isotopic Constraints on the Temporal and Spatial Variability of Chemical Weathering and CO2 Fluxes: An Example From the Australian Victorian Alps

    NASA Astrophysics Data System (ADS)

    Hagedorn, B.; Cartwright, I.

    2007-12-01

    Water from a network of 11 pristine rivers draining the Australian Victorian Alps was collected at different locations during (i) high discharge (June 2006) and (ii) low discharge (February 2007) conditions and was analyzed for dissolved major ions, δ2H and δ18O, and δ34S of dissolved sulphate. River water chemistry implies that solutes are largely derived from precipitation and chemical weathering of silicate lithologies. Cl/Br ratios as low as 30 molar suggest that rivers have not dissolved halite, however, higher salinity (≥100 mmol/L) winter samples have intermediate Cl/Br ratios (600 to 2000 molar) that are attributed to minor halite dissolution at the onset of the rainy season. Subsequent mixing of river water homogenizes ratios and evaporation is the dominant process that increases downstream salinities. Oxygen and Hydrogen isotopes also indicate that mixing and evaporation have occurred. Despite the lack of carbonate outcrops in the study area and uniform negative calcite saturation indices, the dissolution of hydrothermal calcite may account for up to 67% of the total dissolved cations, generating up to 92% of all dissolved Ca and Mg. The sulphur isotope data (16 to 20°CDT) indicates that the dissolved SO4 is derived predominantly from atmospheric deposition and minor gypsum weathering and not from bacterial reduction of FeS. This militates against sulphuric acid weathering in Victorian rivers. Si/(Na* + K*) ratios suggest that silicate weathering is dominated by the transformation of plagioclase (An40) to smectite and, to a lesser extend, the production of kaolinite. In total, chemical weathering consumes 17.6 x 106 (summer) to 71.59 x 106(winter) mol/km2/yr CO2, with the highest values in rivers draining the basement outcrops rather than sedimentary rocks. This range is at the upper end of the global scale and shows that the predominance of fresh silicate lithologies exerts the main control on higher CO2 fluxes; temperature and runoff, in turn, are

  8. Particulate Formation from a Copper Oxide-Based Oxygen Carrier in Chemical Looping Combustion for CO2 Capture.

    PubMed

    He, Feng; Linak, William P; Deng, Shuang; Li, Fanxing

    2017-02-21

    Attrition behavior and particle loss of a copper oxide-based oxygen carrier from a methane chemical looping combustion (CLC) process was investigated in a fluidized bed reactor. The aerodynamic diameters of most elutriated particulates, after passing through a horizontal settling duct, range between 2 and 5 μm. A notable number of submicrometer particulates are also identified. Oxygen carrier attrition was observed to lead to increased CuO loss resulting from the chemical looping reactions, i.e., Cu is enriched in small particles generated primarily from fragmentation in the size range of 10-75 μm. Cyclic reduction and oxidation reactions in CLC have been determined to weaken the oxygen carrier particles, resulting in increased particulate emission rates when compared to those of oxygen carriers without redox reactions. The generation rate for particulates <10 μm was found to decrease with progressive cycles over as-prepared oxygen carrier particles and then reach a steady state. The surface of the oxygen carrier is also found to be coarsened due to a Kirkendall effect, which also explains the enrichment of Cu on particle surfaces and in small particles.

  9. Chemical weathering rate, denudation rate, and atmospheric and soil CO2 consumption of Paraná flood basalts in São Paulo State, Brazil

    NASA Astrophysics Data System (ADS)

    da Conceição, Fabiano Tomazini; dos Santos, Carolina Mathias; de Souza Sardinha, Diego; Navarro, Guillermo Rafael Beltran; Godoy, Letícia Hirata

    2015-03-01

    The chemical weathering rate and atmospheric/soil CO2 consumption of Paraná flood basalts in the Preto Stream basin, São Paulo State, Brazil, were evaluated using major elements as natural tracers. Surface and rain water samples were collected in 2006, and analyses were performed to assess pH, temperature, dissolved oxygen (DO), electrical conductivity (EC) and total dissolved solids (TDS), including SO42-, NO3-, PO43 -, HCO3-, Cl-, SiO2, Ca2 +, Mg2 +, Na+ and K+. Fresh rocks and C horizon samples were also collected, taking into account their geological context, abundance and spatial distribution, to analyze major elements and mineralogy. The Preto Stream, downstream from the city of Ribeirão Preto, receives several elements/compounds as a result of anthropogenic activities, with only sulfate yielding negative flux values. The negative flux of SO42 - can be attributed to atmospheric loading that is mainly related to anthropogenic inputs. After corrections were made for atmospheric inputs, the riverine transport of dissolved material was found to be 30 t km- 2 y- 1, with the majority of the dissolved material transported during the summer (wet) months. The chemical weathering rate and atmospheric/soil CO2 consumption were 6 m/Ma and 0.4 · 106 mol km- 2 y- 1, respectively. The chemical weathering rate falls within the lower range of Paraná flood basalt denudation rates between 135 and 35 Ma previously inferred from chronological studies. This comparison suggests that rates of basalt weathering in Brazil's present-day tropical climate differ by at most one order of magnitude from those prevalent at the time of hothouse Earth. The main weathering process is the monosiallitization of anorthoclase, augite, anorthite and microcline. Magnetite is not weathered and thus remains in the soil profile.

  10. CO2-Neutral Fuels

    NASA Astrophysics Data System (ADS)

    Goede, Adelbert; van de Sanden, Richard

    2016-06-01

    Mimicking the biogeochemical cycle of System Earth, synthetic hydrocarbon fuels are produced from recycled CO2 and H2O powered by renewable energy. Recapturing CO2 after use closes the carbon cycle, rendering the fuel cycle CO2 neutral. Non-equilibrium molecular CO2 vibrations are key to high energy efficiency.

  11. A PCP Pincer Ligand for Coordination Polymers with Versatile Chemical Reactivity: Selective Activation of CO2 Gas over CO Gas in the Solid State.

    PubMed

    He, Junpeng; Waggoner, Nolan W; Dunning, Samuel G; Steiner, Alexander; Lynch, Vincent M; Humphrey, Simon M

    2016-09-26

    A tetra(carboxylated) PCP pincer ligand has been synthesized as a building block for porous coordination polymers (PCPs). The air- and moisture-stable PCP metalloligands are rigid tetratopic linkers that are geometrically akin to ligands used in the synthesis of robust metal-organic frameworks (MOFs). Here, the design principle is demonstrated by cyclometalation with Pd(II) Cl and subsequent use of the metalloligand to prepare a crystalline 3D MOF by direct reaction with Co(II) ions and structural resolution by single crystal X-ray diffraction. The Pd-Cl groups inside the pores are accessible to post-synthetic modifications that facilitate chemical reactions previously unobserved in MOFs: a Pd-CH3 activated material undergoes rapid insertion of CO2 gas to give Pd-OC(O)CH3 at 1 atm and 298 K. However, since the material is highly selective for the adsorption of CO2 over CO, a Pd-N3 modified version resists CO insertion under the same conditions. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Urban energy mining from municipal solid waste (MSW) via the enhanced thermo-chemical process by carbon dioxide (CO2) as a reaction medium.

    PubMed

    Kwon, Eilhann E; Castaldi, Marco J

    2012-12-01

    The enhanced gasification of municipal solid waste (MSW) using carbon dioxide (CO(2)) as the gasification medium was investigated to achieve environmentally benign and energy efficient ways for the disposal of MSW. Two main steps of thermal decomposition of MSW were observed. The first thermal degradation step occurs at temperature between 280 and 350°C and consists of the decomposition of the biomass component into light C(1-3)-hydrocarbons. The second thermal degradation step occurs between 380 and 450°C and is mainly attributed to polymer components, such as plastics and rubber, in MSW. To extend this understanding to a more practical level, MSW samples were tested in a drop tube reactor (DTR) at a temperature range from 500 to 1000°C under various atmospheres with CO(2) concentrations of 0-30%. The release of major chemical species from the DTR has been determined using a micro-GC. For example, CO (≈ 30%), H(2) (≈ 25%) and CH(4) (≈ 10%) were generated. Copyright © 2012. Published by Elsevier Ltd.

  13. Supercritical CO2 extraction, chemical characterisation and antioxidant potential of Brassica oleracea var capitata against HO·, O2(·-) and ROO·.

    PubMed

    Dal Prá, Valéria; Dolwitsch, Carolina Bolssoni; da Silveira, Géssica Domingos; Porte, Liliane; Frizzo, Clarissa; Tres, Marcus Vinicius; Mossi, Vinicius; Mazutti, Marcio Antonio; do Nascimento, Paulo Cícero; Bohrer, Denise; de Carvalho, Leandro Machado; Viana, Carine; da Rosa, Marcelo Barcellos

    2013-12-15

    In this work were extracted bioactive compounds from Brassica oleracea var capitata using supercritical CO2 and evaluated the antioxidant potential of the extracts. Five extractions were accomplished to investigate the influence of pressure (10-25 MPa) and temperature (20-60 °C) in the extraction yield, chemical composition and antioxidant potential towards peroxyl, superoxide and hydroxyl radicals. The highest extraction yield was obtained at 60 °C and 25 MPa, which was 0.47 wt% (run 2). In the characterisation of the extracts obtained was possible the identification of sulforaphane and iberin nitrile that present known biological properties. The extracts of all runs presented antioxidant activities towards the three radicals, but the highest activities for all radicals were using the extracts obtained in the run 2. The use of supercritical CO2 extraction to obtain bioactive compounds of B. oleracea var capitata showed to be a promising alternative to conventional extraction methods, since allowed the extraction of compounds with scientific and industrial interest. Copyright © 2013 Elsevier Ltd. All rights reserved.

  14. Selecting CO2 Sources for CO2 Utilization by Environmental-Merit-Order Curves.

    PubMed

    von der Assen, Niklas; Müller, Leonard J; Steingrube, Annette; Voll, Philip; Bardow, André

    2016-02-02

    Capture and utilization of CO2 as alternative carbon feedstock for fuels, chemicals, and materials aims at reducing greenhouse gas emissions and fossil resource use. For capture of CO2, a large variety of CO2 sources exists. Since they emit much more CO2 than the expected demand for CO2 utilization, the environmentally most favorable CO2 sources should be selected. For this purpose, we introduce the environmental-merit-order (EMO) curve to rank CO2 sources according to their environmental impacts over the available CO2 supply. To determine the environmental impacts of CO2 capture, compression and transport, we conducted a comprehensive literature study for the energy demands of CO2 supply, and constructed a database for CO2 sources in Europe. Mapping these CO2 sources reveals that CO2 transport distances are usually small. Thus, neglecting transport in a first step, we find that environmental impacts are minimized by capturing CO2 first from chemical plants and natural gas processing, then from paper mills, power plants, and iron and steel plants. In a second step, we computed regional EMO curves considering transport and country-specific impacts for energy supply. Building upon regional EMO curves, we identify favorable locations for CO2 utilization with lowest environmental impacts of CO2 supply, so-called CO2 oases.

  15. Assessment of the biospheric contribution to surface atmospheric CO2 concentrations over East Asia with a regional chemical transport model

    NASA Astrophysics Data System (ADS)

    Kou, Xingxia; Zhang, Meigen; Peng, Zhen; Wang, Yinghong

    2015-03-01

    A regional chemical transport model, RAMS-CMAQ, was employed to assess the impacts of biosphere-atmosphere C2 exchange on seasonal variations in atmospheric C2 concentrations over East Asia. Simulated C2 concentrations were compared with observations at 12 surface stations and the comparison showed they were generally in good agreement. Both observations and simulations suggested that surface C2 over East Asia features a summertime trough due to biospheric absorption, while in some urban areas surface C2 has a distinct summer peak, which could be attributed to the strong impact from anthropogenic emissions. Analysis of the model results indicated that biospheric fluxes and fossil-fuel emissions are comparably important in shaping spatial distributions of C2 near the surface over East Asia. Biospheric flux plays an important role in the prevailing spatial pattern of C2 enhancement and reduction on the synoptic scale due to the strong seasonality of biospheric C2 flux. The elevation of C2 levels by the biosphere during winter was found to be larger than 5 ppm in North China and Southeast China, and during summertime a significant depletion (⩾ 7 ppm) occurred in most areas, except for the Indo-China Peninsula where positive bioflux values were found.

  16. Bosch CO2 Reduction System Development

    NASA Technical Reports Server (NTRS)

    Holmes, R. F.; King, C. D.; Keller, E. E.

    1976-01-01

    Development of a Bosch process CO2 reduction unit was continued, and, by means of hardware modifications, the performance was substantially improved. Benefits of the hardware upgrading were demonstrated by extensive unit operation and data acquisition in the laboratory. This work was accomplished on a cold seal configuration of the Bosch unit.

  17. Hydrogenation Reactions of CO and CO2: New Insights through In Situ X-ray Spectroscopy and Chemical Transient Kinetics Experiments on Cobalt Catalysts

    NASA Astrophysics Data System (ADS)

    Ralston, Walter Thomas

    The catalytic hydrogenations of CO and CO2 to more useful chemicals is not only beneficial in producing more valuable products and reducing dependence on fossil fuels, but present a scientific challenge in how to control the selectivity of these reactions. Using colloidal chemistry techniques, a high level of control over the synthesis of nanomaterials can be achieved, and by exploiting this fact a simple model system can be realized to understand the reaction of CO and CO2 on a molecular level. Specifically, this dissertation focuses on understanding cobalt materials for the conversion of CO and CO2 into more useful, valuable chemicals. Colloidally prepared cobalt nanoparticles with a narrow size distribution were supported in mesoporous SiO2 and TiO2 to study the effect of the support on the Co catalyzed hydrogenation of CO and CO2. The 10nm Co/SiO2 and Co/TiO2 catalysts were tested for CO and CO2 hydrogenation at 5 bar with a ratio to hydrogen of 1:2 and 1:3, respectively. In addition, the effect of Co oxidation state was studied by using different reduction pretreatment temperatures (250°C and 450°C). The results showed that for both hydrogenation reactions, Co/TiO2 had a high activity at both reduction temperatures compared to Co/SiO2. However, unlike Co/SiO2 which showed higher activity after 450°C reduction, Co/TiO2 had a higher activity after reduction at 250°C. Through synchrotron x-ray spectroscopy, it was concluded that the TiO2 was wetting the Co particle at higher reduction temperatures and dewetting at lower reduction temperatures. In addition to the wetting, CoO was observed to be the surface species on Co/TiO2 catalyst after reduction at low temperatures, which catalyzed both CO and CO2 hydrogenation reactions with higher activity than the Co metal obtained after reduction at 450°C. Classical steady-state measurements are limited in so much as they are often unable to provide information on individual reaction steps in complex reaction pathways

  18. Closing CO2 Loop in Biogas Production: Recycling Ammonia As Fertilizer.

    PubMed

    He, Qingyao; Yu, Ge; Tu, Te; Yan, Shuiping; Zhang, Yanlin; Zhao, Shuaifei

    2017-08-01

    We propose and demonstrate a novel system for simultaneous ammonia recovery, carbon capture, biogas upgrading, and fertilizer production in biogas production. Biogas slurry pretreatment (adjusting the solution pH, turbidity, and chemical oxygen demand) plays an important role in the system as it significantly affects the performance of ammonia recovery. Vacuum membrane distillation is used to recover ammonia from biogas slurry at various conditions. The ammonia removal efficiency in vacuum membrane distillation is around 75% regardless of the ammonia concentration of the biogas slurry. The recovered ammonia is used for CO2 absorption to realize simultaneous biogas upgrading and fertilizer generation. CO2 absorption performance of the recovered ammonia (absorption capacity and rate) is compared with a conventional model absorbent. Theoretical results on biogas upgrading are also provided. After ammonia recovery, the treated biogas slurry has significantly reduced phytotoxicity, improving the applicability for agricultural irrigation. The novel concept demonstrated in this study shows great potential in closing the CO2 loop in biogas production by recycling ammonia as an absorbent for CO2 absorption associated with producing fertilizers.

  19. Comprehensive structural and chemical (CO2, Fe/Fe Mg, H2O) investigations of Mg-Fe cordierite with micro Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Haefeker, U.; Kaindl, R.; Tropper, P.

    2012-04-01

    The Mg-Fe silicate cordierite with the idealized formula (Fe, Mg)2Al4Si5O18 occurs as a hexagonal and an orthorhombic polymorph with disordered/ordered Al-Si distribution on the tetrahedral sites. Most of the natural cordierites are fully ordered. Six-membered rings of (Si,Al)O4 are piled in the direction of the crystallographic c-axis and form channels, laterally and vertically linked by additional (Al, Si) tetrahedrons. Mg and Fe in varying fractions occupy the octahedrally coordinated M-sites. CO2 and H2O (and other volatiles) can be incorporated into the structural channels, thus cordierite can be used for paleofluid reconstruction. The vibration energies of incorporated volatiles, their interaction with the lattice and variations of certain lattice-vibration energies caused by the Mg-Fe exchange can be determined with Raman spectroscopy, allowing chemical quantifications and structural investigations. A method for the semi-quantitative determination of CO2-contents of natural cordierites by Kaindl et al. (2006) was optimized and enhanced by Haefeker et al. (2007). CO2 contents can be measured in single crystals and thin sections with an error of ± 0.05 - 0.09 wt.-%. Based on the Mg-Fe exchange with garnet, cordierite can be used as a geothermobarometer. Recent investigations of synthetic Mg-Fe cordierites with XFe = 0 - 1 have shown a linear downshift of six selected lattice peaks between 100 and 1250 cm-1 with the Mg-Fe contents. Correlation diagrams allow an estimation of the Mg-Fe contents in synthetic and natural samples. The experimental data are in good agreement with the results of quantum-mechanical calculations of the Raman spectra of Mg- and Fe cordierite (Kaindl et al., 2011) allowing the assignment of the peaks to specific vibrations of tetrahedral and octahedral sites. Natural Mg-Fe cordierites are mainly orthorhombic with a fully ordered Al/Si distribution on the tetrahedral sites. However, the disordered hexagonal polymorph is observed in many

  20. CO2 -Responsive polymers.

    PubMed

    Lin, Shaojian; Theato, Patrick

    2013-07-25

    This Review focuses on the recent progress in the area of CO2 -responsive polymers and provides detailed descriptions of these existing examples. CO2 -responsive polymers can be categorized into three types based on their CO2 -responsive groups: amidine, amine, and carboxyl groups. Compared with traditional temperature, pH, or light stimuli-responsive polymers, CO2 -responsive polymers provide the advantage to use CO2 as a "green" trigger as well as to capture CO2 directly from air. In addition, the current challenges of CO2 -responsive polymers are discussed and the different solution methods are compared. Noteworthy, CO2 -responsive polymers are considered to have a prosperous future in various scientific areas.

  1. CO2 laser modeling

    NASA Technical Reports Server (NTRS)

    Johnson, Barry

    1992-01-01

    The topics covered include the following: (1) CO2 laser kinetics modeling; (2) gas lifetimes in pulsed CO2 lasers; (3) frequency chirp and laser pulse spectral analysis; (4) LAWS A' Design Study; and (5) discharge circuit components for LAWS. The appendices include LAWS Memos, computer modeling of pulsed CO2 lasers for lidar applications, discharge circuit considerations for pulsed CO2 lidars, and presentation made at the Code RC Review.

  2. Novel bifunctional catalysts based on crystalline multi-oxide matrices containing iron ions for CO2 hydrogenation to liquid fuels and chemicals.

    PubMed

    Utsis, N; Vidruk-Nehemya, R; Landau, M V; Herskowitz, M

    2016-07-04

    Seven solid mono-, bi- and tri-metallic oxide matrices where Fe(2+,3+) ions are distributed in different chemical/spatial environments were synthesized and characterized by XRD, N2-adsorption and EDAX methods. After basification with potassium, all matrices were activated by carburization or reduction-carburization under conditions selected based on the TPC/TPR spectra, tailoring the carburization extent of iron. The performances of the activated Fe-based catalysts with respect to CO2 conversion and C5+ selectivity were measured in a fixed-bed reactor under standard conditions in transient and continuous operation modes in units containing one or three reactors in series with water separations between the reactors. The catalysts were characterized by XRD, N2-adsorption, HRTEM-EELS and XPS before and after steady-state operation in the reactors. It was found that the rate of CO2 conversion is not limited by thermodynamic equilibrium but is strongly restricted by water inhibition and it depends on the nature of the Fe-oxide precursor. The ratio between the FTS and RWGS rates, which determines the C5+ hydrocarbons productivity, is strongly affected by the nature of the Fe-oxide matrix. The catalysts derived from the Fe-Al-O spinel and Fe-Ba-hexaaluminate precursors displayed the best balance of the two functions RFTS/RRWGS = 0.77-0.78. They were followed by magnetite, CuFe-delafossite, K-ferrite, Fe-La-hexaaluminate and LaFe-perovskite with a gradual lowering of RFTS/RRWGS from 0.60 to 0.15 and a gradual decrease in the C5+ productivity. The active sites that enhance the RWGS reaction are located on the surface of the Fe-oxide phases, while the FTS and methanation reactions occur on the surface of the Fe-carbide phases.

  3. Different CO2 absorbents-modified SBA-15 sorbent for highly selective CO2 capture

    NASA Astrophysics Data System (ADS)

    Liu, Xiuwu; Zhai, Xinru; Liu, Dongyang; Sun, Yan

    2017-05-01

    Different CO2 absorbents-modified SBA-15 materials are used as CO2 sorbent to improve the selectivity of CH4/CO2 separation. The SBA-15 sorbents modified by physical CO2 absorbents are very limited to increasing CO2 adsorption and present poor selectivity. However, the SBA-15 sorbents modified by chemical CO2 absorbents increase CO2 adsorption capacity obviously. The separation coefficients of CO2/CH4 increase in this case. The adsorption and regeneration properties of the SBA-15 sorbents modified by TEA, MDEA and DIPA have been compared. The SBA-15 modified by triethanolamine (TEA) presents better CO2/CH4 separation performance than the materials modified by other CO2 absorbents.

  4. Vitamin B1-catalyzed acetoin formation from acetaldehyde: a key step for upgrading bioethanol to bulk C₄ chemicals.

    PubMed

    Lu, Ting; Li, Xiukai; Gu, Liuqun; Zhang, Yugen

    2014-09-01

    The production of bulk chemicals and fuels from renewable biobased feedstocks is of significant importance for the sustainability of human society. The production of ethanol from biomass has dramatically increased and bioethanol also holds considerable potential as a versatile building block for the chemical industry. Herein, we report a highly selective process for the conversion of ethanol to C4 bulk chemicals, such as 2,3-butanediol and butene, via a vitamin B1 (thiamine)-derived N-heterocyclic carbene (NHC)-catalyzed acetoin condensation as the key step to assemble two C2 acetaldehydes into a C4 product. The environmentally benign and cheap natural catalyst vitamin B1 demonstrates high selectivity (99%), high efficiency (97% yield), and high tolerance toward ethanol and water impurities in the acetoin reaction. The results enable a novel and efficient process for ethanol upgrading. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Adsorption of carbon dioxide (CO2) at S functionalized boron nitride (BN) and aluminum nitride (AlN) nanotubes (9, 0): A quantum chemical investigation

    NASA Astrophysics Data System (ADS)

    Najafi, Meysam

    2016-10-01

    We employed density functional theory to characterize CO2 adsorption on BNNT and AlNNT surfaces. The effects of S functionalization on the adsorption of CO2 gas on BNNT and AlNNT surfaces were investigated. Results reveal that adsorptions of CO2 on studied nanotubes were exothermic and experimentally possible from the energetic viewpoint. Results show that, Ead values of CO2 on AlNNT surface were more negative than corresponding values of BNNT. Results reveal that, S functionalization of studied nanotubes causes an increase in the absolute values of Ead of CO2 on surface of studied nanotubes. These results show that, there are good linearity dependencies between Ead and orbital energy values of studied nanotubes. Therefore we can conclude the Ead and orbital energy values are highly sensitive to the adsorption process which these may be used for the selection the suitable nanotubes with enhanced CO2 adsorption potential.

  6. Effects of xenon insertion into hydrogen bromide. Comparison of the electronic structure of the HBr···CO2 and HXeBr···CO2 complexes using quantum chemical topology methods: electron localization function, atoms in molecules and symmetry adapted perturbation theory.

    PubMed

    Makarewicz, Emilia; Gordon, Agnieszka J; Mierzwicki, Krzysztof; Latajka, Zdzislaw; Berski, Slawomir

    2014-06-05

    Quantum chemistry methods have been applied to study the influence of the Xe atom inserted into the hydrogen-bromine bond (HBr → HXeBr), particularly on the nature of atomic interactions in the HBr···CO2 and HXeBr···CO2 complexes. Detailed analysis of the nature of chemical bonds has been carried out using topological analysis of the electron localization function, while topological analysis of electron density was used to gain insight into the nature of weak nonbonding interactions. Symmetry-adapted perturbation theory within the orbital approach was applied for greater understanding of the physical contributions to the total interaction energy.

  7. Advanced Technologies for Monitoring CO2 Saturation and Pore Pressure in Geologic Formations: Linking the Chemical and Physical Effects to Elastic and Transport Properties

    SciTech Connect

    Mavko, G.; Vanorio, T.; Vialle, S.; Saxena, N.

    2014-03-31

    Ultrasonic P- and S-wave velocities were measured over a range of confining pressures while injecting CO2 and brine into the samples. Pore fluid pressure was also varied and monitored together with porosity during injection. Effective medium models were developed to understand the mechanisms and impact of observed changes and to provide the means for implementation of the interpretation methodologies in the field. Ultrasonic P- and S-wave velocities in carbonate rocks show as much as 20-50% decrease after injection of the reactive CO2-brine mixture; the changes were caused by permanent changes to the rock elastic frame associated with dissolution of mineral. Velocity decreases were observed under both dry and fluid-saturated conditions, and the amount of change was correlated with the initial pore fabrics. Scanning Electron Microscope images of carbonate rock microstructures were taken before and after injection of CO2-rich water. The images reveal enlargement of the pores, dissolution of micrite (micron-scale calcite crystals), and pitting of grain surfaces caused by the fluid- solid chemical reactivity. The magnitude of the changes correlates with the rock microtexture – tight, high surface area samples showed the largest changes in permeability and smallest changes in porosity and elastic stiffness compared to those in rocks with looser texture and larger intergranular pore space. Changes to the pore space also occurred from flow of fine particles with the injected fluid. Carbonates with grain-coating materials, such as residual oil, experienced very little permanent change during injection. In the tight micrite/spar cement component, dissolution is controlled by diffusion: the mass transfer of products and reactants is thus slow and the fluid is expected to be close to thermodynamical equilibrium with the calcite, leading to very little dissolution, or even precipitation. In the microporous rounded micrite and macropores, dissolution is controlled by

  8. Long-Term Observations of Atmospheric CO2, O3 and BrO over the Transitioning Arctic Ocean Pack-ice: The O-Buoy Chemical Network

    NASA Astrophysics Data System (ADS)

    Matrai, P.

    2016-02-01

    Autonomous, sea ice-tethered O-Buoys have been deployed (2009-2016) across the Arctic sea ice for long-term atmospheric measurements (http://www.o-buoy.org). O-Buoys (15) provide in-situ concentrations of three sentinel atmospheric chemicals, ozone, CO2 and BrO, as well as meteorological parameters and imagery, over the frozen ocean. O-Buoys were designed to transmit daily data over a period of 2 years while deployed in sea ice, as part of automated ice-drifting stations that include snow/ice measurement systems (e.g. Ice Mass Balance buoys) and oceanographic measurements (e.g. Ice Tethered Profilers). Seasonal changes in Arctic atmospheric chemistry are influenced by changes in the characteristics and presence of the sea ice vs. open water as well as air mass trajectories, especially during the winter-spring and summer-fall transitions when sea ice is melting and freezing, respectively. The O-Buoy Chemical Network provides the unique opportunity to observe these transition periods in real-time with high temporal resolution, and to compare them with those collected on land-based monitoring stations located. Due to the logistical challenges of measurements over the Arctic Ocean region, most long term, in-situ observations of atmospheric chemistry have been made at coastal or island sites around the periphery of the Arctic Ocean, leaving large spatial and temporal gaps that O-Buoys overcome. Advances in floatation, communications, power management, and sensor hardware have been made to overcome the challenges of diminished Arctic sea ice. O-Buoy data provide insights into enhanced seasonal, interannual and spatial variability in atmospheric composition, atmospheric boundary layer control on the amount of halogen activation, enhancement of the atmospheric CO2 signal over the more variable and porous pack ice, and to develop an integrated picture of the coupled ocean/ice/atmosphere system. As part of the Arctic Observing Network, we provide data to the community (www.aoncadis.org).

  9. Structurally simple complexes of CO2.

    PubMed

    Murphy, Luke J; Robertson, Katherine N; Kemp, Richard A; Tuononen, Heikki M; Clyburne, Jason A C

    2015-03-07

    The ability to bind CO2 through the formation of low-energy, easily-broken, bonds could prove invaluable in a variety of chemical contexts. For example, weak bonds to CO2 would greatly decrease the cost of the energy-intensive sorbent-regeneration step common to most carbon capture technologies. Furthermore, exploration of this field could lead to the discovery of novel CO2 chemistry. Reduction of complexed carbon dioxide might generate chemical feedstocks for the preparation of value-added products, particularly transportation fuels or fuel precursors. Implementation on a large scale could help to drastically reduce CO2 concentrations in the atmosphere. However, literature examples of weakly bonded complexes of CO2 are relatively few and true coordination complexes to a 'naked' CO2 fragment are nearly unheard of. In this review article, a variety of complexes of CO2 featuring diverse binding modes and reactivity will be examined. Topics covered include: (A) inclusion complexes of CO2 in porous materials. (B) Zwitterionic carbamates produced from the reaction of CO2 with polyamines. (C) Carbamate salts produced from reaction of CO2 with two equivalents of an amine. (D) Insertion products of CO2 into acid-base adducts (e.g., metal complexes). (E) Lewis acid-base activated CO2, such as frustrated Lewis pair complexes. (F) Simple base-CO2 adducts, wherein the base-CO2 bond is the only interaction formed. Complexes in the last category are of particular interest, and include imidazol-2-carboxylates (N-heterocyclic carbene adducts of CO2) as well as a few other examples that lie outside NHC chemistry.

  10. Chemical Formation of Methanol and Hydrocarbon ("Organic") Derivatives from CO2 and H2-Carbon Sources for Subsequent Biological Cell Evolution and Life's Origin.

    PubMed

    Olah, George A; Mathew, Thomas; Prakash, G K Surya

    2017-01-18

    Formation of methanol and hydrocarbon derivatives from CO2 and H2, their simplest molecular building blocks, under biocompatible conditions is proposed. Alternate panspermia of similar extraterrestrially formed and observed hydrocarbons to earth is also discussed. The simple molecular building blocks derived from CO2 and H2 are carbon sources in the initial stage of biological evolution of cells leading to life's origin.

  11. Leaf structural characteristics are less important than leaf chemical properties in determining the response of leaf mass per area and photosynthesis of Eucalyptus saligna to industrial-age changes in [CO2] and temperature.

    PubMed

    Xu, Cheng-Yuan; Salih, Anya; Ghannoum, Oula; Tissue, David T

    2012-10-01

    The rise in atmospheric [CO(2)] is associated with increasing air temperature. However, studies on plant responses to interactive effects of [CO(2)] and temperature are limited, particularly for leaf structural attributes. In this study, Eucalyptus saligna plants were grown in sun-lit glasshouses differing in [CO(2)] (290, 400, and 650 µmol mol(-1)) and temperature (26 °C and 30 °C). Leaf anatomy and chloroplast parameters were assessed with three-dimensional confocal microscopy, and the interactive effects of [CO(2)] and temperature were quantified. The relative influence of leaf structural attributes and chemical properties on the variation of leaf mass per area (LMA) and photosynthesis within these climate regimes was also determined. Leaf thickness and mesophyll size increased in higher [CO(2)] but decreased at the warmer temperature; no treatment interaction was observed. In pre-industrial [CO(2)], warming reduced chloroplast diameter without altering chloroplast number per cell, but the opposite pattern (reduced chloroplast number per cell and unchanged chloroplast diameter) was observed in both current and projected [CO(2)]. The variation of LMA was primarily explained by total non-structural carbohydrate (TNC) concentration rather than leaf thickness. Leaf photosynthetic capacity (light- and [CO(2)]-saturated rate at 28 °C) and light-saturated photosynthesis (under growth [CO(2)] and temperature) were primarily determined by leaf nitrogen contents, while secondarily affected by chloroplast gas exchange surface area and chloroplast number per cell, respectively. In conclusion, leaf structural attributes are less important than TNC and nitrogen in affecting LMA and photosynthesis responses to the studied climate regimes, indicating that leaf structural attributes have limited capacity to adjust these functional traits in a changing climate.

  12. Evidence of the chemical reaction of (18)O-labelled nitrite with CO2 in aqueous buffer of neutral pH and the formation of (18)OCO by isotope ratio mass spectrometry.

    PubMed

    Tsikas, Dimitrios; Böhmer, Anke; Gros, Gerolf; Endeward, Volker

    2016-05-01

    Inorganic nitrite (NO2(-), ON-O(-) ←→ (-)O-NO) is the autoxidation product of nitric oxide (NO). Nitrite can also be formed from inorganic nitrate (ONO2(-)), the major oxidation product of NO in erythrocytes, by the catalytic action of bacterial nitrate reductase in gut and oral microflora. Nitrite can be reduced to NO by certain cellular proteins and enzymes, as well as in the gastric juice under acidic conditions. Hemoglobin, xanthine oxidoreductase and carbonic anhydrase (CA) have been reported to convert nitrite to NO. Renal CA isoforms are involved in the reabsorption of nitrite and may, therefore, play an important role in NO homeostasis. Yet, the mechanisms underlying the action of CA on nitrite are incompletely understood. The nitrate/nitrite system is regarded as a reservoir of NO. We have recently shown that nitrite reacts chemically with carbon dioxide (CO2), the regular substrate of CA. The present communication reports a stable isotope ratio mass spectrometry (IRMS) study on the reaction of NO2(-) and CO2 performed in 50 mM HEPES buffer of pH 7.4 at 37 °C. By using (18)O-labelled nitrite ((18)ON-O(-)/(-18)O-NO) and CO2 we observed formation of (18)O-labelled CO2. This finding is an unequivocal evidence of the chemical reaction of (18)ON-O(-)/(-18)O-NO with CO2. The reaction is rapid and involves nucleophilic attack of the negatively charged nitrite via one of its oxygen atoms on the partially positively charged CO2 molecule to form the putative intermediate (18)ON-O-CO2(-)/(-)O2C-(18)O-NO. The by far largest fraction of this intermediate decomposes back to (18)ON-O(-)/(-18)O-NO and CO2. A very small fraction of the intermediate, however, rearranges and finally decomposes to form (18)OCO and nitrite. This reaction is slower in the presence of an isolated erythrocytic CA isoform II. In summary, NO2(-), CO2 and CA are ubiquitous. The chemical reaction of NO2(-) with CO2 and its modulation by CA isoforms may play important roles in the transport of

  13. CO2 blood test

    MedlinePlus

    Bicarbonate test; HCO3-; Carbon dioxide test; TCO2; Total CO2; CO2 test - serum ... Many medicines can interfere with blood test results. Your health care provider will tell you if you need to stop taking any medicines before you have this test. DO ...

  14. CO2 laser resurfacing.

    PubMed

    Fitzpatrick, R E

    2001-07-01

    The CO2 Laser offers a variety of unique features in resurfacing facial photodamage and acne scarring. These include hemostasis, efficient removal of the epidermis in a single pass, thermally induced tissue tightening, and safe, predictable tissue interaction. Knowledge of these mechanisms will result in the capability of using the CO2 laser effectively and safely whether the goal is superficial or deep treatment.

  15. Incorporation of digestate selectively affects physical, chemical and biochemical properties along with CO2 emissions in two contrasting agricultural soils in the Mediterranean area.

    NASA Astrophysics Data System (ADS)

    Badagliacca, Giuseppe; Petrovičová, Beatrix; Zumbo, Antonino; Romeo, Maurizio; Gullì, Tommaso; Martire, Luigi; Monti, Michele; Gelsomino, Antonio

    2017-04-01

    Soil incorporation of digestate represents a common practice to dispose the solid residues from biogas producing plants. Although the digestate constitutes a residual biomass rich in partially decomposed organic matter and nutrients, whose content is often highly variable and unbalanced, its potential fertilizer value can vary considerably depending on the recipient soil properties. The aim of the work was to assess short-term changes in the fertility status of two contrasting agricultural soils in Southern Italy (Calabria), olive grove on a clay acid soil (Typic Hapludalfs) and citrus grove on a sandy loam slightly calcareous soil (Typic Xerofluvents), respectively located along the Tyrrhenian or the Ionian coast. An amount of 30 t ha-1 digestate was incorporated into the soil by ploughing. Unamended tilled soil was used as control. The following soil physical, chemical and biochemical variables were monitored during the experimental period: aggregate stability, pH, electrical conductivity, organic C, total N, Olsen-P, N-NH4+, N-NO3-, microbial biomass carbon (MBC), microbial biomass nitrogen (MBN) and the mineralization quotient (qM). Moreover, in the olive grove soil CO2 emissions have been continuously measured at field scale for 5 months after digestate incorporation. Digestate application in both site exerted a significant positive effect on soil aggregate stability with a greater increase in clay than in sandy loam soil. Over the experimental period, digestate considerably affected the nutrient availability, namely Olsen-P, N-NH4+, N-NO3-, along with the electrical conductivity. The soil type increased significantly the soil N-NH4+ content, which was always higher in the olive than in citrus grove soil. N-NO3- content was markedly increased soon after the organic amendment, followed by a seasonal decline more evident in the sandy loam soil. Moreover, soil properties as CaCO3 content and the pH selectively affected the Olsen-P dynamics. No appreciable

  16. Effect of chemical functionalization groups on Zr6-AzoBDC to enhance H2, CH4 storage and CO2 capture: a theoretical investigation

    NASA Astrophysics Data System (ADS)

    Trang, Khung M.; Pham, Hung Q.; Pham-Tran, Nguyen-Nguyen

    2015-09-01

    Grand canonical Monte Carlo (GCMC) simulation combined with the ideal adsorbed solution theory (IAST) and a statistical method were utilized to investigate the effect of functional groups on zirconium oxide based metal-organic frameworks (MOFs) Zr6-AzoBDC (Zr6A) for the gases (H2, CH4) adsorption property and CO2/CH4 selectivity under low pressure. The results showed that phenyl groups containing nitrogen (pyridine, pyrimidine) and thiophene group enhance the gas affinity with MOFs, therefore increasing both gravimetric and volumetric uptake. In addition, this behavior can also cause significantly improved selective capture of CO2 from CO2/CH4 gas mixtures. Among functional groups studied, the sulfonic acid group can potentially improve CH4, CO2 uptake and H2 isosteric heat of adsorption. These findings would play a vital role in designing new materials toward gas adsorption properties.

  17. Chemical vs Electrochemical Formation of Li2CO3 as a Discharge Product in Li-O2/CO2 Batteries by Controlling the Superoxide Intermediate.

    PubMed

    Yin, Wei; Grimaud, Alexis; Lepoivre, Florent; Yang, Chunzhen; Tarascon, Jean Marie

    2017-01-05

    The Li-O2/CO2 battery with high capacity has recently been proposed as a new protocol to convert CO2. However, the fundamental mechanism for the reaction still remains hazy. Here, we investigated the discharge processes of Li-O2/CO2 (70%/30%) batteries in two solvents, dimethyl sulfoxide (DMSO) and 1,2-dimethoxyethane (DME). During discharge, both solvents initially show the reduction of oxygen. However, afterward, the solvent affects the reaction pathways of superoxide species by solvating Li(+) with different strength, depending on the so-called donor number. More precisely, the initial formation of CO4(•-) is favored in DMSO at the expense of lithium superoxide formation that we observed in DME. Despite the different intermediate processes, X-ray diffraction showed that Li2CO3 was the final discharge product in both solvents. Moreover, we observed that CO2 cannot be reduced within the electrochemical stability window of DMSO and DME.

  18. CO2 capture in different carbon materials.

    PubMed

    Jiménez, Vicente; Ramírez-Lucas, Ana; Díaz, José Antonio; Sánchez, Paula; Romero, Amaya

    2012-07-03

    In this work, the CO(2) capture capacity of different types of carbon nanofibers (platelet, fishbone, and ribbon) and amorphous carbon have been measured at 26 °C as at different pressures. The results showed that the more graphitic carbon materials adsorbed less CO(2) than more amorphous materials. Then, the aim was to improve the CO(2) adsorption capacity of the carbon materials by increasing the porosity during the chemical activation process. After chemical activation process, the amorphous carbon and platelet CNFs increased the CO(2) adsorption capacity 1.6 times, whereas fishbone and ribbon CNFs increased their CO(2) adsorption capacity 1.1 and 8.2 times, respectively. This increase of CO(2) adsorption capacity after chemical activation was due to an increase of BET surface area and pore volume in all carbon materials. Finally, the CO(2) adsorption isotherms showed that activated amorphous carbon exhibited the best CO(2) capture capacity with 72.0 wt % of CO(2) at 26 °C and 8 bar.

  19. Synthetic biology for CO2 fixation.

    PubMed

    Gong, Fuyu; Cai, Zhen; Li, Yin

    2016-11-01

    Recycling of carbon dioxide (CO2) into fuels and chemicals is a potential approach to reduce CO2 emission and fossil-fuel consumption. Autotrophic microbes can utilize energy from light, hydrogen, or sulfur to assimilate atmospheric CO2 into organic compounds at ambient temperature and pressure. This provides a feasible way for biological production of fuels and chemicals from CO2 under normal conditions. Recently great progress has been made in this research area, and dozens of CO2-derived fuels and chemicals have been reported to be synthesized by autotrophic microbes. This is accompanied by investigations into natural CO2-fixation pathways and the rapid development of new technologies in synthetic biology. This review first summarizes the six natural CO2-fixation pathways reported to date, followed by an overview of recent progress in the design and engineering of CO2-fixation pathways as well as energy supply patterns using the concept and tools of synthetic biology. Finally, we will discuss future prospects in biological fixation of CO2.

  20. Toward the understanding of chemical absorption processes for post-combustion capture of carbon dioxide: electronic and steric considerations from the kinetics of reactions of CO2(aq) with sterically hindered amines.

    PubMed

    Conway, William; Wang, Xiaoguang; Fernandes, Debra; Burns, Robert; Lawrance, Geoffrey; Puxty, Graeme; Maeder, Marcel

    2013-01-15

    The present study reports (a) the determination of both the kinetic rate constants and equilibrium constants for the reaction of CO(2)(aq) with sterically hindered amines and (b) an attempt to elucidate a fundamental chemical understanding of the relationship between the amine structure and chemical properties of the amine that are relevant for postcombustion capture of CO(2) (PCC) applications. The reactions of CO(2)(aq) with a series of linear and methyl substituted primary amines and alkanolamines have been investigated using stopped-flow spectrophotometry and (1)H NMR measurements at 25.0 °C. The specific mechanism of absorption for each of the amines, that is CO(2) hydration and/or carbamate formation, is examined and, based on the mechanism, the kinetic and equilibrium constants for the formation of carbamic acid/carbamates, including protonation constants of the carbamate, are reported for amines that follow this pathway. A Brønsted correlation relating the kinetic rate constants and equilibrium constants for the formation of carbamic acid/carbamates with the protonation constant of the amine is reported. Such a relationship facilitates an understanding of the effects of steric and electronic properties of the amine toward its reactivity with CO(2). Further, such relationships can be used to guide the design of new amines with improved properties relevant to PCC applications.

  1. Outsourcing CO2 Emissions

    NASA Astrophysics Data System (ADS)

    Davis, S. J.; Caldeira, K. G.

    2009-12-01

    CO2 emissions from the burning of fossil fuels are the primary cause of global warming. Much attention has been focused on the CO2 directly emitted by each country, but relatively little attention has been paid to the amount of emissions associated with consumption of goods and services in each country. This consumption-based emissions inventory differs from the production-based inventory because of imports and exports of goods and services that, either directly or indirectly, involved CO2 emissions. Using the latest available data and reasonable assumptions regarding trans-shipment of embodied carbon through third-party countries, we developed a global consumption-based CO2 emissions inventory and have calculated associated consumption-based energy and carbon intensities. We find that, in 2004, 24% of CO2 emissions are effectively outsourced to other countries, with much of the developed world outsourcing CO2 emissions to emerging markets, principally China. Some wealthy countries, including Switzerland and Sweden, outsource over half of their consumption-based emissions, with many northern Europeans outsourcing more than three tons of emissions per person per year. The United States is both a big importer and exporter of emissions embodied in trade, outsourcing >2.6 tons of CO2 per person and at the same time as >2.0 tons of CO2 per person are outsourced to the United States. These large flows indicate that CO2 emissions embodied in trade must be taken into consideration when considering responsibility for increasing atmospheric greenhouse gas concentrations.

  2. Hydrocarbonaceous material upgrading method

    DOEpatents

    Brecher, Lee E.; Mones, Charles G.; Guffey, Frank D.

    2015-06-02

    A hydrocarbonaceous material upgrading method may involve a novel combination of heating, vaporizing and chemically reacting hydrocarbonaceous feedstock that is substantially unpumpable at pipeline conditions, and condensation of vapors yielded thereby, in order to upgrade that feedstock to a hydrocarbonaceous material condensate that meets crude oil pipeline specification.

  3. Porous materials with optimal adsorption thermodynamics and kinetics for CO2 separation.

    PubMed

    Nugent, Patrick; Belmabkhout, Youssef; Burd, Stephen D; Cairns, Amy J; Luebke, Ryan; Forrest, Katherine; Pham, Tony; Ma, Shengqian; Space, Brian; Wojtas, Lukasz; Eddaoudi, Mohamed; Zaworotko, Michael J

    2013-03-07

    The energy costs associated with the separation and purification of industrial commodities, such as gases, fine chemicals and fresh water, currently represent around 15 per cent of global energy production, and the demand for such commodities is projected to triple by 2050 (ref. 1). The challenge of developing effective separation and purification technologies that have much smaller energy footprints is greater for carbon dioxide (CO2) than for other gases; in addition to its involvement in climate change, CO2 is an impurity in natural gas, biogas (natural gas produced from biomass), syngas (CO/H2, the main source of hydrogen in refineries) and many other gas streams. In the context of porous crystalline materials that can exploit both equilibrium and kinetic selectivity, size selectivity and targeted molecular recognition are attractive characteristics for CO2 separation and capture, as exemplified by zeolites 5A and 13X (ref. 2), as well as metal-organic materials (MOMs). Here we report that a crystal engineering or reticular chemistry strategy that controls pore functionality and size in a series of MOMs with coordinately saturated metal centres and periodically arrayed hexafluorosilicate (SiF(2-)(6)) anions enables a 'sweet spot' of kinetics and thermodynamics that offers high volumetric uptake at low CO2 partial pressure (less than 0.15 bar). Most importantly, such MOMs offer an unprecedented CO2 sorption selectivity over N2, H2 and CH4, even in the presence of moisture. These MOMs are therefore relevant to CO2 separation in the context of post-combustion (flue gas, CO2/N2), pre-combustion (shifted synthesis gas stream, CO2/H2) and natural gas upgrading (natural gas clean-up, CO2/CH4).

  4. Potassium-chemical synthesis of 3D graphene from CO2 and its excellent performance in HTM-free perovskite solar cells

    DOE PAGES

    Wei, Wei; Hu, Baoyun; Jin, Fangming; ...

    2017-03-29

    The conversion of greenhouse gas CO2 into novel materials is the most promising approach to solve greenhouse gas issues. In this paper, we report for the first time the reaction of potassium with CO2 to synthesize three-dimensional honeycomb-like structured graphene (3DHG). Furthermore, 3DHG exhibited excellent performance as a counter electrode for hole transport material (HTM)-free perovskite solar cells, leading to a power conversion efficiency of 10.06%. Finally, this work constitutes a new aspect of potassium chemistry for material synthesis from a greenhouse gas and the generation of electrical energy from sunlight.

  5. Chemical microenvironments and single-cell carbon and nitrogen uptake in field-collected colonies of Trichodesmium under different pCO2.

    PubMed

    Eichner, Meri J; Klawonn, Isabell; Wilson, Samuel T; Littmann, Sten; Whitehouse, Martin J; Church, Matthew J; Kuypers, Marcel Mm; Karl, David M; Ploug, Helle

    2017-06-01

    Gradients of oxygen (O2) and pH, as well as small-scale fluxes of carbon (C), nitrogen (N) and O2 were investigated under different partial pressures of carbon dioxide (pCO2) in field-collected colonies of the marine dinitrogen (N2)-fixing cyanobacterium Trichodesmium. Microsensor measurements indicated that cells within colonies experienced large fluctuations in O2, pH and CO2 concentrations over a day-night cycle. O2 concentrations varied with light intensity and time of day, yet colonies exposed to light were supersaturated with O2 (up to ~200%) throughout the light period and anoxia was not detected. Alternating between light and dark conditions caused a variation in pH levels by on average 0.5 units (equivalent to 15 nmol l(-1) proton concentration). Single-cell analyses of C and N assimilation using secondary ion mass spectrometry (SIMS; large geometry SIMS and nanoscale SIMS) revealed high variability in metabolic activity of single cells and trichomes of Trichodesmium, and indicated transfer of C and N to colony-associated non-photosynthetic bacteria. Neither O2 fluxes nor C fixation by Trichodesmium were significantly influenced by short-term incubations under different pCO2 levels, whereas N2 fixation increased with increasing pCO2. The large range of metabolic rates observed at the single-cell level may reflect a response by colony-forming microbial populations to highly variable microenvironments.

  6. Reactive Transport Modeling of Effects of Different (Physical, Chemical and Computational) Factors on the Convection Process during CO2 Geological Sequestration in Deep Saline Aquifers

    NASA Astrophysics Data System (ADS)

    Zhang, W.; Wang, S.

    2014-12-01

    Density-driven convective activity can significantly accelerate the transformation of the injected CO2 from supercritical or gas phase into liquid phase, thus improving the long-term storage security. It is well known that the convective instability is only caused by the heterogeneity of porous medium. However, we found that numerical perturbation resulted from the spatial and temporal discretization and the convergence criteria will affect the modeling results. Partial simulation results as follows: (1) the increase in vertical permeability (kv) has a strong effect on the convection process compared to the increasing horizontal permeability. The higher kv also can accelerate the downward migration of fingers and the CO2 dissolution; (2) increase in magnitude of medium (porosity and permeability) perturbation promotes the onset of convective activity, but does not affect the evolution of convection. However, for same magnitudes of the medium perturbation, the modification in permeability can lead to a more rapid onset of convective activity than that in porosity; and (3) the geochemical reactions and mineral compositions are important not only to the CO2 dissolution, but also to the dissolution of other species from mineral dissolution, which both can increase the water density. In additional, 3D and 2D modeling results indicated that their effect on the convection onset is similar. The CO2 dissolution rate for the higher-resolution 3D model is greatly slower than that for the higher-resolution 2D model, due to the increase in dimension for 3D model enhances the interaction of fingers. However, we found that once the bottom boundary becomes important, the decrease in CO2 dissolution rate for the 2D model is more significant than that for the 3D model. This is because the more significant interaction of fingers in the 3D model than that in the 2D model delays the downward propagation of fingers and then the impact of the bottom boundary.

  7. Integrated supply chain design for commodity chemicals production via woody biomass fast pyrolysis and upgrading.

    PubMed

    Zhang, Yanan; Hu, Guiping; Brown, Robert C

    2014-04-01

    This study investigates the optimal supply chain design for commodity chemicals (BTX, etc.) production via woody biomass fast pyrolysis and hydroprocessing pathway. The locations and capacities of distributed preprocessing hubs and integrated biorefinery facilities are optimized with a mixed integer linear programming model. In this integrated supply chain system, decisions on the biomass chipping methods (roadside chipping vs. facility chipping) are also explored. The economic objective of the supply chain model is to maximize the profit for a 20-year chemicals production system. In addition to the economic objective, the model also incorporates an environmental objective of minimizing life cycle greenhouse gas emissions, analyzing the trade-off between the economic and environmental considerations. The capital cost, operating cost, and revenues for the biorefinery facilities are based on techno-economic analysis, and the proposed approach is illustrated through a case study of Minnesota, with Minneapolis-St. Paul serving as the chemicals distribution hub. Copyright © 2014 Elsevier Ltd. All rights reserved.

  8. Natural Analog for Geologic Storage of CO2: CO2 accumulation in China

    NASA Astrophysics Data System (ADS)

    Liu, L.; Xu, T.; Liu, N.; Zhou, B.

    2012-12-01

    Natural accumulations of CO2 are potential analogues of CO2 geological storage that can provide useful information on the behaviour of supercritical CO2 in reservoirs. Natural CO2 accumulations are common across Northeast China, and, although they occur in a wide variety of geological settings, their distribution is principally controlled by the Mesozoic-Cenozoic rift basins and associated Quaternary volcanism. High CO2 concentrations (>60 CO2%) in natural gas reservoirs are usually related to volcanism and magmatism, and possesses mantle-genetic origin. CO2 reservoirs consist of sandstone, volcanic rocks and carbonate rocks with the buried depth from 2000-3000 m. Dawsonite is recognized in almost all of the CO2-bearing basin, which has been proved to share the same carbon source with CO2 in the reservoirs in Songliao basin, Hailaer basin and Donghai basin. Petrographic data show that dawsonite is abundant in feldspar- rich sandstone, volcanic rock fragment-rich sandstones and tuff. In some cases, high percentage of dawsonite cement constitutes a diagenetic seal, which occurs in the reservoir-mudstone caprock and prevents upward leakage of CO2. Besides dawsonite, mantle-genetic CO2 flux leads to the formation of calcite, ankerite and siderite. The statistics of porosity and permeability measured from the dawsonite-bearing sandstone and dawsonite-absent sandstone with the almost same burial depth in Songliao basin show that the mantle-genetic CO2 flux result in lower reservoir quality, suggesting that mineral trapping for CO2 is significant. Chemical analyses of formation water in Songliao basin and Hailaer basin indicate that the concentrations of TDS, HCO3-,CO32-, Mg2+,Ca2+ and Na+ + K+ in dawsonite-bearing sandstone are higher than that in dawsonite-absent sandstone. Distribution of CO2 and dawsonite is constrainted by the regional caprocks in the Songliao basin. The charging time of the mantle-genetic CO2 in China dates from 50 to 25 Ma.

  9. How does the critical point change during a chemical reaction in supercritical fluids? A study of the hydroformylation of propene in supercritical CO(2).

    PubMed

    Ke, J; Han, B; George, M W; Yan, H; Poliakoff, M

    2001-04-25

    An understanding of homogeneous catalysis in supercritical fluids requires a knowledge of the phase behavior and the variation in critical point as the reaction proceeds. In this paper, the critical temperatures, T(c) and pressures, P(c), have been measured for a considerable number of mixtures representing the various stages of the hydroformylation reaction of propene in supercritical CO(2) and different reactant concentrations. Critical point data have also been measured for all of the binary mixtures of the components (CO(2), H(2), CO, propene, n- and isobutyraldehyde) which are not available from the literature or can be deduced from published data. We use the stoichiometry of the reacting system to simplify greatly the phase behavior problem by defining a path through the otherwise multidimensional "phase space". Satisfactory modeling of the data (0.3% in T(c) and 3.0% in P(c)) has been achieved using the Peng-Robinson equation of state and ignoring all binary interactions which do not involve CO(2). The model is used to explore the strategies needed to avoid phase separation in continuous and batch reactions. At a given temperature, a batch reactor may need to be run under much higher pressures than a flow reactor if single-phase conditions are to be preserved throughout the course of the reaction. Most of the critical point data were measured acoustically, but a selection of points were validated using more traditional view-cell procedures.

  10. Increased chemical weathering of olivine in high-energy shelf seas can counteract human CO2 emissions and ocean acidification against a price well below that of CCS and other methods

    NASA Astrophysics Data System (ADS)

    de Boer, Poppe L.; Schuiling, Roelof D.

    2014-05-01

    In the reaction: Mg(Fe)2SiO4 (olivine) + 4 H2O 2 Mg(Fe)2+ + 4 OH- + H4SiO4, followed by 4 OH- + 4 CO2 4 HCO3-, CO2 is consumed, and Mg2+, Fe2+, H4SiO4 and HCO3- are produced. Contrary to the paradigm that olivine weathering in nature is a slow process, flume experiments show a fast reaction, consuming CO2, and raising the pH at short notice. Only under static conditions a silica coating develops that retards the reaction. In high-energy shallow marine environments such silica coatings are abraded so that the chemical reaction can continue. When kept in motion even large olivine grains and gravels, rubbing and bumping against each other and against other sediment grains, weather quickly. Experiments show that fine micron- to silt-sized olivine particles are produced, and that the chemical reaction is fast. The chemical weathering of 7 km3 olivine is needed on a yearly basis in order to compensate the human CO2 emissions. This seems much, but is of the same order of magnitude as the volume of fossil fuels (in oil equivalents ~10 km3) that are burnt annually. Olivine is readily available at the Earth' surface on all continents, and such volume of 7 km3 is exceeded by existing mines; e.g. the Bingham Canyon open pit mine in Utah has an excavated volume of 25 km3. Hydrocarbons, on the other hand, are commonly retrieved with great efforts, from great depths, and often at remote locations. Spreading of large amounts of olivine (and/or serpentinite) in high-energy shelf seas where coarse sand and gravel can be transported, will counteract human CO2 production by fossil fuel burning and ocean acidification against a price well below that of other methods; order of US 10.- per ton CO2. For example part of the continental shelf between the Shetland Isles and France, that is the Southern Bight of the North Sea, the English Channel and the Irish Sea, is covered with sand waves, and in and around the English Channel an area of well over 100,000 km2 experiences bed shear stresses

  11. Underwater CO2 Sequestration Program in Korea

    NASA Astrophysics Data System (ADS)

    Kang, S.; Park, Y.; Choi, S.; Kim, Y.; Hwang, J.; Lee, J.

    2008-12-01

    In Korea an interdisciplinary project on underwater CO2 sequestration has been started. One of the main potential sites for the sequestration is the "DolGoRae (Dolphin)" gas field located over the southwestern part of the East/Japan Sea. We plan to deliver CO2 captured from the largest steel company in Korea (POSCO) to this site through pipe lines. To meet this end, chemical engineers study the behavior of CO2 hydrates, mechanical engineers design the pipe lines and injection systems, geologists and geological engineers survey the geological structure of the potential sites, and oceanographers assess the environmental effects. From a preliminary study, we find that we can store captured CO2 to the gas filed safely. In case the CO2 leaks from the storage site it would move to the north along the Korean coast on the average.

  12. [Technology upgrades and exposure to chemical agents: results of the PPTP study in the footwear industry].

    PubMed

    Gianoli, Enrica; Brusoni, Daniela; Cornaggia, Nicoletta; Saretto, Gianni

    2012-01-01

    In the present work the chemical compositions of the products used in shoes manufacturing are reported. The data were collected over the period 2004-2007 in 156 shoe factories in Vigevano area during a study aiming the evaluation of safety conditions and occupational exposure to hazardous chemicals of the employees. The study was part of a regional project for "Occupational cancer prevention in the footwear industry". In the first phase of the study an information form on production cycle, products used and their composition was filled during preliminary audit. In the second phase of the study an in depth qualitative/quantitative evaluation of professional exposure was conducted in 13 selected shoe factories. Data analysis showed the increase in use of water-based adhesives at expense of solvent-based adhesives, the reduction to less than 3.5 weight %, and up to 1 weight %, of n-hexane concentration in solvent mixtures, the increase in use of products containing less hazardous ketones, esters, cyclohexane and heptane. Only in very few cases, products containing from 4 to 12 weight% of toluene were used. These data attest a positive trend in workers risks prevention in shoes industry.

  13. CO2 on Titan

    NASA Technical Reports Server (NTRS)

    Samuelson, R. E.; Maguire, W. C.; Hanel, R. A.; Kunde, V. G.; Jennings, D. E.; Yung, Y. L.; Aikin, A. C.

    1983-01-01

    A sharp stratospheric emission feature at 667/cm in the Voyager infrared spectra of Titan is associated with the nu2 Q branch of CO2. A coupling of photochemical and radiative-transfer theory yields an average mole fraction above the 110 mbar level of (1.5 + 1.5 or - 0.8) x 10 to the -9th, with most of the uncertainty being due to imprecise knowledge of the vertical distribution. CO2 is found to be in a steady state, with its abundance being regulated principally by the 72 K cold trap near the tropopause and secondarily by the rate at which water-bearing meteoritic material enters the top of the atmosphere. An influx of water about 0.4 times that at the top of the terrestrial atmosphere is consistent with a combination of the observed CO2 abundance and a steady-state CO mole fraction of 0.00011; the thoeretical value for CO is close to the value observed by Lutz et al. (1983), although there are large margins for error in both numbers. If steady-state conditions for CO prevail, little information is available regarding the evolution of Titan's atmosphere.

  14. The Twelve Principles of CO2 CHEMISTRY.

    PubMed

    Poliakoff, Martyn; Leitner, Walter; Streng, Emilia S

    2015-01-01

    This paper introduces a set of 12 Principles, based on the acronym CO2 CHEMISTRY, which are intended to form a set of criteria for assessing the viability of different processes or reactions for using CO2 as a feedstock for making organic chemicals. The principles aim to highlight the synergy of Carbon Dioxide Utilisation (CDU) with the components of green and sustainable chemistry as well as briefly pointing out the connection to the energy sector.

  15. How much CO2 is trapped in carbonate minerals of a natural CO2 occurrence?

    NASA Astrophysics Data System (ADS)

    Király, Csilla; Szabó, Zsuzsanna; Szamosfalvi, Ágnes; Cseresznyés, Dóra; Király, Edit; Szabó, Csaba; Falus, György

    2017-04-01

    Carbon Capture and Storage (CCS) is a transitional technology to decrease CO2 emissions from human fossil fuel usage and, therefore, to mitigate climate change. The most important criteria of a CO2 geological storage reservoir is that it must hold the injected CO2 for geological time scales without its significant seepage. The injected CO2 undergoes physical and chemical reactions in the reservoir rocks such as structural-stratigraphic, residual, dissolution or mineral trapping mechanisms. Among these, the safest is the mineral trapping, when carbonate minerals such as calcite, ankerite, siderite, dolomite and dawsonite build the CO2 into their crystal structures. The study of natural CO2 occurrences may help to understand the processes in CO2 reservoirs on geological time scales. This is the reason why the selected, the Mihályi-Répcelak natural CO2 occurrence as our research area, which is able to provide particular and highly significant information for the future of CO2 storage. The area is one of the best known CO2 fields in Central Europe. The main aim of this study is to estimate the amount of CO2 trapped in the mineral phase at Mihályi-Répcelak CO2 reservoirs. For gaining the suitable data, we apply petrographic, major and trace element (microprobe and LA-ICP-MS) and stable isotope analysis (mass spectrometry) and thermodynamic and kinetic geochemical models coded in PHREEQC. Rock and pore water compositions of the same formation, representing the pre-CO2 flooding stages of the Mihályi-Répcelak natural CO2 reservoirs are used in the models. Kinetic rate parameters are derived from the USGS report of Palandri and Kharaka (2004). The results of petrographic analysis show that a significant amount of dawsonite (NaAlCO3(OH)2, max. 16 m/m%) precipitated in the rock due to its reactions with CO2 which flooded the reservoir. This carbonate mineral alone traps about 10-30 kg/m3 of the reservoir rock from the CO2 at Mihályi-Répcelak area, which is an

  16. Regenerable Sorbent for CO2 Removal

    NASA Technical Reports Server (NTRS)

    Alptekin, Gokhan; Jayaraman, Ambal

    2013-01-01

    A durable, high-capacity regenerable sorbent can remove CO2 from the breathing loop under a Martian atmosphere. The system design allows near-ambient temperature operation, needs only a small temperature swing, and sorbent regeneration takes place at or above 8 torr, eliminating the potential for Martian atmosphere to leak into the regeneration bed and into the breathing loop. The physical adsorbent can be used in a metabolic, heat-driven TSA system to remove CO2 from the breathing loop of the astronaut and reject it to the Martian atmosphere. Two (or more) alternating sorbent beds continuously scrub and reject CO2 from the spacesuit ventilation loop. The sorbent beds are cycled, alternately absorbing CO2 from the vent loop and rejecting the adsorbed material into the environment at a high CO2 partial pressure (above 8 torr). The system does not need to run the adsorber at cryogenic temperatures, and uses a much smaller temperature swing. The sorbent removes CO2 via a weak chemical interaction. The interaction is strong enough to enable CO2 adsorption even at 3 to 7.6 torr. However, because the interaction between the surface adsorption sites and the CO2 is relatively weak, the heat input needed to regenerate the sorbent is much lower than that for chemical absorbents. The sorbent developed in this project could potentially find use in a large commercial market in the removal of CO2 emissions from coal-fired power plants, if regulations are put in place to curb carbon emissions from power plants.

  17. Silvering substrates after CO2 snow cleaning

    NASA Astrophysics Data System (ADS)

    Zito, Richard R.

    2005-09-01

    There have been some questions in the astronomical community concerning the quality of silver coatings deposited on substrates that have been cleaned with carbon dioxide snow. These questions center around the possible existence of carbonate ions left behind on the substrate by CO2. Such carbonate ions could react with deposited silver to produce insoluble silver carbonate, thereby reducing film adhesion and reflectivity. Carbonate ions could be produced from CO2 via the following mechanism. First, during CO2 snow cleaning, a small amount of moisture can condense on a surface. This is especially true if the jet of CO2 is allowed to dwell on one spot. CO2 gas can dissolve in this moisture, producing carbonic acid, which can undergo two acid dissociations to form carbonate ions. In reality, it is highly unlikely that charged carbonate ions will remain stable on a substrate for very long. As condensed water evaporates, Le Chatelier's principle will shift the equilibrium of the chain of reactions that produced carbonate back to CO2 gas. Furthermore, the hydration of CO2 reaction of CO2 with H20) is an extremely slow process, and the total dehydrogenation of carbonic acid is not favored. Living tissues that must carry out the equilibration of carbonic acid and CO2 use the enzyme carbonic anhydrase to speed up the reaction by a factor of one million. But no such enzymatic action is present on a clean mirror substrate. In short, the worst case analysis presented below shows that the ratio of silver atoms to carbonate radicals must be at least 500 million to one. The results of chemical tests presented here support this view. Furthermore, film lift-off tests, also presented in this report, show that silver film adhesion to fused silica substrates is actually enhanced by CO2 snow cleaning.

  18. The ATLAS IBL CO2 cooling system

    NASA Astrophysics Data System (ADS)

    Verlaat, B.; Ostrega, M.; Zwalinski, L.; Bortolin, C.; Vogt, S.; Godlewski, J.; Crespo-Lopez, O.; Van Overbeek, M.; Blaszcyk, T.

    2017-02-01

    The ATLAS Pixel detector has been equipped with an extra pixel layer in the space obtained by a smaller radius beam pipe. This new pixel layer called the Insertable B-Layer (IBL) was installed in 2014 and is operational in the current ATLAS data taking. The IBL detector is cooled with evaporative CO2 and is the first of its kind in ATLAS. The ATLAS IBL CO2 cooling system is designed for lower temperature operation (< ‑35oC) than the previous developed CO2 cooling systems in High Energy Physics experiments. The cold temperatures are required to protect the pixel sensors for the expected high radiation dose received at an integrated luminosity of 550 fb1. This paper describes the design, development, construction and commissioning of the IBL CO2 cooling system. It describes the challenges overcome and the important lessons learned for the development of future systems which are now under design for the Phase-II upgrade detectors.

  19. Engineered yeast for enhanced CO2 mineralization†

    PubMed Central

    Barbero, Roberto; Carnelli, Lino; Simon, Anna; Kao, Albert; Monforte, Alessandra d’Arminio; Riccò, Moreno; Bianchi, Daniele; Belcher, Angela

    2014-01-01

    In this work, a biologically catalyzed CO2 mineralization process for the capture of CO2 from point sources was designed, constructed at a laboratory scale, and, using standard chemical process scale-up protocols, was modeled and evaluated at an industrial scale. A yeast display system in Saccharomyces cerevisae was used to screen several carbonic anhydrase isoforms and mineralization peptides for their impact on CO2 hydration, CaCO3 mineralization, and particle settling rate. Enhanced rates for each of these steps in the CaCO3 mineralization process were confirmed using quantitative techniques in lab-scale measurements. The effect of these enhanced rates on the CO2 capture cost in an industrial scale CO2 mineralization process using coal fly ash as the CaO source was evaluated. The model predicts a process using bCA2- yeast and fly ash is ~10% more cost effective per ton of CO2 captured than a process with no biological molecules, a savings not realized by wild-type yeast and high-temperature stable recombinant CA2 alone or in combination. The levelized cost of electricity for a power plant using this process was calculated and scenarios in which this process compares favorably to CO2 capture by MEA absorption process are presented. PMID:25289021

  20. Engineered yeast for enhanced CO2 mineralization.

    PubMed

    Barbero, Roberto; Carnelli, Lino; Simon, Anna; Kao, Albert; Monforte, Alessandra d'Arminio; Riccò, Moreno; Bianchi, Daniele; Belcher, Angela

    2013-02-01

    In this work, a biologically catalyzed CO2 mineralization process for the capture of CO2 from point sources was designed, constructed at a laboratory scale, and, using standard chemical process scale-up protocols, was modeled and evaluated at an industrial scale. A yeast display system in Saccharomyces cerevisae was used to screen several carbonic anhydrase isoforms and mineralization peptides for their impact on CO2 hydration, CaCO3 mineralization, and particle settling rate. Enhanced rates for each of these steps in the CaCO3 mineralization process were confirmed using quantitative techniques in lab-scale measurements. The effect of these enhanced rates on the CO2 capture cost in an industrial scale CO2 mineralization process using coal fly ash as the CaO source was evaluated. The model predicts a process using bCA2- yeast and fly ash is ~10% more cost effective per ton of CO2 captured than a process with no biological molecules, a savings not realized by wild-type yeast and high-temperature stable recombinant CA2 alone or in combination. The levelized cost of electricity for a power plant using this process was calculated and scenarios in which this process compares favorably to CO2 capture by MEA absorption process are presented.

  1. CO2 laser preionisation

    NASA Technical Reports Server (NTRS)

    Spiers, Gary D.

    1991-01-01

    The final report for work done during the reporting period of January 25, 1990 to January 24, 1991 is presented. A literature survey was conducted to identify the required parameters for effective preionization in TEA CO2 lasers and the methods and techniques for characterizing preionizers are reviewed. A numerical model of the LP-140 cavity was used to determine the cause of the transverse mode stability improvement obtained when the cavity was lengthened. The measurement of the voltage and current discharge pulses on the LP-140 were obtained and their subsequent analysis resulted in an explanation for the low efficiency of the laser. An assortment of items relating to the development of high-voltage power supplies is also provided. A program for analyzing the frequency chirp data files obtained with the HP time and frequency analyzer is included. A program to calculate the theoretical LIMP chirp is also included and a comparison between experiment and theory is made. A program for calculating the CO2 linewidth and its dependence on gas composition and pressure is presented. The program also calculates the number of axial modes under the FWHM of the line for a given resonator length. A graphical plot of the results is plotted.

  2. CO2 pulses

    NASA Astrophysics Data System (ADS)

    Bell, Peter M.

    Studies of the sources and the increases of carbon dioxide in the atmosphere have been both frustrating and alarming; frustrating because so little is known and alarming because the potential consequences could be so grave (Eos, November 15, 1983, p. 929). The nature of the complexities have recently been focused upon by studies of the carbon cycle at the earth's surface and its influence on the atmosphere. It turns out that most of the increases of atmospheric carbon dioxide are from two sources: (1) petroleum and coal use and (2) the clearing of major forested lands.It is generally acknowledged that fossil fuel use has declined sharply during the past several years and that the deforestation of large areas under development will end. A recent review of current thinking on the effects of global deforestation by G.M. Woodwell and others stated that, “appropriate action taken now might reduce or eliminate the problem. Stabilization of the rate of combustion of fossil fuels combined with a program of reforestation would contribute toward stabilizing the CO2 content of the atmosphere … we need not accept as inexorable a global warming due to the accumulation of CO2 in the atmosphere” (Science, 222, 1081-1086, 1983).

  3. An X-band Co2+ EPR study of Zn1-xCoxO (x=0.005-0.1) nanoparticles prepared by chemical hydrolysis methods using diethylene glycol and denaturated alcohol at 5 K

    NASA Astrophysics Data System (ADS)

    Misra, Sushil K.; Andronenko, S. I.; Srinivasa Rao, S.; Chess, Jordan; Punnoose, A.

    2015-11-01

    EPR investigations on two types of dilute magnetic semiconductor (DMS) ZnO nanoparticles doped with 0.5-10% Co2+ ions, prepared by two chemical hydrolysis methods, using: (i) diethylene glycol ((CH2CH2OH)2O) (NC-rod-like samples), and (ii) denatured ethanol (CH3CH2OH) solutions (QC-spherical samples), were carried out at X-band (9.5 GHz) at 5 K. The analysis of EPR data for NC samples revealed the presence of several types of EPR lines: (i) two types, intense and weak, of high-spin Co2+ ions in the samples with Co concentration >0.5%; (ii) surface oxygen vacancies, and (iii) a ferromagnetic resonance (FMR) line. QC samples exhibit an intense FMR line and an EPR line due to high-spin Co2+ ions. FMR line is more intense, than the corresponding line exhibited by NC samples. These EPR spectra varied for sample with different doping concentrations. The magnetic states of these samples as revealed by EPR spectra, as well as the origin of ferromagnetism DMS samples are discussed.

  4. Measuring Nitrous Oxide Mass Transfer into Non-Aqueous CO2BOL CO2 Capture Solvents

    SciTech Connect

    Whyatt, Greg A.; Freeman, Charles J.; Zwoster, Andy; Heldebrant, David J.

    2016-03-28

    This paper investigates CO2 absorption behavior in CO2BOL solvents by decoupling the physical and chemical effects using N2O as a non-reactive mimic. Absorption measurements were performed using a wetted-wall contactor. Testing was performed using a “first generation” CO2 binding organic liquid (CO2BOL), comprised of an independent base and alcohol. Measurements were made with N2O at a lean (0.06 mol CO2/mol BOL) and rich (0.26 mol CO2/mol BOL) loading, each at three temperatures (35, 45 and 55 °C). Liquid-film mass transfer coefficients (kg') were calculated by subtracting the gas film resistance – determined from a correlation from literature – from the overall mass transfer measurement. The resulting kg' values for N2O in CO2BOLs were found to be higher than that of 5 M aqueous MEA under comparable conditions, which is supported by published measurements of Henry’s coefficients for N2O in various solvents. These results suggest that the physical solubility contribution for CO2 absorption in CO2BOLs is greater than that of aqueous amines, an effect that may pertain to other non-aqueous solvents.

  5. CO2-Water-Rock Wettability: Variability, Influencing Factors, and Implications for CO2 Geostorage.

    PubMed

    Iglauer, Stefan

    2017-05-16

    Carbon geosequestration (CGS) has been identified as a key technology to reduce anthropogenic greenhouse gas emissions and thus significantly mitigate climate change. In CGS, CO2 is captured from large point-source emitters (e.g., coal fired power stations), purified, and injected deep underground into geological formations for disposal. However, the CO2 has a lower density than the resident formation brine and thus migrates upward due to buoyancy forces. To prevent the CO2 from leaking back to the surface, four trapping mechanisms are used: (1) structural trapping (where a tight caprock acts as a seal barrier through which the CO2 cannot percolate), (2) residual trapping (where the CO2 plume is split into many micrometer-sized bubbles, which are immobilized by capillary forces in the pore network of the rock), (3) dissolution trapping (where CO2 dissolves in the formation brine and sinks deep into the reservoir due to a slight increase in brine density), and (4) mineral trapping (where the CO2 introduced into the subsurface chemically reacts with the formation brine or reservoir rock or both to form solid precipitates). The efficiency of these trapping mechanisms and the movement of CO2 through the rock are strongly influenced by the CO2-brine-rock wettability (mainly due to the small capillary-like pores in the rock which form a complex network), and it is thus of key importance to rigorously understand CO2-wettability. In this context, a substantial number of experiments have been conducted from which several conclusions can be drawn: of prime importance is the rock surface chemistry, and hydrophilic surfaces are water-wet while hydrophobic surfaces are CO2-wet. Note that CO2-wet surfaces dramatically reduce CO2 storage capacities. Furthermore, increasing pressure, salinity, or dissolved ion valency increases CO2-wettability, while the effect of temperature is not well understood. Indeed theoretical understanding of CO2-wettability and the ability to

  6. Chemical composition of Lycium europaeum fruit oil obtained by supercritical CO2 extraction and evaluation of its antioxidant activity, cytotoxicity and cell absorption.

    PubMed

    Rosa, Antonella; Maxia, Andrea; Putzu, Danilo; Atzeri, Angela; Era, Benedetta; Fais, Antonella; Sanna, Cinzia; Piras, Alessandra

    2017-09-01

    We studied the total phenols and flavonoids, liposoluble antioxidants, fatty acid and triacylglycerol profiles, and oxidative status of oil obtained from Lycium europaeum fruits following supercritical CO2 extraction (at 30MPa and 40°C). Linoleic (52%), palmitic (18%), oleic (13%), and α-linolenic (6%) were the main oil fatty acids, while trilinolein and palmitodilinolein/oleodilinolein represented the main triacylglycerols. The oil was characterized by high levels of all-trans-zeaxanthin and all-trans-β-carotene (755 and 332μg/g of oil, respectively), α-tocopherol (308μg/g of oil), total phenols (13.6mg gallic acid equivalents/g of oil), and total flavonoids (6.8mg quercetin equivalents/g of oil). The oil showed radical scavenging activities (ABTS and DPPH assays) and inhibited Caco-2 cell growth. Moreover, the incubation of differentiated Caco-2 cells with a non-toxic oil concentration (100μg/mL) induced a significant intracellular accumulation of essential fatty acids. The results qualify L. europaeum oil as a potential source for food/pharmaceutical applications. Copyright © 2017 Elsevier Ltd. All rights reserved.

  7. CO2 Laser Market

    NASA Astrophysics Data System (ADS)

    Simonsson, Samuel

    1989-03-01

    It gives me a great deal of pleasure to introduce our final speaker of this morning's session for two reasons: First of all, his company has been very much in the news not only in our own community but in the pages of Wall Street Journal and in the world economic press. And, secondly, we would like to welcome him to our shores. He is a temporary resident of the United States, for a few months, forsaking his home in Germany to come here and help with the start up of a new company which we believe, probably, ranks #1 as the world supplier of CO2 lasers now, through the combination of former Spectra Physics Industrial Laser Division and Rofin-Sinar GMBH. Samuel Simonsson is the Chairman of the Board of Rofin-Sinar, Inc., here in the U.S. and managing director of Rofin-Sinar GMBH. It is a pleasure to welcome him.

  8. Capture and Sequestration of CO2 at the Boise White Paper Mill

    SciTech Connect

    B.P. McGrail; C.J. Freeman; G.H. Beeman; E.C. Sullivan; S.K. Wurstner; C.F. Brown; R.D. Garber; D. Tobin E.J. Steffensen; S. Reddy; J.P. Gilmartin

    2010-06-16

    This report documents the efforts taken to develop a preliminary design for the first commercial-scale CO2 capture and sequestration (CCS) project associated with biomass power integrated into a pulp and paper operation. The Boise Wallula paper mill is located near the township of Wallula in Southeastern Washington State. Infrastructure at the paper mill will be upgraded such that current steam needs and a significant portion of the current mill electric power are supplied from a 100% biomass power source. A new biomass power system will be constructed with an integrated amine-based CO2 capture plant to capture approximately 550,000 tons of CO2 per year for geologic sequestration. A customized version of Fluor Corporation’s Econamine Plus™ carbon capture technology will be designed to accommodate the specific chemical composition of exhaust gases from the biomass boiler. Due to the use of biomass for fuel, employing CCS technology represents a unique opportunity to generate a net negative carbon emissions footprint, which on an equivalent emissions reduction basis is 1.8X greater than from equivalent fossil fuel sources (SPATH and MANN, 2004). Furthermore, the proposed project will offset a significant amount of current natural gas use at the mill, equating to an additional 200,000 tons of avoided CO2 emissions. Hence, the total net emissions avoided through this project equates to 1,100,000 tons of CO2 per year. Successful execution of this project will provide a clear path forward for similar kinds of emissions reduction that can be replicated at other energy-intensive industrial facilities where the geology is suitable for sequestration. This project also represents a first opportunity for commercial development of geologic storage of CO2 in deep flood basalt formations. The Boise paper mill site is host to a Phase II pilot study being carried out under DOE’s Regional Carbon Partnership Program. Lessons learned from this pilot study and other separately

  9. Volatile Organic Compounds (VOCs) and Elevated Concentrations of Carbon Dioxide (CO2) in Unsaturated-Zone Vapors Near a Chemical and Low-Level Radioactivity Waste-Disposal Facility, Amargosa Desert Research Site, Nye County, Nevada

    NASA Astrophysics Data System (ADS)

    Baker, R. J.; Andraski, B. J.; Walvoord, M. A.; Stonestrom, D. A.; Prudic, D. E.; Luo, W.

    2003-12-01

    As part of its Toxic Substances Hydrology Program, the U.S. Geological Survey is studying contaminant-transport processes in an arid environment at the Amargosa Desert Research Site (http://nevada.usgs.gov/adrs/). The site is near waste-disposal facilities 20 kilometers east of Death Valley National Park. Low-level radioactive waste was buried in unlined trenches of varying depth during 1962-92. Hazardous chemical waste was buried in unlined trenches at an adjacent facility during 1970-88. Mean annual precipitation at the site from 1981 to 2000 was 108 millimeters. The unsaturated zone is aerobic down to the water table, which is about 110 m (meters) deep. Sampling infrastructure south and west of the facility includes a grid of vapor probes 1.5 m deep, a 23.8-m-deep background borehole (JFDB), and two approximately 100-m-deep boreholes (UZB-2 and UZB-3), which are 160 m and 100 m from the nearest trench, respectively, and are instrumented for multi-level sampling. Analytes detected in unsaturated-zone-vapor samples include elevated concentrations of tritium and carbon-14; three chlorofluorocarbon (CFC) compounds, eight chlorinated solvent compounds, and toluene, all at concentrations exceeding 1,000 parts per billion (ppb) in UZB-3, and at lower concentrations in UZB-2 and in the shallow-vapor-probe grid; and CO2 in concentrations up to 2% in UZB-3, whereas maximum CO2 concentrations in JFDB are less than 0.2%. With the notable exception of toluene, VOCs that are known to be highly biodegradable are generally absent or occur at low concentrations (<100 ppb). The trends in the CO2 concentration profiles approximately parallel those of CFCs and radionuclides. The following preliminary conclusions have been drawn from the radionuclide, VOC, and CO2 data: 1. Biodegradation of organic substances is a reasonable explanation for the presence of CO2 in UZB-3 at concentrations greater those in JFDB (background), which are attributed to near-surface natural biological

  10. Acid Gas Capture Using CO2-Binding Organic Liquids

    SciTech Connect

    Heldebrant, David J.; Koech, Phillip K.; Rainbolt, James E.; Zheng, Feng

    2010-11-10

    Current chemical CO2 scrubbing technology is primarily aqueous alkanolamine based. These systems rapidly bind CO2 (forming water-soluble carbamate and bicarbonate salts) however, the process has serious disadvantages. The concentration of monoethanolamine rarely exceeds 30 wt % due to the corrosive nature of the solution, and this reduces the maximum CO2 volumetric (≤108 g/L) and gravimetric capacity (≤7 wt%) of the CO2 scrubber. The ≤30 wt % loading of ethanolamine also means that a large excess of water must be pumped and heated during CO2 capture and release, and this greatly increases the energy requirements especially considering the high specific heat of water (4 j/g-1K-1). Our approach is to switch to organic systems that chemically bind CO2 as liquid alkylcarbonate salts. Our CO2-binding organic liquids have higher CO2 solubility, lower specific heats, potential for less corrosion and lower binding energies for CO2 than aqueous systems. CO2BOLs also reversibly bind and release mixed sulfur oxides. Furthermore the CO2BOL system can be direct solvent replacements for any solvent based CO2 capture systems because they are commercially available reagents and because they are fluids they would not require extensive process re-engineering.

  11. Modeling global atmospheric CO2 with improved emission inventories and CO2 production from the oxidation of other carbon species

    NASA Astrophysics Data System (ADS)

    Nassar, R.; Jones, D. B. A.; Suntharalingam, P.; Chen, J. M.; Andres, R. J.; Wecht, K. J.; Yantosca, R. M.; Kulawik, S. S.; Bowman, K. W.; Worden, J. R.; Machida, T.; Matsueda, H.

    2010-12-01

    The use of global three-dimensional (3-D) models with satellite observations of CO2 in inverse modeling studies is an area of growing importance for understanding Earth's carbon cycle. Here we use the GEOS-Chem model (version 8-02-01) CO2 mode with multiple modifications in order to assess their impact on CO2 forward simulations. Modifications include CO2 surface emissions from shipping (~0.19 Pg C yr-1), 3-D spatially-distributed emissions from aviation (~0.16 Pg C yr-1), and 3-D chemical production of CO2 (~1.05 Pg C yr-1). Although CO2 chemical production from the oxidation of CO, CH4 and other carbon gases is recognized as an important contribution to global CO2, it is typically accounted for by conversion from its precursors at the surface rather than in the free troposphere. We base our model 3-D spatial distribution of CO2 chemical production on monthly-averaged loss rates of CO (a key precursor and intermediate in the oxidation of organic carbon) and apply an associated surface correction for inventories that have counted emissions of CO2 precursors as CO2. We also explore the benefit of assimilating satellite observations of CO into GEOS-Chem to obtain an observation-based estimate of the CO2 chemical source. The CO assimilation corrects for an underestimate of atmospheric CO abundances in the model, resulting in increases of as much as 24% in the chemical source during May-June 2006, and increasing the global annual estimate of CO2 chemical production from 1.05 to 1.18 Pg C. Comparisons of model CO2 with measurements are carried out in order to investigate the spatial and temporal distributions that result when these new sources are added. Inclusion of CO2 emissions from shipping and aviation are shown to increase the global CO2 latitudinal gradient by just over 0.10 ppm (~3%), while the inclusion of CO2 chemical production (and the surface correction) is shown to decrease the latitudinal gradient by about 0.40 ppm (~10%) with a complex spatial structure

  12. Modeling global atmospheric CO2 with improved emission inventories and CO2 production from the oxidation of other carbon species

    SciTech Connect

    Nassar, Ray; Jones, DBA; Suntharalingam, P; Chen, j.; Andres, Robert Joseph; Wecht, K. J.; Yantosca, R. M.; Kulawik, SS; Bowman, K; Worden, JR; Machida, T; Matsueda, H

    2010-01-01

    The use of global three-dimensional (3-D) models with satellite observations of CO2 in inverse modeling studies is an area of growing importance for understanding Earth s carbon cycle. Here we use the GEOS-Chem model (version 8-02-01) CO2 mode with multiple modifications in order to assess their impact on CO2 forward simulations. Modifications include CO2 surface emissions from shipping (0.19 PgC yr 1), 3-D spatially-distributed emissions from aviation (0.16 PgC yr 1), and 3-D chemical production of CO2 (1.05 PgC yr 1). Although CO2 chemical production from the oxidation of CO, CH4 and other carbon gases is recognized as an important contribution to global CO2, it is typically accounted for by conversion from its precursors at the surface rather than in the free troposphere. We base our model 3-D spatial distribution of CO2 chemical production on monthly-averaged loss rates of CO (a key precursor and intermediate in the oxidation of organic carbon) and apply an associated surface correction for inventories that have counted emissions of CO2 precursors as CO2. We also explore the benefit of assimilating satellite observations of CO into GEOS-Chem to obtain an observation-based estimate of the CO2 chemical source. The CO assimilation corrects for an underestimate of atmospheric CO abundances in the model, resulting in increases of as much as 24% in the chemical source during May June 2006, and increasing the global annual estimate of CO2 chemical production from 1.05 to 1.18 Pg C. Comparisons of model CO2 with measurements are carried out in order to investigate the spatial and temporal distributions that result when these new sources are added. Inclusion of CO2 emissions from shipping and aviation are shown to increase the global CO2 latitudinal gradient by just over 0.10 ppm (3%), while the inclusion of CO2 chemical production (and the surface correction) is shown to decrease the latitudinal gradient by about 0.40 ppm (10%) with a complex spatial structure

  13. Physical and Chemical Effects of Two-Phase Brine/Supercritical-CO2 Fluid Flow on Clastic Rocks: Real-Time Monitoring and NMR Imaging of Flow-Through Core Experiments

    NASA Astrophysics Data System (ADS)

    Shaw, C. A.; Vogt, S.; Maneval, J. E.; Brox, T.; Skidmore, M. L.; Codd, S. L.; Seymour, J. D.

    2010-12-01

    Sandstone core samples were challenged with a supercritical CO2-saturated brine mixture in a laboratory flow-through core reactor system over a range of temperatures and brine strengths. Cores of quartz arenite from the Berea formation were selected to represent ideal ‘clean’ sandstone These laboratory experiments potentially provide an analog for the acidification of pore fluids near the brine/CO2 interface during CO2 flooding of depleted clastic hydrocarbon reservoirs for carbon sequestration. Flow in the reactor was perpendicular to bedding. Initial experiments were run at 50°C and 100°C with brine concentrations of 1g/L and 10g/L (TDS) to test effects of different temperatures and brine compositions. Real-time monitoring of fluid pH and conductivity provided a measure of reaction rates. Introduction of supercritical CO2 into the brine-saturated cores initiated a reduction in pH accompanied by an increase in conductivity. NMR images of fresh cores were compared with images of challenged cores using a protocol for pixel-by-pixel comparison to determine the effects on bulk pore volume and geometry. Two types of imaging experiments were conducted: multi-slice spin echo and 3-D spin echo images. Multi-slice experiments had a slice thickness of 1.5 mm and an in-plane resolution of 0.27 mm x 0.27 mm, and 3-D experiments had a resolution of 0.47 mm x 0.55 mm x 0.55mm. Imaging results reflected the observed changes in the physical and chemical structure post-challenge. Two-dimensional relaxation correlation experiments were also conducted to probe the pore sizes, connectivity and fluid saturation of the rock cores before and after challenging. Chemical analyses and microscopic examination of the challenged cores will provide a better understanding of alteration in the cores and the changes in the volume, geometry and connectivity of pore space.

  14. CO2 mineralization-bridge between storage and utilization of CO2.

    PubMed

    Geerlings, Hans; Zevenhoven, Ron

    2013-01-01

    CO2 mineralization comprises a chemical reaction between suitable minerals and the greenhouse gas carbon dioxide. The CO2 is effectively sequestered as a carbonate, which is stable on geological timescales. In addition, the variety of materials that can be produced through mineralization could find applications in the marketplace, which makes implementation of the technology more attractive. In this article, we review recent developments and assess the current status of the CO2 mineralization field. In an outlook, we briefly describe a few mineralization routes, which upon further development have the potential to be implemented on a large scale.

  15. Forecasting global atmospheric CO2

    NASA Astrophysics Data System (ADS)

    Agustí-Panareda, A.; Massart, S.; Chevallier, F.; Boussetta, S.; Balsamo, G.; Beljaars, A.; Ciais, P.; Deutscher, N. M.; Engelen, R.; Jones, L.; Kivi, R.; Paris, J.-D.; Peuch, V.-H.; Sherlock, V.; Vermeulen, A. T.; Wennberg, P. O.; Wunch, D.

    2014-11-01

    A new global atmospheric carbon dioxide (CO2) real-time forecast is now available as part of the pre-operational Monitoring of Atmospheric Composition and Climate - Interim Implementation (MACC-II) service using the infrastructure of the European Centre for Medium-Range Weather Forecasts (ECMWF) Integrated Forecasting System (IFS). One of the strengths of the CO2 forecasting system is that the land surface, including vegetation CO2 fluxes, is modelled online within the IFS. Other CO2 fluxes are prescribed from inventories and from off-line statistical and physical models. The CO2 forecast also benefits from the transport modelling from a state-of-the-art numerical weather prediction (NWP) system initialized daily with a wealth of meteorological observations. This paper describes the capability of the forecast in modelling the variability of CO2 on different temporal and spatial scales compared to observations. The modulation of the amplitude of the CO2 diurnal cycle by near-surface winds and boundary layer height is generally well represented in the forecast. The CO2 forecast also has high skill in simulating day-to-day synoptic variability. In the atmospheric boundary layer, this skill is significantly enhanced by modelling the day-to-day variability of the CO2 fluxes from vegetation compared to using equivalent monthly mean fluxes with a diurnal cycle. However, biases in the modelled CO2 fluxes also lead to accumulating errors in the CO2 forecast. These biases vary with season with an underestimation of the amplitude of the seasonal cycle both for the CO2 fluxes compared to total optimized fluxes and the atmospheric CO2 compared to observations. The largest biases in the atmospheric CO2 forecast are found in spring, corresponding to the onset of the growing season in the Northern Hemisphere. In the future, the forecast will be re-initialized regularly with atmospheric CO2 analyses based on the assimilation of CO2 products retrieved from satellite measurements and

  16. Modeling global atmospheric CO2 with improved emission inventories and CO2 production from the oxidation of other carbon species

    NASA Astrophysics Data System (ADS)

    Nassar, R.; Jones, D. B. A.; Suntharalingam, P.; Chen, J. M.; Andres, R. J.; Wecht, K. J.; Yantosca, R. M.; Kulawik, S. S.; Bowman, K. W.; Worden, J. R.; Machida, T.; Matsueda, H.

    2010-07-01

    The use of global three-dimensional (3-D) models with satellite observations of CO2 in inverse modeling studies is an area of growing importance for understanding Earth's carbon cycle. Here we use the GEOS-Chem model (version 8-02-01) CO2 simulation with multiple modifications in order to assess their impact on CO2 forward simulations. Modifications include CO2 surface emissions from shipping (~0.19 Pg C/yr), 3-D spatially-distributed emissions from aviation (~0.16 Pg C/yr), and 3-D chemical production of CO2 (~1.05 Pg C/yr). Although CO2 chemical production from the oxidation of CO, CH4 and other carbon gases is recognized as an important contribution to global CO2, it is typically accounted for by conversion from its precursors at the surface rather than in the free troposphere. We base our model 3-D spatial distribution of CO2 chemical production on monthly-averaged loss rates of CO (a key precursor and intermediate in the oxidation of organic carbon) and apply an associated surface correction for inventories that have counted emissions of carbon precursor as CO2. We also explore the benefit of assimilating satellite observations of CO into GEOS-Chem to obtain an observation-based estimate of the CO2 chemical source. The CO assimilation corrects for an underestimate of atmospheric CO abundances in the model, resulting in increases of as much as 24% in the chemical source during May-June 2006, and increasing the global annual estimate of CO2 chemical production from 1.05 to 1.18 Pg C. Comparisons of model CO2 with measurements are carried out in order to investigate the spatial and temporal distributions that result when these new sources are added. Inclusion of CO2 emissions from shipping and aviation are shown to increase the global CO2 latitudinal gradient by just over 0.10 ppm (~3%), while the inclusion of CO2 chemical production (and the surface correction) is shown to decrease the latitudinal gradient by about 0.40 ppm (~10%) with a complex spatial

  17. Forecasting global atmospheric CO2

    NASA Astrophysics Data System (ADS)

    Agustí-Panareda, A.; Massart, S.; Chevallier, F.; Boussetta, S.; Balsamo, G.; Beljaars, A.; Ciais, P.; Deutscher, N. M.; Engelen, R.; Jones, L.; Kivi, R.; Paris, J.-D.; Peuch, V.-H.; Sherlock, V.; Vermeulen, A. T.; Wennberg, P. O.; Wunch, D.

    2014-05-01

    A new global atmospheric carbon dioxide (CO2) real-time forecast is now available as part of the pre-operational Monitoring of Atmospheric Composition and Climate - Interim Implementation (MACC-II) service using the infrastructure of the European Centre for Medium-Range Weather Forecasts (ECMWF) Integrated Forecasting System (IFS). One of the strengths of the CO2 forecasting system is that the land surface, including vegetation CO2 fluxes, is modelled online within the IFS. Other CO2 fluxes are prescribed from inventories and from off-line statistical and physical models. The CO2 forecast also benefits from the transport modelling from a state-of-the-art numerical weather prediction (NWP) system initialized daily with a wealth of meteorological observations. This paper describes the capability of the forecast in modelling the variability of CO2 on different temporal and spatial scales compared to observations. The modulation of the amplitude of the CO2 diurnal cycle by near-surface winds and boundary layer height is generally well represented in the forecast. The CO2 forecast also has high skill in simulating day-to-day synoptic variability. In the atmospheric boundary layer, this skill is significantly enhanced by modelling the day-to-day variability of the CO2 fluxes from vegetation compared to using equivalent monthly mean fluxes with a diurnal cycle. However, biases in the modelled CO2 fluxes also lead to accumulating errors in the CO2 forecast. These biases vary with season with an underestimation of the amplitude of the seasonal cycle both for the CO2 fluxes compared to total optimized fluxes and the atmospheric CO2 compared to observations. The largest biases in the atmospheric CO2 forecast are found in spring, corresponding to the onset of the growing season in the Northern Hemisphere. In the future, the forecast will be re-initialized regularly with atmospheric CO2 analyses based on the assimilation of CO2 satellite retrievals, as they become available in

  18. CO2 laser cutting of natural granite

    NASA Astrophysics Data System (ADS)

    Riveiro, A.; Mejías, A.; Soto, R.; Quintero, F.; del Val, J.; Boutinguiza, M.; Lusquiños, F.; Pardo, J.; Pou, J.

    2016-01-01

    Commercial black granite boards (trade name: "Zimbabwe black granite") 10 mm thick, were successfully cut by a 3.5 kW CO2 laser source. Cutting quality, in terms of kerf width and roughness of the cut wall, was assessed by means of statistically planned experiments. No chemical modification of the material in the cutting walls was detected by the laser beam action. Costs associated to the process were calculated, and the main factors affecting them were identified. Results reported here demonstrate that cutting granite boards could be a new application of CO2 laser cutting machines provided a supersonic nozzle is used.

  19. Co2 geological sequestration

    SciTech Connect

    Xu, Tianfu

    2004-11-18

    Human activities are increasingly altering the Earth's climate. A particular concern is that atmospheric concentrations of carbon dioxide (CO{sub 2}) may be rising fast because of increased industrialization. CO{sub 2} is a so-called ''greenhouse gas'' that traps infrared radiation and may contribute to global warming. Scientists project that greenhouse gases such as CO{sub 2} will make the arctic warmer, which would melt glaciers and raise sea levels. Evidence suggests that climate change may already have begun to affect ecosystems and wildlife around the world. Some animal species are moving from one habitat to another to adapt to warmer temperatures. Future warming is likely to exceed the ability of many species to migrate or adjust. Human production of CO{sub 2} from fossil fuels (such as at coal-fired power plants) is not likely to slow down soon. It is urgent to find somewhere besides the atmosphere to put these increased levels of CO{sub 2}. Sequestration in the ocean and in soils and forests are possibilities, but another option, sequestration in geological formations, may also be an important solution. Such formations could include depleted oil and gas reservoirs, unmineable coal seams, and deep saline aquifers. In many cases, injection of CO2 into a geological formation can enhance the recovery of hydrocarbons, providing value-added byproducts that can offset the cost of CO{sub 2} capture and sequestration. Before CO{sub 2} gas can be sequestered from power plants and other point sources, it must be captured. CO{sub 2} is also routinely separated and captured as a by-product from industrial processes such as synthetic ammonia production, H{sub 2} production, and limestone calcination. Then CO{sub 2} must be compressed into liquid form and transported to the geological sequestration site. Many power plants and other large emitters of CO{sub 2} are located near geological formations that are amenable to CO{sub 2} sequestration.

  20. India Co2 Emissions

    NASA Astrophysics Data System (ADS)

    Sharan, S.; Diffenbaugh, N. S.

    2010-12-01

    created a balance in between the “developed” and developing countries. If India was producing the same amounts of emissions per capita as the it would have a total of 20 billion metric tons of CO2 emissions annually.

  1. Hydrogen production with CO 2 capture by coupling steam reforming of methane and chemical-looping combustion: Use of an iron-based waste product as oxygen carrier burning a PSA tail gas

    NASA Astrophysics Data System (ADS)

    Ortiz, María; Gayán, Pilar; de Diego, Luis F.; García-Labiano, Francisco; Abad, Alberto; Pans, Miguel A.; Adánez, Juan

    In this work it is analyzed the performance of an iron waste material as oxygen carrier for a chemical-looping combustion (CLC) system. CLC is a novel combustion technology with the benefit of inherent CO 2 separation that can be used as a source of energy for the methane steam reforming process (SR). The tail gas from the PSA unit is used as fuel in the CLC system. The oxygen carrier behaviour with respect to gas combustion was evaluated in a continuous 500 W th CLC prototype using a simulated PSA off-gas stream as fuel. Methane or syngas as fuel were also studied for comparison purposes. The oxygen carrier showed enough high oxygen transport capacity and reactivity to fully convert syngas at 880 °C. However, lower conversion of the fuel was observed with methane containing fuels. An estimated solids inventory of 1600 kg MW th -1 would be necessary to fully convert the PSA off-gas to CO 2 and H 2O. An important positive effect of the oxygen carrier-to-fuel ratio up to 1.5 and the reactor temperature on the combustion efficiency was found. A characterization of the calcined and after-used particles was carried out showing that this iron-based material can be used as oxygen carrier in a CLC plant since particles maintain their properties (reactivity, no agglomeration, high durability, etc.) after more than 111 h of continuous operation.

  2. Development of Novel CO2 Adsorbents for Capture of CO2 from Flue Gas

    SciTech Connect

    Fauth, D.J.; Filburn, T.P.; Gray, M.L.; Hedges, S.W.; Hoffman, J.; Pennline, H.W.; Filburn, T.

    2007-06-01

    Capturing CO2 emissions generated from fossil fuel-based power plants has received widespread attention and is considered a vital course of action for CO2 emission abatement. Efforts are underway at the Department of Energy’s National Energy Technology Laboratory to develop viable energy technologies enabling the CO2 capture from large stationary point sources. Solid, immobilized amine sorbents (IAS) formulated by impregnation of liquid amines within porous substrates are reactive towards CO2 and offer an alternative means for cyclic capture of CO2 eliminating, to some degree, inadequacies related to chemical absorption by aqueous alkanolamine solutions. This paper describes synthesis, characterization, and CO2 adsorption properties for IAS materials previously tested to bind and release CO2 and water vapor in a closed loop life support system. Tetraethylenepentamine (TEPA), acrylonitrile-modified tetraethylenepentamine (TEPAN), and a single formulation consisting of TEPAN and N, N’-bis(2-hydroxyethyl)ethylenediamine (BED) were individually supported on a poly (methyl methacrylate) (PMMA) substrate and examined. CO2 adsorption profiles leading to reversible CO2 adsorption capacities were obtained using thermogravimetry. Under 10% CO2 in nitrogen at 25°C and 1 atm, TEPA supported on PMMA over 60 minutes adsorbed ~3.2 mmol/g{sorbent} whereas, TEPAN supported on PMMA along with TEPAN and BED supported on PMMA adsorbed ~1.7 mmol/g{sorbent} and ~2.3 mmol/g{sorbent} respectively. Cyclic experiments with a 1:1 weight ratio of TEPAN and BED supported on poly (methyl methacrylate) beads utilizing a fixed-bed flow system with 9% CO2, 3.5% O2, nitrogen balance with trace gas constituents were studied. CO2 adsorption capacity was ~ 3 mmols CO2/g{sorbent} at 40°C and 1.4 atm. No beneficial effect on IAS performance was found using a moisture-laden flue gas mixture. Tests with 750 ppmv NO in a humidified gas stream revealed negligible NO sorption onto the IAS. A high SO2

  3. CO2 adsorption isotherm on clay minerals and the CO2 accessibility into the clay interlayer

    NASA Astrophysics Data System (ADS)

    Gensterblum, Yves; Bertier, Pieter; Busch, Andreas; Rother, Gernot; Krooß, Bernhard

    2013-04-01

    Large-scale CO2 storage in porous rock formations at 1-3 km depth is seen as a global warming mitigation strategy. In this process, CO2 is separated from the flue gas of coal or gas power plants, compressed, and pumped into porous subsurface reservoirs with overlying caprocks (seals). Good seals are mechanically and chemically stable caprocks with low porosity and permeability. They prevent leakage of buoyant CO2 from the reservoir. Caprocks are generally comprised of thick layers of shale, and thus mainly consist of clay minerals. These clays can be affected by CO2-induced processes, such as swelling or dissolution. The interactions of CO2 with clay minerals in shales are at present poorly understood. Sorption measurements in combination scattering techniques could provide fundamental insight into the mechanisms governing CO2-clay interaction. Volumetric sorption techniques have assessed the sorption of supercritical CO2 onto coal (Gensterblum et al., 2010; Gensterblum et al., 2009), porous silica (Rother et al., 2012a) and clays as a means of exploring the potential of large-scale storage of anthropogenic CO2 in geological reservoirs (Busch et al., 2008). On different clay minerals and shales, positive values of excess sorption were measured at gas pressures up to 6 MPa, where the interfacial fluid is assumed to be denser than the bulk fluid. However, zero and negative values were obtained at higher densities, which suggests the adsorbed fluid becomes equal to and eventually less dense than the corresponding bulk fluid, or that the clay minerals expand on CO2 charging. Using a combination of neutron diffraction and excess sorption measurements, we recently deduced the interlayer density of scCO2 in Na-montmorillonite clay in its single-layer hydration state (Rother et al., 2012b), and confirmed its low density, as well as the expansion of the basal spacings. We performed neutron diffraction experiments at the FRMII diffractometer on smectite, kaolinite and illite

  4. Is CO2 ice permanent?

    NASA Technical Reports Server (NTRS)

    Lindner, Bernhard Lee

    1992-01-01

    Carbon dioxide ice has been inferred to exist at the south pole in summertime, but Earth based measurements in 1969 of water vapor in the Martian atmosphere suggest that all CO2 ice sublined from the southern polar cap and exposed underlying water ice. This implies that the observed summertime CO2 ice is of recent origin. It appears possible to construct an energy balance model that maintains seasonal CO2 ice at the south pole year round and still reasonably simulates the polar cap regression and atmospheric pressure data. This implies that the CO2 ice observed in the summertime south polar cap could be seasonal in origin, and that minor changes in climate could cause CO2 ice to completely vanish, as would appear to have happened in 1969. However, further research remains before it is certain whether the CO2 ice observed in the summertime south polar cap is seasonal or is part of a permanent reservoir.

  5. Catalytic hydrothermal upgrading of crude bio-oils produced from different thermo-chemical conversion routes of microalgae.

    PubMed

    Duan, Peigao; Wang, Bing; Xu, Yuping

    2015-06-01

    This study presents experimental results that compare the use of hydrothermal liquefaction (HTL), alcoholysis (Al), pyrolysis (Py) and hydropyrolysis (HPy) for the production of bio-oil from a microalga (Chlorella pyrenoidosa) and the catalytic hydrothermal upgrading of crude bio-oils produced by these four conversion routes. The yields and compositions of bio-oil, solid residue, and gases were evaluated and compared. HTL resulted in a bio-oil that has a higher energy density and superior fuel properties, such as thermal and storage stabilities, compared with the other three conversion routes. The N in crude bio-oils produced from Py and HPy is more easily removed than that in the bio-oils produced from HTL and Al. The upgraded bio-oils contain reduced amounts of certain O-containing and N-containing compounds and significantly increased saturated hydrocarbon contents. All of the upgraded bio-oils have a larger fraction boiling below 350°C than their corresponding crude bio-oils.

  6. Elevated CO(2) and drought stress effects on the chemical composition of maize plants, their ruminal fermentation and microbial diversity in vitro.

    PubMed

    Meibaum, Birgit; Riede, Susanne; Schröder, Bernd; Manderscheid, Remy; Weigel, Hans-Joachim; Breves, Gerhard

    2012-12-01

    Climate changes are supposed to influence productivity and chemical composition of plants. In the present experiments, it was hypothesised that the incubation of plants exposed to elevated atmospheric carbon dioxide concentrations ([CO₂]) and drought stress will result in different ruminal fermentation pattern and microbial diversity compared to unaffected plants. Maize plants were grown, well-watered under ambient (380 ppm CO₂, Variant A) and elevated [CO₂] (550 ppm CO₂, Variant B). Furthermore, each CO₂ treatment was also exposed to drought stress (380 ppm and 550 ppm CO₂,Variants C and D, respectively), which received only half as much water as the well-watered plants. Plant material from these treatments was incubated in a semi-continuous in vitro fermentation experiment using the rumen simulation technique. Single strand conformation polymorphism (SSCP) analysis was conducted for Bacteria and Archaea specific profiles. The analysis of crude nutrients showed higher contents of fibre fraction in drought stress Variants C and D. Crude protein content was increased by drought stress under ambient but not under elevated [CO₂]. Fermentation of drought stress variants resulted in significantly increased pH values, decreased digestibilities of organic matter and increased ammonia-N (NH₃-N) concentrations compared with well-watered variants. Additionally, the 550 ppm CO₂ Variants B and D showed significantly lower NH₃-N concentrations than Variants A and C. The Bacteria- and Archaea-specific SSCP profiles as well as the production rates of short-chain fatty acids and their molar percentages were not affected by treatments. During the first four days of equilibration period, a decrease of molar percentage of acetate and increased molar percentages of propionate were observed for all treatments. These alterations might have been induced by adaptation of the in vitro system to the new substrate. The rumen microflora appeared to be highly adaptive and

  7. CO2 interaction with geomaterials.

    SciTech Connect

    Guthrie, George D.; Al-Saidi, Wissam A.; Jordan, Kenneth D.; Voora, Vamsee, K.; Romanov, Vyacheslav N.; Lopano, Christina L; Myshakin, Eugene M.; Hur, Tae Bong; Warzinski, Robert P.; Lynn, Ronald J.; Howard, Bret H.; Cygan, Randall Timothy

    2010-09-01

    This work compares the sorption and swelling processes associated with CO2-coal and CO2-clay interactions. We investigated the mechanisms of interaction related to CO2 adsortion in micropores, intercalation into sub-micropores, dissolution in solid matrix, the role of water, and the associated changes in reservoir permeability, for applications in CO2 sequestration and enhanced coal bed methane recovery. The structural changes caused by CO2 have been investigated. A high-pressure micro-dilatometer was equipped to investigate the effect of CO2 pressure on the thermoplastic properties of coal. Using an identical dilatometer, Rashid Khan (1985) performed experiments with CO2 that revealed a dramatic reduction in the softening temperature of coal when exposed to high-pressure CO2. A set of experiments was designed for -20+45-mesh samples of Argonne Premium Pocahontas No.3 coal, which is similar in proximate and ultimate analysis to the Lower Kittanning seam coal that Khan used in his experiments. No dramatic decrease in coal softening temperature has been observed in high-pressure CO2 that would corroborate the prior work of Khan. Thus, conventional polymer (or 'geopolymer') theories may not be directly applicable to CO2 interaction with coals. Clays are similar to coals in that they represent abundant geomaterials with well-developed microporous structure. We evaluated the CO2 sequestration potential of clays relative to coals and investigated the factors that affect the sorption capacity, rates, and permanence of CO2 trapping. For the geomaterials comparison studies, we used source clay samples from The Clay Minerals Society. Preliminary results showed that expandable clays have CO2 sorption capacities comparable to those of coal. We analyzed sorption isotherms, XRD, DRIFTS (infrared reflectance spectra at non-ambient conditions), and TGA-MS (thermal gravimetric analysis) data to compare the effects of various factors on CO2 trapping. In montmorillonite, CO2

  8. Vertical transport rates and concentrations of OH and Cl radicals in the Tropical Tropopause Layer from observations of CO2 and halocarbons: implications for distributions of long- and short-lived chemical species

    NASA Astrophysics Data System (ADS)

    Park, S.; Atlas, E. L.; Jiménez, R.; Daube, B. C.; Gottlieb, E. W.; Nan, J.; Jones, D. B. A.; Pfister, L.; Conway, T. J.; Bui, T. P.; Gao, R.-S.; Wofsy, S. C.

    2010-07-01

    Rates for large-scale vertical transport of air in the Tropical Tropopause Layer (TTL) were determined using high-resolution, in situ observations of CO2 concentrations in the tropical upper troposphere and lower stratosphere during the NASA Tropical Composition, Cloud and Climate Coupling (TC4) campaign in August 2007. Upward movement of trace gases in the deep tropics was notably slower in TC4 than during the Costa Rica AURA Validation Experiment (CR-AVE), in January 2006. Transport rates in the TTL were combined with in situ measurements of chlorinated and brominated organic compounds from whole air samples to determine chemical loss rates for reactive chemical species, providing empirical vertical profiles for 24-h mean concentrations of hydroxyl radicals (OH) and chlorine atoms in the TTL. The analysis shows that important short-lived species such as CHCl3, CH2Cl2, and CH2Br2 have longer chemical lifetimes than the time for transit of the TTL, implying that these species, which are not included in most models, could readily reach the stratosphere and make significant contributions of chlorine and/or bromine to stratospheric loading.

  9. Vertical transport rates and concentrations of OH and Cl radicals in the Tropical Tropopause Layer from Observations of CO2 and halocarbons: implications for distributions of long- and short-lived chemical species

    NASA Astrophysics Data System (ADS)

    Park, S.; Atlas, E. L.; Jiménez, R.; Daube, B. C.; Gottlieb, E. W.; Nan, J.; Jones, D. B. A.; Pfister, L.; Conway, T. J.; Bui, T. P.; Gao, R.-S.; Wofsy, S. C.

    2010-03-01

    Rates for large-scale vertical transport of air in the Tropical Tropopause Layer (TTL) were determined using high-resolution, in situ observations of CO2 concentrations in the tropical upper troposphere and lower stratosphere during the NASA Tropical Composition, Cloud and Climate Coupling (TC4) campaign in August 2007. Upward movement of trace gases in the deep tropics was notably slower in TC4 than during the Costa Rica AURA Validation Experiment (CR-AVE), in January 2006. Transport rates in the TTL were combined with in situ measurements of chlorinated and brominated organic compounds from whole air samples to determine chemical loss rates for reactive chemical species, providing empirical vertical profiles for 24-h mean concentrations of hydroxyl radicals (OH) and chlorine atoms in the TTL. The analysis shows that important short-lived species such as CHCl3, CH2Cl2, and CH2Br2 have longer chemical lifetimes than the time for transit of the TTL, implying that these species, which are not included in most models, could readily reach the stratosphere and make significant contributions of chlorine and/or bromine to stratospheric loading.

  10. Reinforced photocatalytic reduction of CO2 to CO by a ternary metal oxide NiCo2O4.

    PubMed

    Wang, Zhaoyu; Jiang, Min; Qin, Jiani; Zhou, Han; Ding, Zhengxin

    2015-06-28

    The work reported herein was the facile preparation of uniform urchin-like NiCo2O4 microspheres, and their use as an efficient and stable cocatalyst for photocatalytic CO2 reduction catalysis. A combined solvothermal-calcination strategy was applied to synthesize the NiCo2O4 material that was systematically characterized by physical and chemical measurements (e.g. SEM, TEM, XRD, XPS, EDX, elemental mapping and N2 physisorption analysis). By cooperation with a visible light photosensitizer, the NiCo2O4 material effectively promoted the deoxygenative reduction of CO2 to CO by more than twenty times under mild reaction conditions. The carbon origin of CO evolution was validated by (13)CO2 isotope tracer experiments. Various reaction parameters were examined and optimized, and a possible reaction mechanism was proposed. Furthermore, the stability and reusability of NiCo2O4 cocatalysts were firmly confirmed.

  11. Leaves: Elevated CO2 levels

    USDA-ARS?s Scientific Manuscript database

    Burning fossil fuels and land use changes such as deforestation and urbanization have led to a dramatic rise in the concentration of carbon dioxide (CO2) in the atmosphere since the onset of the Industrial Revolution. The highly dilute CO2 from the atmosphere enters plant leaves where it is concentr...

  12. The LHCb VELO upgrade

    NASA Astrophysics Data System (ADS)

    Dosil Suárez, Álvaro

    2016-07-01

    The upgrade of the LHCb experiment, planned for 2019, will transform the experiment to a trigger-less system reading out the full detector at 40 MHz event rate. All data reduction algorithms will be executed in a high-level software farm. The upgraded detector will run at luminosities of 2×1033 cm-2 s-1 and probe physics beyond the Standard Model in the heavy flavour sector with unprecedented precision. The Vertex Locator (VELO) is the silicon vertex detector surrounding the interaction region. The current detector will be replaced with a hybrid pixel system equipped with electronics capable of reading out at 40 MHz. The detector comprises silicon pixel sensors with 55×55 μm2 pitch, read out by the VeloPix ASIC, based on the TimePix/MediPix family. The hottest region will have pixel hit rates of 900 Mhits/s yielding a total data rate more than 3 Tbit/s for the upgraded VELO. The detector modules are located in a separate vacuum, separated from the beam vacuum by a thin custom made foil. The detector halves are retracted when the beams are injected and closed at stable beams, positioning the first sensitive pixel at 5.1 mm from the beams. The material budget will be minimised by the use of evaporative CO2 coolant circulating in microchannels within 400 μm thick silicon substrates.

  13. Enhancing CO2 Capture using Robust Superomniphobic Membranes.

    PubMed

    Geyer, Florian; Schönecker, Clarissa; Butt, Hans-Jürgen; Vollmer, Doris

    2017-02-01

    Superomniphobic membranes for post-combustion CO2 capture are introduced. Concentrated aqueous amine solutions stay on the topmost part of the membranes, providing a large liquid/CO2 interface. Wetting of the membrane, which reduces the capture efficiency, is prevented. The CO2 capture rates using the chemically, mechanically, and thermally stable superomniphobic membranes are enhanced by up to 40% relative to commercial membranes.

  14. CO2 Sequestration short course

    SciTech Connect

    DePaolo, Donald J.; Cole, David R; Navrotsky, Alexandra; Bourg, Ian C

    2014-12-08

    Given the public’s interest and concern over the impact of atmospheric greenhouse gases (GHGs) on global warming and related climate change patterns, the course is a timely discussion of the underlying geochemical and mineralogical processes associated with gas-water-mineral-interactions encountered during geological sequestration of CO2. The geochemical and mineralogical processes encountered in the subsurface during storage of CO2 will play an important role in facilitating the isolation of anthropogenic CO2 in the subsurface for thousands of years, thus moderating rapid increases in concentrations of atmospheric CO2 and mitigating global warming. Successful implementation of a variety of geological sequestration scenarios will be dependent on our ability to accurately predict, monitor and verify the behavior of CO2 in the subsurface. The course was proposed to and accepted by the Mineralogical Society of America (MSA) and The Geochemical Society (GS).

  15. Leak Path Development in CO2 Wells

    NASA Astrophysics Data System (ADS)

    Torsater, M.; Todorovic, J.; Opedal, N.; Lavrov, A.

    2014-12-01

    Wells have in numerous scientific works been denoted the "weak link" of safe and cost-efficient CO2 Capture and Storage (CCS). Whether they are active or abandoned, all wells are man-made intrusions into the storage reservoir with sealing abilities depending on degradable materials like steel and cement. If dense CO2 is allowed to expand (e.g. due to leakage) it will cool down its surroundings and cause strong thermal and mechanical loading on the wellbore. In addition, CO2 reacts chemically with rock, cement and steel. To ensure long-term underground containment, it is therefore necessary to study how, why, where and when leakage occurs along CO2wells. If cement bonding to rock or casing is poor, leak paths can form already during drilling and completion of the well. In the present work, we have mapped the bonding quality of cement-rock and cement-steel interfaces - and measured their resistance towards CO2 flow. This involved a large experimental matrix including different rocks, steels, cement types and well fluids. The bonding qualities were measured on composite cores using micro computed tomography (µ-CT), and CO2 was flooded through the samples to determine leakage rates. These were further compared to numerical simulations of leakage through the digitalized µ-CT core data, and CO2chemical interactions with the materials were mapped using electron microscopy. We also present a new laboratory set-up for measuring how well integrity is affected by downhole temperature variations - and we showcase some initial results. Our work concludes that leak path development in CO2 wells depends critically on the drilling fluids and presflushes/spacers chosen already during drilling and completion of a well. Fluid films residing on rock and casing surfaces strongly degrade the quality of cement bonding. The operation of the well is also important, as even slight thermal cycling (between 10°C and 95°C on casing) leads to significant de-bonding of the annular cement.

  16. Fluid chemistry of the onshore CO2 sequestration formation at Nagaoka, Japan: 5 years passed since CO2 injection

    NASA Astrophysics Data System (ADS)

    Mito, S.; Asahara, Y.; Xue, Z.

    2011-12-01

    The CO2 injection into structural reservoirs in deep permeable geologic formations is now expected one of the most realizable methods from the point of view of the cost and the CO2 preserving capability of the geological reservoirs. The first Japanese pilot-scale CO2 sequestration project has been done in an onshore saline aquifer at Nagaoka-site, Japan. 10,400 tones of CO2 were injected into a thin aquifer at the depth of 1110 m at a rate of 20-40 tones from July 2003 to January 2005. To investigate a chemical reaction between CO2 fluids and rock forming minerals at the sequestration formation, formation water was collected before and after 1year of the injection (Mito et al., 2008). The result of chemical analyses exhibited a high concentration of HCO3-, Ca, Mg, Fe, Mn and Si in the post-CO2 injection samples compared to the original formation water. The result indicated that a chemical reaction between CO2 and formation water and rock forming minerals had occurred in the sequestration formation at the early stage of CO2 storage. A continuous resistivity monitoring from 2003 to 2011 showed an existence of stagnant free CO2 at the depth of 1110m and gradual spreading of CO2 dissolved water at a top and a bottom of the free CO2 layer (Mito and Xue 2011). This observation suggests that the CO2 trapped by formation water have gradually diffused and chemical trapping of CO2 by surrounding minerals have progressed in the formation. For long-term CO2 storage, we should clarify the reaction between CO2 and minerals occurred at the edge of the spreading CO2 fluids. We are going to collect formation water in the sequestration site at November 2011. We will show the analytical result of the sampled water and discuss about the long-term chemical reaction between the diffused CO2 fluids and rock forming minerals at the Nagaoka sequestration site. References Mito et al., 2008. International Journal of Greenhouse Gas Control, 2, 309-318. Mito and Xue 2011. Energy procedia, 4

  17. Synthesis, structure and chemical bonding of CaFe2-xRhxSi2 (x=0, 1.32, and 2) and SrCo2Si2

    NASA Astrophysics Data System (ADS)

    Hlukhyy, Viktor; Hoffmann, Andrea V.; Fässler, Thomas F.

    2013-07-01

    The finding of superconductivity in Ba0.6K0.4Fe2As2 put the attention on the investigation of compounds that crystallize with ThCr2Si2 structure type such as AT2X2 (A=alkali/alkaline earth/rare earth element; T=transition metal and X=element of the 13-15th group). In this context the silicides CaFe2Si2, CaFe0.68(6)Rh1.32(6)Si2, CaRh2Si2 and SrCo2Si2 have been synthesized by reaction of the elements under an argon atmosphere. Single crystals were obtained by special heat treatment in welded niobium/tantalum ampoules. The compounds were investigated by means of powder and single crystal X-ray diffraction. All compounds crystallize in the ThCr2Si2-type structure with space group I4/mmm (No. 139): a=3.939(1) Å, c=10.185(1) Å, R1=0.045, 85 F2 values, 8 variable parameters for CaFe2Si2; a=4.0590(2) Å, c=9.9390(8) Å, R1=0.030, 90 F2 values, 10 variable parameters for CaFe0.68(6)Rh1.32(6)Si2; a=4.0695(1) Å, c=9.9841(3) Å, R1=0.031, 114 F2 values, 9 variable parameters for CaRh2Si2; and a=3.974(1) Å, c=10.395(1) Å, R1=0.036, 95 F2 values, 8 variable parameters for SrCo2Si2. The structure of SrCo2Si2 contains isolated [Co2Si2]2- 2D-layers in the ab-plane whereas in CaFe2-xRhxSi2 the [T2Si2] layers (T=Fe and Rh) are interconnected along the c-axis via Si3Si bonds resulting in a three-dimentional (3D) [T2Si2]2- polyanions and therefore belong to the so-called collapsed form of the ThCr2Si2-type structure. The SrCo2Si2 and CaRh2Si2 are isoelectronic to the parent 122 iron-pnictide superconductors AeFe2As2 (Ae=alkaline earth elements), whereas CaFe2Si2 is a full substituted variant (As/Si) of CaFe2As2. The crystal chemistry and chemical bonding in the title compounds are discussed in terms of LMTO band structure calculations and a topological analysis using the Electron Localization Function (ELF).

  18. Methanol from CO2 by organo-cocatalysis: CO2 capture and hydrogenation in one process step.

    PubMed

    Reller, Christian; Pöge, Matthias; Lißner, Andreas; Mertens, Florian O R L

    2014-12-16

    Carbon dioxide chemically bound to alcohol-amines was hydrogenated to methanol under retrieval of these industrially used CO2 capturing reagents. The energetics of the process can be seen as a partial cancellation of the exothermic heat of reaction of the hydrogenation with the endothermic one of the CO2 release from the capturing reagent. The process provides a means to significantly improve the energy efficiency of CO2 to methanol conversions.

  19. Effects of elevated CO2 concentrations on denitrifying and nitrifying popualtions at terrestrial CO2 leakeage analogous sites

    NASA Astrophysics Data System (ADS)

    Christine, Dictor Marie; Catherine, Joulian; Valerie, Laperche; Stephanie, Coulon; Dominique, Breeze

    2010-05-01

    CO2 capture and geological storage (CCS) is recognized to be an important option for carbon abatement in Europe. One of the risks of CCS is the leakage from storage site. A laboratory was conducted on soil samples sampled near-surface from a CO2 leakage analogous site (Latera, Italy) in order to evaluate the impact of an elevated soil CO2 concentration on terrestrial bacterial ecosystems form near surface terrestrial environments and to determine a potential bacterial indicator of CO2 leakage from storage site. Surveys were conducted along a 50m long transect across the vent centre, providing a spectrum of CO2 flux rates, soil gas concentrations and compositions (Beaubien et al., 2007). A bacterial diversity studies, performed by CE-SSCP technique, on a soil profile with increasing CO2 soil concentrations (from 0.3% to 100%) showed that a change on bacterial diversity was noted when CO2 concentration was above 50 % of CO2. From this result, 3 soil samples were taken at 70 cm depth in 3 distinct zones (background soil CO2 content, soil CO2 content of 20% and soil CO2 content of 50%). Then theses soil samples were incubated under closed jars flushed with different air atmospheres (20, 50 and 90 % of CO2) during 18 months. At initial, 3, 6, 12 and 18 months, some soil samples were collected in order to estimate the denitrifying, nitrifying activities as a function of CO2 concentration content and times. Theses enzymatic activities were chosen because one occurs under anaerobic conditions (denitrification) and the other occurs under aerobic conditions (nitrification). Both of them were involved in the nitrogen cycle and are major actors of soil function and groundwater quality preservation. Metabolic diversity using BIOLOG Ecoplates was determined on every soil samples. Physico-chemical parameters (e.g. pH, bulk chemistry, mineralogy) were analyzed to have some information about the evolution of the soil during the incubation with increasing soil CO2 concentrations

  20. CO2 laser design procedure.

    NASA Technical Reports Server (NTRS)

    Fahlen, T. S.

    1973-01-01

    A simple but powerful formalism is presented that allows one to physically design a sealed CO2 laser of any specified fundamental transverse-mode output power. The design material presented, graphically whenever possible, also allows one to determine the effect on the others of varying one design parameter. Although the formalism presented is based on some empirical and some theoretical parametric interrelationships pertinent to the CO2 laser, the treatment is general and with appropriate adjustments can be applied to other laser systems as well. The design of a 5-W sealed CO2 laser is presented to illustrate the use of the formalism developed.

  1. Infrared spectroscopy of Mg-CO2 and Al-CO2 complexes in helium nanodroplets.

    PubMed

    Thomas, Brandon J; Harruff-Miller, Barbara A; Bunker, Christopher E; Lewis, William K

    2015-05-07

    The catalytic reduction of CO2 to produce hydrocarbon fuels is a topic that has gained significant attention. Development of efficient catalysts is a key enabler to such approaches, and metal-based catalysts have shown promise towards this goal. The development of a fundamental understanding of the interactions between CO2 molecules and metal atoms is expected to offer insight into the chemistry that occurs at the active site of such catalysts. In the current study, we utilize helium droplet methods to assemble complexes composed of a CO2 molecule and a Mg or Al atom. High-resolution infrared (IR) spectroscopy and optically selected mass spectrometry are used to probe the structure and binding of the complexes, and the experimental observations are compared with theoretical results determined from ab initio calculations. In both the Mg-CO2 and Al-CO2 systems, two IR bands are obtained: one assigned to a linear isomer and the other assigned to a T-shaped isomer. In the case of the Mg-CO2 complexes, the vibrational frequencies and rotational constants associated with the two isomers are in good agreement with theoretical values. In the case of the Al-CO2 complexes, the vibrational frequencies agree with theoretical predictions; however, the bands from both structural isomers exhibit significant homogeneous broadening sufficient to completely obscure the rotational structure of the bands. The broadening is consistent with an upper state lifetime of 2.7 ps for the linear isomer and 1.8 ps for the T-shaped isomer. The short lifetime is tentatively attributed to a prompt photo-induced chemical reaction between the CO2 molecule and the Al atom comprising the complex.

  2. Ocean acidification: the other CO2 problem.

    PubMed

    Doney, Scott C; Fabry, Victoria J; Feely, Richard A; Kleypas, Joan A

    2009-01-01

    Rising atmospheric carbon dioxide (CO2), primarily from human fossil fuel combustion, reduces ocean pH and causes wholesale shifts in seawater carbonate chemistry. The process of ocean acidification is well documented in field data, and the rate will accelerate over this century unless future CO2 emissions are curbed dramatically. Acidification alters seawater chemical speciation and biogeochemical cycles of many elements and compounds. One well-known effect is the lowering of calcium carbonate saturation states, which impacts shell-forming marine organisms from plankton to benthic molluscs, echinoderms, and corals. Many calcifying species exhibit reduced calcification and growth rates in laboratory experiments under high-CO2 conditions. Ocean acidification also causes an increase in carbon fixation rates in some photosynthetic organisms (both calcifying and noncalcifying). The potential for marine organisms to adapt to increasing CO2 and broader implications for ocean ecosystems are not well known; both are high priorities for future research. Although ocean pH has varied in the geological past, paleo-events may be only imperfect analogs to current conditions.

  3. Co2 On Titan's Surface

    NASA Astrophysics Data System (ADS)

    McCord, Thomas B.; Combe, J.; Hayne, P.; Hansen, G. B.

    2007-10-01

    Evidence is reported for the presence of CO2 on the surface of Titan from the Cassini VIMS (an imaging visual and IR spectrometer) data (McCord et al., 2006, 2007). CO2 can be expected on Titan from basic planetary evolution models. It was also suggested as a plausible spectral component for bright material near the Huygens landing site (Rodriguez et al., 2006), based on structure in the 1.59-µm region. Hartung et al. (2006) searched for CO2 in one hemisphere, but they were able only to set an upper limit on the possible spatial coverage by pure CO2. Barnes et al., (2006) suggested CO2 as a possible candidate material for a 5-µm-bright region, named Tsegihi, based on the high 5-µm reflectance. However, these results are not inconsistent with our report. The evidence we report is three-fold: 1) A weak absorption near 4.9 µm in the 5-µm methane window for the Tui Regio region; 2) The spectral contrast between the 2.7- and 2.8-µm methane subwindows for the regions exhibiting the 4.9-µm absorption, with stronger absorption correlating with stronger contrast; and 3) the overall shape of the CO2 spectrum (for several grain-sizes) is consistent with the spectrum of one of the fundamental surface spectral components, as deduced by spectral mixture analysis modeling. The Tui Regio feature exhibits the strongest evidence in all three categories. Studies of this feature's morphology and albedo markings have suggested to some that it may be an active cryovolcanic feature (Barnes et al., 2006). If so, CO2 could be erupting and depositing as a frost. This likely happened elsewhere and at other times. Thus, CO2 could be a major constituent of the surface, but over time it may be mixed with other constituents, such as spectrally neutral organics raining from the atmosphere, thereby reducing the strength of its spectral signature.

  4. CO2 Storage related Groundwater Impacts and Protection

    NASA Astrophysics Data System (ADS)

    Fischer, Sebastian; Knopf, Stefan; May, Franz; Rebscher, Dorothee

    2016-03-01

    Injection of CO2 into the deep subsurface will affect physical and chemical conditions in the storage environment. Hence, geological CO2 storage can have potential impacts on groundwater resources. Shallow freshwater can only be affected if leakage pathways facilitate the ascent of CO2 or saline formation water. Leakage associated with CO2 storage cannot be excluded, but potential environmental impacts could be reduced by selecting suitable storage locations. In the framework of risk assessment, testing of models and scenarios against operational data has to be performed repeatedly in order to predict the long-term fate of CO2. Monitoring of a storage site should reveal any deviations from expected storage performance, so that corrective measures can be taken. Comprehensive R & D activities and experience from several storage projects will enhance the state of knowledge on geological CO2 storage, thus enabling safe storage operations at well-characterised and carefully selected storage sites while meeting the requirements of groundwater protection.

  5. Natural analogue study of CO2 storage monitoring using probability statistics of CO2-rich groundwater chemistry

    NASA Astrophysics Data System (ADS)

    Kim, K. K.; Hamm, S. Y.; Kim, S. O.; Yun, S. T.

    2016-12-01

    For confronting global climate change, carbon capture and storage (CCS) is one of several very useful strategies as using capture of greenhouse gases like CO2 spewed from stacks and then isolation of the gases in underground geologic storage. CO2-rich groundwater could be produced by CO2 dissolution into fresh groundwater around a CO2 storage site. As consequence, natural analogue studies related to geologic storage provide insights into future geologic CO2 storage sites as well as can provide crucial information on the safety and security of geologic sequestration, the long-term impact of CO2 storage on the environment, and field operation and monitoring that could be implemented for geologic sequestration. In this study, we developed CO2 leakage monitoring method using probability density function (PDF) by characterizing naturally occurring CO2-rich groundwater. For the study, we used existing data of CO2-rich groundwaters in different geological regions (Gangwondo, Gyeongsangdo, and Choongchungdo provinces) in South Korea. Using PDF method and QI (quantitative index), we executed qualitative and quantitative comparisons among local areas and chemical constituents. Geochemical properties of groundwater with/without CO2 as the PDF forms proved that pH, EC, TDS, HCO3-, Ca2+, Mg2+, and SiO2 were effective monitoring parameters for carbonated groundwater in the case of CO2leakage from an underground storage site. KEY WORDS: CO2-rich groundwater, CO2 storage site, monitoring parameter, natural analogue, probability density function (PDF), QI_quantitative index Acknowledgement This study was supported by the "Basic Science Research Program through the National Research Foundation of Korea (NRF), which is funded by the Ministry of Education (NRF-2013R1A1A2058186)" and the "R&D Project on Environmental Management of Geologic CO2 Storage" from KEITI (Project number: 2014001810003).

  6. Polyurethane Foam-Based Ultramicroporous Carbons for CO2 Capture.

    PubMed

    Ge, Chao; Song, Jian; Qin, Zhangfeng; Wang, Jianguo; Fan, Weibin

    2016-07-27

    A series of sustainable porous carbon materials were prepared from waste polyurethane foam and investigated for capture of CO2. The effects of preparation conditions, such as precarbonization, KOH to carbon precursor weight ratio, and activation temperature, on the porous structure and CO2 adsorption properties were studied for the purpose of controlling pore sizes and nitrogen content and developing high-performance materials for capture of CO2. The sample prepared at optimum conditions shows CO2 adsorption capacities of 6.67 and 4.33 mmol·g(-1) at 0 and 25 °C under 1 bar, respectively, which are comparable to those of the best reported porous carbons prepared from waste materials. The HCl treatment experiment reveals that about 80% of CO2 adsorption capacity arises from physical adsorption, while the other 20% is due to the chemical adsorption originated from the interaction of basic N groups and CO2 molecules. The relationship between CO2 uptake and pore size at different temperatures indicates that the micropores with pore size smaller than 0.86 and 0.70 nm play a dominant role in the CO2 adsorption at 0 and 25 °C, respectively. It was found that the obtained carbon materials exhibited high recyclability and high selectivity to adsorption of CO2 from the CO2 and N2 mixture.

  7. Spectroscopic study of low pressure, low temperature H2-CH4-CO2 microwave plasmas used for large area deposition of nanocrystalline diamond films. Part II: on plasma chemical processes

    NASA Astrophysics Data System (ADS)

    Nave, A. S. C.; Baudrillart, B.; Hamann, S.; Bénédic, F.; Lombardi, G.; Gicquel, A.; van Helden, J. H.; Röpcke, J.

    2016-12-01

    In a distributed antenna array (DAA) reactor, microwave H2 plasmas with admixtures of 2.5% CH4 and 1% CO2 used for the deposition of nanocrystalline diamond films have been studied by infrared laser absorption and optical emission spectroscopy (OES) techniques. The experiments were carried out in order to analyze the dependence of plasma chemical phenomena on power and pressure at relatively low pressures, up to 0.55 mbar, and power values, up to 3 kW. The evolution of the concentration of the methyl radical, CH3, of five stable molecules, CH4, CO2, CO, C2H2 and C2H6, and of vibrationally excited CO in the first and second hot band was monitored in the plasma processes by in situ infrared laser absorption spectroscopy using tunable lead salt diode lasers (TDL) and an external-cavity quantum cascade laser (EC-QCL) as radiation sources. OES was applied simultaneously to obtain complementary information about the degree of dissociation of the H2 precursor and of its gas temperature. The experimental results are presented in two separate parts. In Part I, the first paper in a two-part series, the measurement of the gas (T gas), rotational (T rot) and vibrational (T vib) temperatures of the various species in the complex plasma was the main focus of interest. Depending on the different plasma zones the gas temperature was found to range between about 360 and 1000 K inside the DAA reactor (Nave et al 2016 Plasma Sources Sci. Technol. 25 065002). In Part II, the present paper, taking into account the temperatures determined in the first paper, the concentrations of the various species, which were found to be in a range between 1011 and 1015 cm-3, are the focus of interest. The influence of the discharge parameters power and pressure on the molecular concentrations has been studied. To achieve further insight into general plasma chemical aspects the dissociation of the carbon precursor gases including their fragmentation and conversion to the reaction products has been

  8. Subsurface oxide plays a critical role in CO2 activation by Cu(111) surfaces to form chemisorbed CO2, the first step in reduction of CO2.

    PubMed

    Favaro, Marco; Xiao, Hai; Cheng, Tao; Goddard, William A; Yano, Junko; Crumlin, Ethan J

    2017-06-27

    A national priority is to convert CO2 into high-value chemical products such as liquid fuels. Because current electrocatalysts are not adequate, we aim to discover new catalysts by obtaining a detailed understanding of the initial steps of CO2 electroreduction on copper surfaces, the best current catalysts. Using ambient pressure X-ray photoelectron spectroscopy interpreted with quantum mechanical prediction of the structures and free energies, we show that the presence of a thin suboxide structure below the copper surface is essential to bind the CO2 in the physisorbed configuration at 298 K, and we show that this suboxide is essential for converting to the chemisorbed CO2 in the presence of water as the first step toward CO2 reduction products such as formate and CO. This optimum suboxide leads to both neutral and charged Cu surface sites, providing fresh insights into how to design improved carbon dioxide reduction catalysts.

  9. Subsurface oxide plays a critical role in CO2 activation by Cu(111) surfaces to form chemisorbed CO2, the first step in reduction of CO2

    PubMed Central

    Favaro, Marco; Yano, Junko; Crumlin, Ethan J.

    2017-01-01

    A national priority is to convert CO2 into high-value chemical products such as liquid fuels. Because current electrocatalysts are not adequate, we aim to discover new catalysts by obtaining a detailed understanding of the initial steps of CO2 electroreduction on copper surfaces, the best current catalysts. Using ambient pressure X-ray photoelectron spectroscopy interpreted with quantum mechanical prediction of the structures and free energies, we show that the presence of a thin suboxide structure below the copper surface is essential to bind the CO2 in the physisorbed configuration at 298 K, and we show that this suboxide is essential for converting to the chemisorbed CO2 in the presence of water as the first step toward CO2 reduction products such as formate and CO. This optimum suboxide leads to both neutral and charged Cu surface sites, providing fresh insights into how to design improved carbon dioxide reduction catalysts. PMID:28607092

  10. Breadboard CO2 and humidity control system

    NASA Technical Reports Server (NTRS)

    Boehm, A. M.

    1976-01-01

    A regenerable CO2 and humidity control system is being developed for potential use on shuttle as an alternate to the baseline lithium hydroxide (LiOH)/condensing heat exchanger system. The system utilizes a sorbent material, designated HS-C, to adsorb CO2 and water vapor from the cabin atmosphere. The material is regenerated by exposing it to space vacuum. A half-size breadboard system, utilizing a flight representative HS-C canister, was designed, built, and performance tested to shuttle requirements for total CO2 and total humidity removal. The use of a new chemical matrix material allowed significant optimization of the system design by packing the HS-C chemical into the core of a heat exchanger which is manifolded to form two separate and distinct beds. Breadboard system performance was proven by parametric testing and simulated mission testing over the full range of shuttle crew sizes and metabolic loadings. Vacuum desorption testing demonstrated considerable savings in previously projected shuttle vacuum duct sizing.

  11. Synthesis, physical-chemical characterization and electrochemical performance of GdBaCo2-xNixO5+δ (x = 0-0.8) as cathode materials for IT-SOFC application

    NASA Astrophysics Data System (ADS)

    Hu, Y.; Bogicevic, C.; Bouffanais, Y.; Giot, M.; Hernandez, O.; Dezanneau, G.

    2013-11-01

    GdBaCo2-xNixO5+δ (x = 0-0.8) cathode materials have been synthesized by a citrate-gel modified chemical route, by which we have achieved a high level of substitution up to x = 0.8. Oxygen stoichiometry at room temperature has been determined by iodometry and the structural evolution as a function of Ni content has been extracted from XRD patterns analysis. All compounds are orthorhombic at room temperature and a DSC analysis reveals that the high-temperature orthorhombic-to-tetragonal phase transition is observed at lower temperature as Ni substitution increases. Three compositions, with x = 0, 0.3 and 0.6, were then chosen for further characterization: high-temperature XRD has been performed confirming the abovementioned structural evolution with temperature and allowing to determine that Ni doping diminishes slightly the thermal expansion coefficient. According to 4-probe measurements, we show that these compounds present a high electronic conductivity, suitable for cathode materials. Finally, electrochemical characterization has been performed by AC impedance spectroscopy with symmetric cells using composite electrode showing an improvement of performance at intermediate substitution levels.

  12. CO2 Sequestration Crosswell Monitoring

    NASA Astrophysics Data System (ADS)

    Morency, C.; Luo, Y.; Tromp, J.

    2010-12-01

    Geologic sequestration of CO2, a green house gas, represents an effort to reduce the large amount of CO2 generated as a by-product of fossil fuels combustion and emitted into the atmosphere. This process of sequestration involves CO2 storage deep underground into highly permeable porous media sealed by caprock. "4D seismics" is a natural non-intrusive monitoring technique which involves 3D time-lapse seismic surveys. The success of monitoring CO2 movement relies upon a proper description of the physics of the problem. We realize time-lapse migrations comparing acoustic, elastic (with or without Gassmann's formulae), and poroelastic simulations of 4D seismic imaging. This approach highlights the influence of using different physical theories on interpreting seismic data, and, more importantly, on extracting the CO2 signature from the seismic wave field. We investigate various types of inversions using (1) P-wave traveltimes, (2) P- & S-wave traveltimes and (3) P- & S-wave traveltimes and amplitudes. Simulations are performed using a spectral-element method, and finite-frequency sensitivity kernels, used in the non-linear iterative inversions, are calculated based on an adjoint method. Biot's equations are implemented in the forward and adjoint simulations to account for poroelastic effects.

  13. ACCURACY OF CO2 SENSORS

    SciTech Connect

    Fisk, William J.; Faulkner, David; Sullivan, Douglas P.

    2008-10-01

    Are the carbon dioxide (CO2) sensors in your demand controlled ventilation systems sufficiently accurate? The data from these sensors are used to automatically modulate minimum rates of outdoor air ventilation. The goal is to keep ventilation rates at or above design requirements while adjusting the ventilation rate with changes in occupancy in order to save energy. Studies of energy savings from demand controlled ventilation and of the relationship of indoor CO2 concentrations with health and work performance provide a strong rationale for use of indoor CO2 data to control minimum ventilation rates1-7. However, this strategy will only be effective if, in practice, the CO2 sensors have a reasonable accuracy. The objective of this study was; therefore, to determine if CO2 sensor performance, in practice, is generally acceptable or problematic. This article provides a summary of study methods and findings ? additional details are available in a paper in the proceedings of the ASHRAE IAQ?2007 Conference8.

  14. Enhancing the Ocean's Role in CO2 Mitigation

    NASA Astrophysics Data System (ADS)

    Rau, G. H.

    2012-12-01

    The possibility of safely increasing the ocean's significant, natural consumption and storage of excess CO2 deserves consideration since land-based efforts are thus far failing to stabilize atmospheric CO2 and associated climate and ocean chemistry impacts. Of the approximately 34 GT/yr of CO2 currently emitted to the atmosphere by human activity, the ocean consumes the equivalent of about 8 GT/yr of these emissions. These fluxes are, however, dwarfed by the annual gross amount of CO2 naturally taken up and released by the ocean, in excess of 300 GT CO2/yr. Additionally, the carbon content in the ocean is about 50 times that of the atmosphere, with the majority in a form (HCO2-) that can, through equilibrium reactions, interact with atmospheric CO2. Marine chemical, biological and physical processes that naturally affect ocean CO2 gain and loss thus intimately influence the natural carbon content of the atmosphere. Indeed, ocean chemistry in conjunction with carbonate and silicate mineral weathering is the primary mechanism that naturally moderates and consumes excess atmospheric CO2 on geologic timescales. The ocean is therefore a logical place to explore means of enhancing atmospheric and anthropogenic carbon uptake and/or sequestration in efforts to stabilize or possibly reduce atmospheric CO2 concentrations. Modification of such global processes (often only relatively slightly) forms the basis for many of the ocean-based CO2 mitigation approaches thus far proposed. These include: 1) the storage in or under the ocean of molecular CO2, or organic or inorganic derivatives that have been captured or formed on land; 2) the removal of ocean/atmosphere CO2 via biological uptake enhanced by artificially increased upwelling or nutrient addition; 3) the chemical, geochemical, or electrochemical alkalization of the ocean to increase ocean CO2 uptake with chemical transformation to bicarbonates or carbonates, and subsequent ocean storage; and 4) increased production and

  15. Update on CO2 emissions

    SciTech Connect

    Friedingstein, P.; Houghton, R.A.; Marland, Gregg; Hackler, J.; Boden, Thomas A; Conway, T.J.; Canadell, J.G.; Raupach, Mike; Ciais, Philippe; Le Quere, Corrine

    2010-12-01

    Emissions of CO2 are the main contributor to anthropogenic climate change. Here we present updated information on their present and near-future estimates. We calculate that global CO2 emissions from fossil fuel burning decreased by 1.3% in 2009 owing to the global financial and economic crisis that started in 2008; this is half the decrease anticipated a year ago1. If economic growth proceeds as expected2, emissions are projected to increase by more than 3% in 2010, approaching the high emissions growth rates that were observed from 2000 to 20081, 3, 4. We estimate that recent CO2 emissions from deforestation and other land-use changes (LUCs) have declined compared with the 1990s, primarily because of reduced rates of deforestation in the tropics5 and a smaller contribution owing to forest regrowth elsewhere.

  16. Tuning of CO2 Reduction Selectivity on Metal Electrocatalysts.

    PubMed

    Wang, Yuhang; Liu, Junlang; Wang, Yifei; Al-Enizi, Abdullah M; Zheng, Gengfeng

    2017-09-14

    Climate change, caused by heavy CO2 emissions, is driving new demands to alleviate the rising concentration of atmospheric CO2 levels. Enlightened by the photosynthesis of green plants, photo(electro)chemical catalysis of CO2 reduction, also known as artificial photosynthesis, is emerged as a promising candidate to address these demands and is widely investigated during the past decade. Among various artificial photosynthetic systems, solar-driven electrochemical CO2 reduction is widely recognized to possess high efficiencies and potentials for practical application. The efficient and selective electroreduction of CO2 is the key to the overall solar-to-chemical efficiency of artificial photosynthesis. Recent studies show that various metallic materials possess the capability to play as electrocatalysts for CO2 reduction. In order to achieve high selectivity for CO2 reduction products, various efforts are made including studies on electrolytes, crystal facets, oxide-derived catalysts, electronic and geometric structures, nanostructures, and mesoscale phenomena. In this Review, these methods for tuning the selectivity of CO2 electrochemical reduction of metallic catalysts are summarized. The challenges and perspectives in this field are also discussed. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Structural Motifs of [Fe(CO2)n](-) Clusters (n = 3-7).

    PubMed

    Thompson, Michael C; Dodson, Leah G; Weber, J Mathias

    2017-06-01

    We present IR spectra and quantum chemical calculations for anionic iron-CO2 clusters of the form [Fe(CO2)n](-) (n = 3-7). All observed clusters have at least two CO2 units strongly bound to the metal atom. These strongly bound iron-CO2 complexes form the core ions of the clusters and are solvated by additional, weakly bound CO2 molecules. Larger clusters show clear infrared signatures of core ion isomers with three CO2 moieties as well. Dominant structural motifs are based on bidentate CO2 ligands with Fe-O/Fe-C bonds, oxalate ligands, and metal insertion into a CO bond.

  18. The CO2nnect activities

    NASA Astrophysics Data System (ADS)

    Eugenia, Marcu

    2014-05-01

    Climate change is one of the biggest challenges we face today. A first step is the understanding the problem, more exactly what is the challenge and the differences people can make. Pupils need a wide competencies to meet the challenges of sustainable development - including climate change. The CO2nnect activities are designed to support learning which can provide pupils the abilities, skills, attitudes and awareness as well as knowledge and understanding of the issues. The project "Together for a clean and healthy world" is part of "The Global Educational Campaign CO2nnect- CO2 on the way to school" and it was held in our school in the period between February and October 2009. It contained a variety of curricular and extra-curricular activities, adapted to students aged from 11 to 15. These activities aimed to develop in students the necessary skills to understanding man's active role in improving the quality of the environment, putting an end to its degrading process and to reducing the effects of climate changes caused by the human intervention in nature, including transport- a source of CO2 pollution. The activity which I propose can be easily adapted to a wide range of age groups and linked to the curricula of many subjects: - Investigate CO2 emissions from travel to school -Share the findings using an international database -Compare and discuss CO2 emissions -Submit questions to a climate- and transport expert -Partner with other schools -Meet with people in your community to discuss emissions from transport Intended learning outcomes for pupils who participate in the CO2nnect campaign are: Understanding of the interconnected mobility- and climate change issue climate change, its causes and consequences greenhouse-gas emissions from transport and mobility the interlinking of social, environmental, cultural and economic aspects of the local transport system how individual choices and participation can contribute to creating a more sustainable development

  19. Sequestering CO2 in the Ocean: Options and Consequences

    NASA Astrophysics Data System (ADS)

    Rau, G. H.; Caldeira, K.

    2002-12-01

    The likelihood of negative climate and environmental impacts associated with increasing atmospheric CO2 has prompted serious consideration of various CO2 mitigation strategies. Among these are methods of capturing and storing of CO2 in the ocean. Two approaches that have received the most attention in this regard have been i) ocean fertilization to enhanced biological uptake and fixation of CO2, and ii) the chemical/mechanical capture and injection of CO2 into the deep ocean. Both methods seek to enhance or speed up natural mechanisms of CO2 uptake and storage by the ocean, namely i) the biological CO2 "pump" or ii) the passive diffusion of CO2 into the surface ocean and subsequent mixing into the deep sea. However, as will be reviewed, concerns about the capacity and effectiveness of either strategy in long-term CO2 sequestration have been raised. Both methods are not without potentially significant environmental impacts, and the costs of CO2 capture and injection (option ii) are currently prohibitive. An alternate method of ocean CO2 sequestration would be to react and hydrate CO2 rich waste gases (e.g., power plant flue gas) with seawater and to subsequently neutralize the resulting carbonic acid with limestone to produce calcium and bicarbonate ions in solution. This approach would simply speed up the CO2 uptake and sequestration that naturally (but very slowly) occurs via global carbonate weathering. This would avoid much of the increased acidity associated with direct CO2 injection while obviating the need for costly CO2 separation and capture. The addition of the resulting bicarbonate- and carbonate-rich solution to the ocean would help to counter the decrease in pH and carbonate ion concentration, and hence loss of biological calcification that is presently occurring as anthropogenic CO2 invades the ocean from the atmosphere. However, as with any approach to CO2 mitigation, the costs, impacts, risks, and benefits of this method need to be better understood

  20. CO2CRC's Otway Residual Saturation and Dissolution Test: Using Reactive Ester Tracers to Determine Residual CO2 Saturation

    NASA Astrophysics Data System (ADS)

    Myers, M.; Stalker, L.; LaForce, T.; Pejcic, B.; Dyt, C.; Ho, K.; Ennis-King, J.

    2013-12-01

    Residual trapping, that is CO2 held in the rock pore space due to capillarity, is an important storage mechanism in geo-sequestration of over the short to medium term (up to 1000 years). As such residual CO2 saturation is a critical reservoir parameter for assessing the storage capacity and security of carbon capture and storage (CCS). As a component of the CO2CRC's Residual Gas Saturation and Dissolution Test at the CO2CRC Otway Project site in Victoria (Australia), we have recently tested a suite of reactive esters (triacetin, tripropionin and propylene glycol diacetate) in a single well chemical tracer test to determine residual CO2 saturation. The goal of this project was to assess and validate a suite of possible tests that could be implemented to determine residual CO2 saturation. For this test, the chemical tracers were injected with a saturated CO2/water mixture into the formation (that is already at residual CO2 saturation) where they were allowed to 'soak' for approximately 10 days allowing for the partial hydrolysis of the esters to their corresponding carboxylic acids and alcohols. Water containing the tracers was then produced from the well resulting in over 600 tracer samples over a period of 12 hours. A selection of these samples were analysed for tracer content and to establish tracer breakthrough curves. To understand the behaviour of these chemical tracers in the downhole environment containing residually trapped supercritical CO2 and formation water, it is necessary to determine the supercritical CO2/water partition coefficients. We have previously determined these in the laboratory (Myers et al., 2012) and they are used here to model the tracer behaviour and provide an estimate of the residual CO2 saturation. Two different computational simulators were used to analyse the tracer breakthrough profiles. The first is based on simple chromatographic retardation and has been used extensively in single well chemical tracer tests to determine residual

  1. Reducing cement's CO2 footprint

    USGS Publications Warehouse

    van Oss, Hendrik G.

    2011-01-01

    The manufacturing process for Portland cement causes high levels of greenhouse gas emissions. However, environmental impacts can be reduced by using more energy-efficient kilns and replacing fossil energy with alternative fuels. Although carbon capture and new cements with less CO2 emission are still in the experimental phase, all these innovations can help develop a cleaner cement industry.

  2. Is guava phenolic metabolism influenced by elevated atmospheric CO2?

    PubMed

    Mendes de Rezende, Fernanda; Pereira de Souza, Amanda; Silveira Buckeridge, Marcos; Maria Furlan, Cláudia

    2015-01-01

    Seedlings of Psidium guajava cv. Pedro Sato were distributed into four open-top chambers: two with ambient CO(2) (∼390 ppm) and two with elevated CO(2) (∼780 ppm). Monthly, five individuals of each chamber were collected, separated into root, stem and leaves and immediately frozen in liquid nitrogen. Chemical parameters were analyzed to investigate how guava invests the surplus carbon. For all classes of phenolic compounds analyzed only tannins showed significant increase in plants at elevated CO(2) after 90 days. There was no significant difference in dry biomass, but the leaves showed high accumulation of starch under elevated CO(2). Results suggest that elevated CO(2) seems to be favorable to seedlings of P. guajava, due to accumulation of starch and tannins, the latter being an important anti-herbivore substance.

  3. Efficient electrochemical CO2 conversion powered by renewable energy

    DOE PAGES

    Kauffman, Douglas R.; Thakkar, Jay; Siva, Rajan; ...

    2015-06-29

    Here, the catalytic conversion of CO2 into industrially relevant chemicals is one strategy for mitigating greenhouse gas emissions. Along these lines, electrochemical CO2 conversion technologies are attractive because they can operate with high reaction rates at ambient conditions. However, electrochemical systems require electricity, and CO2 conversion processes must integrate with carbon-free, renewable-energy sources to be viable on larger scales. We utilize Au25 nanoclusters as renewably powered CO2 conversion electrocatalysts with CO2 → CO reaction rates between 400 and 800 L of CO2 per gram of catalytic metal per hour and product selectivities between 80 and 95%. These performance metrics correspondmore » to conversion rates approaching 0.8–1.6 kg of CO2 per gram of catalytic metal per hour. We also present data showing CO2 conversion rates and product selectivity strongly depend on catalyst loading. Optimized systems demonstrate stable operation and reaction turnover numbers (TONs) approaching 6 × 106 mol CO2 molcatalyst–1 during a multiday (36 hours total hours) CO2electrolysis experiment containing multiple start/stop cycles. TONs between 1 × 106 and 4 × 106 molCO2 molcatalyst–1 were obtained when our system was powered by consumer-grade renewable-energy sources. Daytime photovoltaic-powered CO2 conversion was demonstrated for 12 h and we mimicked low-light or nighttime operation for 24 h with a solar-rechargeable battery. This proof-of-principle study provides some of the initial performance data necessary for assessing the scalability and technical viability of electrochemical CO2 conversion technologies. Specifically, we show the following: (1) all electrochemical CO2 conversion systems will produce a net increase in CO2 emissions if they do not integrate with renewable-energy sources, (2) catalyst loading vs activity trends can be used to tune process rates and product distributions, and (3) state-of-the-art renewable-energy technologies

  4. Sedimentary reservoir oxidation during geologic CO2 sequestration

    NASA Astrophysics Data System (ADS)

    Lammers, Laura N.; Brown, Gordon E.; Bird, Dennis K.; Thomas, Randal B.; Johnson, Natalie C.; Rosenbauer, Robert J.; Maher, Katharine

    2015-04-01

    Injection of carbon dioxide into subsurface geologic reservoirs during geologic carbon sequestration (GCS) introduces an oxidizing supercritical CO2 phase into a subsurface geologic environment that is typically reducing. The resulting redox disequilibrium provides the chemical potential for the reduction of CO2 to lower free energy organic species. However, redox reactions involving carbon typically require the presence of a catalyst. Iron oxide minerals, including magnetite, are known to catalyze oxidation and reduction reactions of C-bearing species. If the redox conditions in the reservoir are modified by redox transformations involving CO2, such changes could also affect mineral stability, leading to dissolution and precipitation reactions and alteration of the long-term fate of CO2 in GCS reservoirs. We present experimental evidence that reservoirs with reducing redox conditions are favorable environments for the relatively rapid abiotic reduction of CO2 to organic molecules. In these experiments, an aqueous suspension of magnetite nanoparticles was reacted with supercritical CO2 under pressure and temperature conditions relevant to GCS in sedimentary reservoirs (95-210 °C and ∼100 bars of CO2). Hydrogen production was observed in several experiments, likely caused by Fe(II) oxidation either at the surface of magnetite or in the aqueous phase. Heating of the Fe(II)-rich system resulted in elevated PH2 and conditions favorable for the reduction of CO2 to acetic acid. Implications of these results for the long-term fate of CO2 in field-scale systems were explored using reaction path modeling of CO2 injection into reservoirs containing Fe(II)-bearing primary silicate minerals, with kinetic parameters for CO2 reduction obtained experimentally. The results of these calculations suggest that the reaction of CO2 with reservoir constituents will occur in two primary stages (1) equilibration of CO2 with organic acids resulting in mineral-fluid disequilibrium, and

  5. Efficient electrochemical CO2 conversion powered by renewable energy.

    PubMed

    Kauffman, Douglas R; Thakkar, Jay; Siva, Rajan; Matranga, Christopher; Ohodnicki, Paul R; Zeng, Chenjie; Jin, Rongchao

    2015-07-22

    The catalytic conversion of CO2 into industrially relevant chemicals is one strategy for mitigating greenhouse gas emissions. Along these lines, electrochemical CO2 conversion technologies are attractive because they can operate with high reaction rates at ambient conditions. However, electrochemical systems require electricity, and CO2 conversion processes must integrate with carbon-free, renewable-energy sources to be viable on larger scales. We utilize Au25 nanoclusters as renewably powered CO2 conversion electrocatalysts with CO2 → CO reaction rates between 400 and 800 L of CO2 per gram of catalytic metal per hour and product selectivities between 80 and 95%. These performance metrics correspond to conversion rates approaching 0.8-1.6 kg of CO2 per gram of catalytic metal per hour. We also present data showing CO2 conversion rates and product selectivity strongly depend on catalyst loading. Optimized systems demonstrate stable operation and reaction turnover numbers (TONs) approaching 6 × 10(6) molCO2 molcatalyst(-1) during a multiday (36 h total hours) CO2 electrolysis experiment containing multiple start/stop cycles. TONs between 1 × 10(6) and 4 × 10(6) molCO2 molcatalyst(-1) were obtained when our system was powered by consumer-grade renewable-energy sources. Daytime photovoltaic-powered CO2 conversion was demonstrated for 12 h and we mimicked low-light or nighttime operation for 24 h with a solar-rechargeable battery. This proof-of-principle study provides some of the initial performance data necessary for assessing the scalability and technical viability of electrochemical CO2 conversion technologies. Specifically, we show the following: (1) all electrochemical CO2 conversion systems will produce a net increase in CO2 emissions if they do not integrate with renewable-energy sources, (2) catalyst loading vs activity trends can be used to tune process rates and product distributions, and (3) state-of-the-art renewable-energy technologies are sufficient

  6. Intercomparison of two cavity ring-down spectroscopy analyzers for atmospheric 13CO2 / 12CO2 measurement

    NASA Astrophysics Data System (ADS)

    Pang, Jiaping; Wen, Xuefa; Sun, Xiaomin; Huang, Kuan

    2016-08-01

    Isotope ratio infrared spectroscopy (IRIS) permits continuous in situ measurement of CO2 isotopic composition under ambient conditions. Previous studies have mainly focused on single IRIS instrument performance; few studies have considered the comparability among different IRIS instruments. In this study, we carried out laboratory and ambient measurements using two Picarro CO2δ13C analyzers (G1101-i and G2201-i (newer version)) and evaluated their performance and comparability. The best precision was 0.08-0.15 ‰ for G1101-i and 0.01-0.04 ‰ for G2201-i. The dependence of δ13C on CO2 concentration was 0.46 ‰ per 100 ppm and 0.09 ‰ per 100 ppm, the instrument drift ranged from 0.92-1.09 ‰ and 0.19-0.37 ‰, and the sensitivity of δ13C to the water vapor mixing ratio was 1.01 ‰ / % H2O and 0.09 ‰ / % H2O for G1101-i and G2201-i, respectively. The accuracy after correction by the two-point mixing ratio gain and offset calibration method ranged from -0.04-0.09 ‰ for G1101-i and -0.13-0.03 ‰ for G2201-i. The sensitivity of δ13C to the water vapor mixing ratio improved from 1.01 ‰ / % H2O before the upgrade of G1101-i (G1101-i-original) to 0.15 ‰ / % H2O after the upgrade of G1101-i (G1101-i-upgraded). Atmospheric δ13C measured by G1101-i and G2201-i captured the rapid changes in atmospheric δ13C signals on hourly to diurnal cycle scales, with a difference of 0.07 ± 0.24 ‰ between G1101-i-original and G2201-i and 0.05 ± 0.30 ‰ between G1101-i-upgraded and G2201-i. A significant linear correlation was observed between the δ13C difference of G1101-i-original and G2201-i and the water vapor concentration, but there was no significant correlation between the δ13C difference of G1101-i-upgraded and G2201-i and the water vapor concentration. The difference in the Keeling intercept values decreased from 1.24 ‰ between G1101-i-original and G2201-i to 0.36 ‰ between G1101-i-upgraded and G2201-i, which indicates the importance of consistency

  7. Crystal structures and dynamical properties of dense CO2

    PubMed Central

    Yong, Xue; Liu, Hanyu; Wu, Min; Yao, Yansun; Tse, John S.; Dias, Ranga; Yoo, Choong-Shik

    2016-01-01

    Structural polymorphism in dense carbon dioxide (CO2) has attracted significant attention in high-pressure physics and chemistry for the past two decades. Here, we have performed high-pressure experiments and first-principles theoretical calculations to investigate the stability, structure, and dynamical properties of dense CO2. We found evidence that CO2-V with the 4-coordinated extended structure can be quenched to ambient pressure below 200 K—the melting temperature of CO2-I. CO2-V is a fully coordinated structure formed from a molecular solid at high pressure and recovered at ambient pressure. Apart from confirming the metastability of CO2-V (I-42d) at ambient pressure at low temperature, results of ab initio molecular dynamics and metadynamics (MD) simulations provided insights into the transformation processes and structural relationship from the molecular to the extended phases. In addition, the simulation also predicted a phase V′(Pna21) in the stability region of CO2-V with a diffraction pattern similar to that previously assigned to the CO2-V (P212121) structure. Both CO2-V and -V′ are predicted to be recoverable and hard with a Vicker hardness of ∼20 GPa. Significantly, MD simulations found that the CO2 in phase IV exhibits large-amplitude bending motions at finite temperatures and high pressures. This finding helps to explain the discrepancy between earlier predicted static structures and experiments. MD simulations clearly indicate temperature effects are critical to understanding the high-pressure behaviors of dense CO2 structures—highlighting the significance of chemical kinetics associated with the transformations. PMID:27647887

  8. Distribution and nature of CO2 on Enceladus

    NASA Astrophysics Data System (ADS)

    Combe, J. P.; McCord, T. B.; Matson, D.; Johnson, T. V.; Scipioni, F.; Tosi, F.

    2015-12-01

    We present the first global mapping and analysis of CO2 on the surface of Enceladus, and we report the largest concentrations of free CO2 on the southern polar region using the Visual and Infrared Mapping Spectrometer (VIMS) on Cassini. Free CO2 ice and complexed CO2 were already reported near the South Pole (Brown et al., Science, 2006; Hansen, LPSC, 2010). Our work focuses on determining the amount, location and molecular state of CO2 on Enceladus, which could help identify and model geophysical processes that currently occur in the interior. One hypothesis for bringing heat and chemicals to the surface is a warm subsurface ocean containing dissolved gases, mostly CO2 (Postberg F. et al., Nature, 2009). Therefore, our observations are consistent with erupted and condensed materials onto Enceladus' surface (Matson et al., Icarus, 2012; Matson et al. AGU Fall meeting 2015). Free CO2 ice absorbs at 4.268 µm (Sandford and Allamandola, 1990) and CO2 complexed with other molecules absorbs at 4.247 μm (Chaban et al., Icarus, 2007). The Enceladus case is complicated because both free and complexed CO2 are present, and the absorption band of interest is shallow and close to the instrument detection limit. Many of the few Enceladus VIMS data sets have significant and sometimes unusual noise, which we attempted to avoid or remove. We utilized all VIMS data sets available that were collected over ten years of the Cassini mission as a way to improve the detection statistics and signal to noise. We also used wavelengths near 2.7 μm where CO2 has a narrow absorption as a filter to help identify CO2-rich areas. Finally, we selected observations that have spatial resolution better than 100 km in order to create a map that can be compared with the largest fractures, known as Tiger Stripes, in the southern polar region.

  9. 5% CO2 is a potent, fast acting inhalation anticonvulsant

    PubMed Central

    Tolner, Else A.; Hochman, Daryl W.; Hassinen, Pekka; Otáhal, Jakub; Gaily, Eija; Haglund, Michael M.; Kubová, Hana; Schuchmann, Sebastian; Vanhatalo, Sampsa; Kaila, Kai

    2010-01-01

    Purpose CO2 has been long recognized for its anticonvulsant properties. We aimed to determine whether inhaling 5% CO2 can be used to suppress seizures in epilepsy patients. The effect of CO2 on cortical epileptic activity accompanying behavioral seizures was studied in rats and a non-human primate and based on these data, preliminary tests were carried out in humans. Methods In freely moving rats, cortical afterdischarges paralleled by myoclonic convulsions were evoked by sensorimotor cortex stimulation. 5% CO2 was applied for 5 minutes, 3 minutes before stimulation. In macaque monkeys, hypercarbia was induced by hypoventilation while seizure activity was electrically or chemically evoked in the sensorimotor cortex. Seven patients with drug-resistant partial epilepsy were examined with video-EEG and received 5% CO2 in medical carbogen shortly after electrographic seizure onset. Results In rats, 5% CO2 strongly suppressed cortical afterdischarges, by ca. 75%, while responses to single-pulse stimulation were reduced by about 15% only. In macaques, increasing pCO2 from 37 to 44-45 mmHg (corresponding to inhalation of 5% CO2 or less) suppressed stimulation-induced cortical afterdischarges by about 70% and single, bicuculline-induced epileptiform spikes by ca. 25%. In a pilot trial carried out in 7 patients, a rapid termination of electrographic seizures was seen despite the fact that the application of 5% CO2 was started after seizure generalization. Conclusions 5% CO2 has a fast and potent anticonvulsant action. The present data suggest that medical carbogen with 5% CO2 can be used for acute treatment to suppress seizures in epilepsy patients. PMID:20887367

  10. Crystal structures and dynamical properties of dense CO2.

    PubMed

    Yong, Xue; Liu, Hanyu; Wu, Min; Yao, Yansun; Tse, John S; Dias, Ranga; Yoo, Choong-Shik

    2016-10-04

    Structural polymorphism in dense carbon dioxide (CO2) has attracted significant attention in high-pressure physics and chemistry for the past two decades. Here, we have performed high-pressure experiments and first-principles theoretical calculations to investigate the stability, structure, and dynamical properties of dense CO2 We found evidence that CO2-V with the 4-coordinated extended structure can be quenched to ambient pressure below 200 K-the melting temperature of CO2-I. CO2-V is a fully coordinated structure formed from a molecular solid at high pressure and recovered at ambient pressure. Apart from confirming the metastability of CO2-V (I-42d) at ambient pressure at low temperature, results of ab initio molecular dynamics and metadynamics (MD) simulations provided insights into the transformation processes and structural relationship from the molecular to the extended phases. In addition, the simulation also predicted a phase V'(Pna21) in the stability region of CO2-V with a diffraction pattern similar to that previously assigned to the CO2-V (P212121) structure. Both CO2-V and -V' are predicted to be recoverable and hard with a Vicker hardness of ∼20 GPa. Significantly, MD simulations found that the CO2 in phase IV exhibits large-amplitude bending motions at finite temperatures and high pressures. This finding helps to explain the discrepancy between earlier predicted static structures and experiments. MD simulations clearly indicate temperature effects are critical to understanding the high-pressure behaviors of dense CO2 structures-highlighting the significance of chemical kinetics associated with the transformations.

  11. Improving CO2 permeation and separation performance of CO2-philic polymer membrane by blending CO2 absorbents

    NASA Astrophysics Data System (ADS)

    Cheng, Jun; Hu, Leiqing; Li, Yannan; Liu, Jianzhong; Zhou, Junhu; Cen, Kefa

    2017-07-01

    To research effects of CO2 absorption capacity and type of CO2 absorbent on the CO2 separation and free-volume properties of facilitated transport membranes, two types of CO2 absorbents, namely monoethanolamine (MEA) and ionic liquids (ILs:[P66614][Triz] and [P66614][2-Op]), were adopted. The CO2 absorption capacities of MEA, [P66614][Triz] and [P66614][2-Op] were about 0.561 mol CO2 per mol, 0.95 mol CO2 per mol and 1.60 mol CO2 per mol, respectively. All mean free-volume hole radiuses of membranes decreased after blending CO2 absorbents. After polymer membrane blended with two ILs, number of free-volume hole increased, resulting in modest increase of the fractional free volume. Both CO2 permeability and selectivity increased after blending MEA and ILs. The increasing range of CO2 permeability corresponded with CO2 absorption capacity of CO2 absorbents, and membrane blending with [P66614][2-Op] showed the highest CO2 permeability of 672.1 Barrers at 25 °C. Pebax/PEGDME membrane blending with MEA obtained the highest CO2/H2 and CO2/CH4 selectivity at 17.8 and 20.5, respectively.

  12. CO2 Acquisition Membrane (CAM)

    NASA Technical Reports Server (NTRS)

    Mason, Larry W.; Way, J. Douglas; Vlasse, Marcus

    2003-01-01

    The objective of CAM is to develop, test, and analyze thin film membrane materials for separation and purification of carbon dioxide (CO2) from mixtures of gases, such as those found in the Martian atmosphere. The membranes are targeted toward In Situ Resource Utilization (ISRU) applications that will operate in extraterrestrial environments and support future unmanned and human space missions. A primary application is the Sabatier Electrolysis process that uses Mars atmosphere CO2 as raw material for producing water, oxygen, and methane for rocket fuel and habitat support. Other applications include use as an inlet filter to collect and concentrate Mars atmospheric argon and nitrogen gases for habitat pressurization, and to remove CO2 from breathing gases in Closed Environment Life Support Systems (CELSS). CAM membrane materials include crystalline faujasite (FAU) zeolite and rubbery polymers such as silicone rubber (PDMS) that have been shown in the literature and via molecular simulation to favor adsorption and permeation of CO2 over nitrogen and argon. Pure gas permeation tests using commercial PDMS membranes have shown that both CO2 permeance and the separation factor relative to other gases increase as the temperature decreases, and low (Delta)P(Sub CO2) favors higher separation factors. The ideal CO2/N2 separation factor increases from 7.5 to 17.5 as temperature decreases from 22 C to -30 C. For gas mixtures containing CO2, N2, and Ar, plasticization decreased the separation factors from 4.5 to 6 over the same temperature range. We currently synthesize and test our own Na(+) FAU zeolite membranes using standard formulations and secondary growth methods on porous alumina. Preliminary tests with a Na(+) FAU membrane at 22 C show a He/SF6 ideal separation factor of 62, exceeding the Knudsen diffusion selectivity by an order of magnitude. This shows that the membrane is relatively free from large defects and associated non-selective (viscous flow) transport

  13. CO2 Acquisition Membrane (CAM)

    NASA Technical Reports Server (NTRS)

    Mason, Larry W.; Way, J. Douglas; Vlasse, Marcus

    2003-01-01

    The objective of CAM is to develop, test, and analyze thin film membrane materials for separation and purification of carbon dioxide (CO2) from mixtures of gases, such as those found in the Martian atmosphere. The membranes are targeted toward In Situ Resource Utilization (ISRU) applications that will operate in extraterrestrial environments and support future unmanned and human space missions. A primary application is the Sabatier Electrolysis process that uses Mars atmosphere CO2 as raw material for producing water, oxygen, and methane for rocket fuel and habitat support. Other applications include use as an inlet filter to collect and concentrate Mars atmospheric argon and nitrogen gases for habitat pressurization, and to remove CO2 from breathing gases in Closed Environment Life Support Systems (CELSS). CAM membrane materials include crystalline faujasite (FAU) zeolite and rubbery polymers such as silicone rubber (PDMS) that have been shown in the literature and via molecular simulation to favor adsorption and permeation of CO2 over nitrogen and argon. Pure gas permeation tests using commercial PDMS membranes have shown that both CO2 permeance and the separation factor relative to other gases increase as the temperature decreases, and low (Delta)P(Sub CO2) favors higher separation factors. The ideal CO2/N2 separation factor increases from 7.5 to 17.5 as temperature decreases from 22 C to -30 C. For gas mixtures containing CO2, N2, and Ar, plasticization decreased the separation factors from 4.5 to 6 over the same temperature range. We currently synthesize and test our own Na(+) FAU zeolite membranes using standard formulations and secondary growth methods on porous alumina. Preliminary tests with a Na(+) FAU membrane at 22 C show a He/SF6 ideal separation factor of 62, exceeding the Knudsen diffusion selectivity by an order of magnitude. This shows that the membrane is relatively free from large defects and associated non-selective (viscous flow) transport

  14. Outsourcing CO2 within China.

    PubMed

    Feng, Kuishuang; Davis, Steven J; Sun, Laixiang; Li, Xin; Guan, Dabo; Liu, Weidong; Liu, Zhu; Hubacek, Klaus

    2013-07-09

    Recent studies have shown that the high standard of living enjoyed by people in the richest countries often comes at the expense of CO2 emissions produced with technologies of low efficiency in less affluent, developing countries. Less apparent is that this relationship between developed and developing can exist within a single country's borders, with rich regions consuming and exporting high-value goods and services that depend upon production of low-cost and emission-intensive goods and services from poorer regions in the same country. As the world's largest emitter of CO2, China is a prominent and important example, struggling to balance rapid economic growth and environmental sustainability across provinces that are in very different stages of development. In this study, we track CO2 emissions embodied in products traded among Chinese provinces and internationally. We find that 57% of China's emissions are related to goods that are consumed outside of the province where they are produced. For instance, up to 80% of the emissions related to goods consumed in the highly developed coastal provinces are imported from less developed provinces in central and western China where many low-value-added but high-carbon-intensive goods are produced. Without policy attention to this sort of interprovincial carbon leakage, the less developed provinces will struggle to meet their emissions intensity targets, whereas the more developed provinces might achieve their own targets by further outsourcing. Consumption-based accounting of emissions can thus inform effective and equitable climate policy within China.

  15. Capture of CO2 From Recirculating Flue Gas Boilers

    SciTech Connect

    Ochs, Thomas L.

    2003-01-01

    The possible need for an economical method for the separation of CO2 from flue gas adds a new set of challenges to power plant design, construction, operation, and maintenance. Many of the new requirements of CO2 separation are similar in nature to those addressed by the mature chemical engineering processes used in petroleum refining and industrial chemical production. Chemical engineering processes are regularly used to separate heterogeneous vapors in processes such as the fractionation of hydrocarbons or the separation of the components of air. This paper addresses the application of chemical engineering processes to the mixtures of gases and vapors found in the flue gas of recirculating boilers. Adaptation of these techniques can lead to a reduction in the energy required to capture CO2.

  16. Dehydrated Prussian Blues for CO2 Storage and Separation Applications

    SciTech Connect

    Motkuri, Radha K.; Thallapally, Praveen K.; McGrail, B. Peter; Ghorishi, Behrooz S.

    2010-08-13

    Adsorption isotherms of pure gases present in flue and natural gas including CO2, N2, CH4 and water were studied using prussian blues of chemical formula M3[Co(CN)6]2 (M = Cu, Ni, Mn). These materials adsorbed 8-12 wt % of CO2 at room temperature and 1 bar of pressure with heats of adsorption ranging from 6 to 16 kcal/mol.

  17. Isotopic disequilibrium during uptake of atmospheric CO2 into mine process waters: implications for CO2 sequestration.

    PubMed

    Wilson, Siobhan A; Barker, Shaun L L; Dipple, Gregory M; Atudorei, Viorel

    2010-12-15

    Dypingite, a hydrated Mg-carbonate mineral, was precipitated from high-pH, high salinity solutions to investigate controls on carbon fixation and to identify the isotopic characteristics of mineral sequestration in mine tailings. δ(13)C values of dissolved inorganic carbon content and synthetic dypingite are significantly more negative than those predicted for equilibrium exchange of CO(2) gas between the atmosphere and solution. The measured δ(13)C of aqueous carbonate species is consistent with a kinetic fractionation that results from a slow diffusion of atmospheric CO(2) into solution. During dypingite precipitation, dissolved inorganic carbon concentrations decrease and δ(13)C values become more negative, indicating that the rate of CO(2) uptake into solution was outpaced by the rate of carbon fixation within the precipitate. This implies that CO(2) gas uptake is rate-limiting to CO(2) fixation. δ(13)C of carbonate mineral precipitates in mine tailings and of DIC in mine process waters display similar (13)C-depletions that are inconsistent with equilibrium fractionation. Thus, the rate of carbon fixation in mine tailings may also be limited by supply of CO(2). Carbon sequestration could be accelerated by increasing the partial pressure of CO(2) in tailings ponds or by using chemicals that enhance the uptake of gaseous CO(2) into aqueous solution.

  18. Lessons from Natural CO2 Leakage Analogue Site Studies and their Application to Secure CO2 Storage and Monitoring

    NASA Astrophysics Data System (ADS)

    Han, W.; McPherson, B. J.; Kim, K.; Chae, G.; Yum, B.

    2011-12-01

    related chemical reactions in the observation wells and tested with numerical simulation tools, which predicted thermal processes caused by solid NaCl precipitation, buoyancy-driven supercritical CO2 migration, and potential non-isothermal effects. Simulation results suggest that these processes - solid NaCl precipitation, buoyancy effects, Joule-Thomson cooling, water vaporization, and exothermic CO2 reactions - are strongly coupled and dynamic (transient). Overall, a fundamental understanding of potential thermal processes investigated through this research will be beneficial in the collection and analysis of temperature signals collectively measured from monitoring wells.

  19. Assessment of full-scale biological nutrient removal systems upgraded with physico-chemical processes for the removal of emerging pollutants present in wastewaters from Mexico.

    PubMed

    Estrada-Arriaga, Edson Baltazar; Cortés-Muñoz, Juana Enriqueta; González-Herrera, Arturo; Calderón-Mólgora, César Guillermo; de Lourdes Rivera-Huerta, Ma; Ramírez-Camperos, Esperanza; Montellano-Palacios, Leticia; Gelover-Santiago, Silvia Lucila; Pérez-Castrejón, Sara; Cardoso-Vigueros, Lina; Martín-Domínguez, Alejandra; García-Sánchez, Liliana

    2016-11-15

    Two full-scale biological nutrient removal systems upgraded with three physico-chemical processes (coagulation, chemical precipitation, and neutral Fenton) were evaluated in order to determine the removal of emerging pollutants (EPs) present in municipal wastewater from Mexico. Between 41 and 55 EPs were detected in the influents of two wastewater treatment plants (WWTPs), including personal care products (PPCPs), antibiotics, analgesics, antiepileptics, antilipidemics, antihypertensives, antiseptics, stimulants, and hormones. Emerging pollutants were detected at concentrations ranging from 0.69ng/L to 94,600ng/L. High concentrations of emerging pollutants were found during dry season. WWTP 1, integrated by oxidation ditches and UV light lamps, showed removal efficiencies of EPs between 20% and 22%. On the other hand, WWTP 2 consisted of anaerobic/anoxic/aerobic tanks coupled with two disinfection processes; chlorine dioxide and UV light lamps, for which the removal of EPs was significant (up to 80%). The concentrations of emerging pollutants in WWTP 1 effluent was found within a range

  20. Estimation of continuous anthropogenic CO2 using CO2, CO, δ13C(CO2) and Δ14C(CO2)

    NASA Astrophysics Data System (ADS)

    Vardag, S. N.; Gerbig, C.; Janssens-Maenhout, G.; Levin, I.

    2015-07-01

    We investigate different methods for estimating anthropogenic CO2 using modelled continuous atmospheric concentrations of CO2 alone, as well as CO2 in combination with the surrogate tracers CO, δ13C(CO2) and Δ14C(CO2). These methods are applied at three hypothetical stations representing rural, urban and polluted conditions. We find that independent of the tracer used, an observation-based estimate of continuous anthropogenic CO2 is not feasible at rural measurement sites due to the low signal to noise ratio of anthropogenic CO2 estimates at such settings. At urban and polluted sites, potential future continuous Δ14C(CO2) measurements with a precision of 5 ‰ or better are most promising for anthropogenic CO2 determination (precision ca. 10-20%), but the insensitivity against CO2 contributions from biofuel emissions may reduce its accuracy in the future. Other tracers, such as δ13C(CO2) and CO could provide an accurate and already available alternative if all CO2 sources in the catchment area are well characterized with respect to their isotopic signature and CO to anthropogenic CO2 ratio. We suggest a strategy for calibrating these source characteristics on an annual basis using precise Δ14C(CO2) measurements on grab samples. The precision of anthropogenic CO2 determination using δ13C(CO2) is largely determined by the measurement precision of δ13C(CO2) and CO2. The precision when using the CO-method is mainly limited by the variation of natural CO sources and CO sinks. At present, continuous anthropogenic CO2 could be determined using the tracers δ13C(CO2) and/or CO with a precision of about 30 %, a mean bias of about 10 % and without significant diurnal discrepancies. This allows significant improvement, validation and bias reduction of highly resolved emission inventories using atmospheric observation and regional modelling.

  1. Surface Condensation of CO2 onto Kaolinite

    SciTech Connect

    Schaef, Herbert T.; Glezakou, Vassiliki Alexandra; Owen, Antionette T.; Ramprasad, Sudhir; Martin, Paul F.; McGrail, B. Peter

    2014-02-11

    The fundamental adsorption behavior of gaseous and supercritical carbon dioxide (CO2) onto poorly crystalline kaolinite (KGa-2) at conditions relevant to geologic sequestration has been investigated using a quartz crystal microbalance (QCM) and density functional theory (DFT) methods. The QCM data indicated linear adsorption of CO2 (0-0.3 mmol CO2/g KGa-2) onto the kaolinite surface up through the gaseous state (0.186 g/cm3). However in the supercritical region, CO2 adsorption increases dramatically, reaching a peak (0.9-1.0 mmol CO2/g KGa-2) near 0.43 g/cm3, before declining rapidly to surface adsorption values equivalent or below gaseous CO2. This adsorption profile was not observed with He or N2. Comparative density functional studies of CO2 interactions with kaolinite surface models rule out CO2 intercalation and confirm that surface adsorption is favored up to approximately 0.35 g/cm3 of CO2, showing distorted T-shaped CO2-CO2 clustering, typical of supercritical CO2 aggregation over the surface as the density increases. Beyond this point, the adsorption energy gain for any additional CO2 becomes less than the CO2 interaction energy (~0.2 eV) in the supercritical medium resulting in overall desorption of CO2 from the kaolinite surface.

  2. Outsourcing CO2 within China

    PubMed Central

    Feng, Kuishuang; Davis, Steven J.; Sun, Laixiang; Li, Xin; Guan, Dabo; Liu, Weidong; Liu, Zhu; Hubacek, Klaus

    2013-01-01

    Recent studies have shown that the high standard of living enjoyed by people in the richest countries often comes at the expense of CO2 emissions produced with technologies of low efficiency in less affluent, developing countries. Less apparent is that this relationship between developed and developing can exist within a single country’s borders, with rich regions consuming and exporting high-value goods and services that depend upon production of low-cost and emission-intensive goods and services from poorer regions in the same country. As the world’s largest emitter of CO2, China is a prominent and important example, struggling to balance rapid economic growth and environmental sustainability across provinces that are in very different stages of development. In this study, we track CO2 emissions embodied in products traded among Chinese provinces and internationally. We find that 57% of China’s emissions are related to goods that are consumed outside of the province where they are produced. For instance, up to 80% of the emissions related to goods consumed in the highly developed coastal provinces are imported from less developed provinces in central and western China where many low–value-added but high–carbon-intensive goods are produced. Without policy attention to this sort of interprovincial carbon leakage, the less developed provinces will struggle to meet their emissions intensity targets, whereas the more developed provinces might achieve their own targets by further outsourcing. Consumption-based accounting of emissions can thus inform effective and equitable climate policy within China. PMID:23754377

  3. Surface modification induced enhanced CO2 sorption in cucurbit[6]uril, an organic porous material.

    PubMed

    Mohan, Midhun; Suzuki, T; Nair, Akhil K; Pillai, Saju; Warrier, K G K; Hareesh, U S; Nair, Balagopal N; Gale, J D

    2017-09-13

    The CO2 adsorption properties of an organic macrocycle, cucurbit[6]uril (CB[6]), have been evaluated through experimental and theoretical studies. Quantum mechanical calculations show that CB[6] is capable of adsorbing the CO2 molecule selectively within its cavity relative to nitrogen. Adsorption experiments at 298 K and at 1 bar pressure gave a CO2 adsorption value of 1.23 mmol g(-1) for the unmodified material. Significant enhancements in the CO2 adsorption capacity of the material were experimentally demonstrated through surface modification using physical and chemical methods. Ethanolamine (EA) modified CB[6] provided an excellent sorption selectivity value of 121.4 for CO2/N2 at 323 K and is unique with respect to its discrimination potential between CO2 and N2. The chemical nature of the interaction between CO2 and amine is shown to be the primary mechanism for the enhanced CO2 absorption performance.

  4. Synthesis, characterization and application of alkanolamidines and alkanolguanidines in CO(2) capture

    SciTech Connect

    Koech, Phillip K; Heldebrant, David J; Lee, Suh-Jane; Rainbolt, James E; Smurthwaite, Tricia D

    2011-03-01

    Global carbon dioxide (CO2) emission to the atmosphere is partly responsible for climate change. In order to mitigate these environmental effects CO2 capture and storage is required. Solvents currently used for this application are the energy intensive aqueous amines. Here we present the synthesis, characterization and CO2 uptake of new advanced solvents called alkanolamidines and alkanolguanidines otherwise known as CO2-binding organic Liquids (CO2BOLs). These solvents have been designed to have decreased vapor pressure and low viscosity in order to increase the CO2 uptake capacity while minimizing evaporative losses. Alkanolamidines were synthesized in 1-3 steps from commercially available materials. These compounds bind CO2 chemically via the alcohol moiety forming zwitterionic alkylcarbonates. The alkanolamidines can be regenerated thermally by heating the alkylcarbonate to 75 °C. CO2 binding capacities up to 10 wt% were achieved using these compounds. These compounds have the potential to be energy efficient CO2 capture solvents.

  5. Technological advances in CO2 conversion electro-biorefinery: A step toward commercialization.

    PubMed

    ElMekawy, Ahmed; Hegab, Hanaa M; Mohanakrishna, Gunda; Elbaz, Ashraf F; Bulut, Metin; Pant, Deepak

    2016-09-01

    The global atmospheric warming due to increased emissions of carbon dioxide (CO2) has attracted great attention in the last two decades. Although different CO2 capture and storage platforms have been proposed, the utilization of captured CO2 from industrial plants is progressively prevalent strategy due to concerns about the safety of terrestrial and aquatic CO2 storage. Two utilization forms were proposed, direct utilization of CO2 and conversion of CO2 to chemicals and energy products. The latter strategy includes the bioelectrochemical techniques in which electricity can be used as an energy source for the microbial catalytic production of fuels and other organic products from CO2. This approach is a potential technique in which CO2 emissions are not only reduced, but it also produce more value-added products. This review article highlights the different methodologies for the bioelectrochemical utilization of CO2, with distinctive focus on the potential opportunities for the commercialization of these techniques.

  6. The reactivity of CO2 with K atoms adsorbed on MgO powders.

    PubMed

    Preda, Gloria; Pacchioni, Gianfranco; Chiesa, Mario; Giamello, Elio

    2009-10-01

    In this combined quantum chemical and EPR study we have investigated the formation of CO(2)(-) radicals by contact of CO(2) molecules with a K precovered MgO surface. K atoms have been deposited on polycrystalline MgO samples, and then exposed to CO(2). The typical EPR signal of the isolated K atoms disappears when the reaction with CO(2) takes place and a new paramagnetic species attributed to CO(2)(-) is observed. DFT cluster model calculations show that there is a spontaneous electron transfer from the adsorbed K atom to the CO(2) molecule, with formation of K(+)CO(2)(-) surface complexes. These species have the same electronic characteristics and spin distribution of gas-phase M(+)CO(2)(-) (M = Li, Na, K) molecules, but are stabilized by the presence of the ionic surface. The most stable MgO sites where the adsorption of CO(2) occurs and the computed EPR properties are discussed.

  7. Environmental potential of the use of CO2 from alcoholic fermentation processes. The CO2-AFP strategy.

    PubMed

    Alonso-Moreno, Carlos; García-Yuste, Santiago

    2016-10-15

    A novel Carbon Dioxide Utilization (CDU) approach from a relatively minor CO2 emission source, i.e., alcoholic fermentation processes (AFP), is presented. The CO2 produced as a by-product from the AFP is estimated by examining the EtOH consumed per year reported by the World Health Organization in 2014. It is proposed that the extremely pure CO2 from the AFP is captured in NaOH solutions to produce one of the Top 10 commodities in the chemical industry, Na2CO3, as a good example of an atomic economy process. The novel CDU strategy could yield over 30.6Mt of Na2CO3 in oversaturated aqueous solution on using ca. 12.7Mt of captured CO2 and this process would consume less energy than the synthetic methodology (Solvay ammonia soda process) and would not produce low-value by-products. The quantity of Na2CO3 obtained by this strategy could represent ca. 50% of the world Na2CO3 production in one year. In terms of the green economy, the viability of the strategy is discussed according to the recommendations of the CO2Chem network, and an estimation of the CO2negative emission achieved suggests a capture of around 280.0Mt of CO2 from now to 2020 or ca. 1.9Gt from now to 2050. Finally, the results obtained for this new CDU proposal are discussed by considering different scenarios; the CO2 production in a typical winemaking corporation, the CO2 released in the most relevant wine-producing countries, and the use of CO2 from AFP as an alternative for the top Na2CO3-producing countries.

  8. Integrated electromicrobial conversion of CO2 to higher alcohols.

    PubMed

    Li, Han; Opgenorth, Paul H; Wernick, David G; Rogers, Steve; Wu, Tung-Yun; Higashide, Wendy; Malati, Peter; Huo, Yi-Xin; Cho, Kwang Myung; Liao, James C

    2012-03-30

    One of the major challenges in using electrical energy is the efficiency in its storage. Current methods, such as chemical batteries, hydraulic pumping, and water splitting, suffer from low energy density or incompatibility with current transportation infrastructure. Here, we report a method to store electrical energy as chemical energy in higher alcohols, which can be used as liquid transportation fuels. We genetically engineered a lithoautotrophic microorganism, Ralstonia eutropha H16, to produce isobutanol and 3-methyl-1-butanol in an electro-bioreactor using CO(2) as the sole carbon source and electricity as the sole energy input. The process integrates electrochemical formate production and biological CO(2) fixation and higher alcohol synthesis, opening the possibility of electricity-driven bioconversion of CO(2) to commercial chemicals.

  9. CO2 Infrared Phonon Modes in Interstellar Ice Mixtures

    NASA Astrophysics Data System (ADS)

    Cooke, Ilsa R.; Fayolle, Edith C.; Öberg, Karin I.

    2016-11-01

    CO2 ice is an important reservoir of carbon and oxygen in star- and planet-forming regions. Together with water and CO, CO2 sets the physical and chemical characteristics of interstellar icy grain mantles, including desorption and diffusion energies for other ice constituents. A detailed understanding of CO2 ice spectroscopy is a prerequisite to characterize CO2 interactions with other volatiles both in interstellar ices and in laboratory experiments of interstellar ice analogs. We report laboratory spectra of the CO2 longitudinal optical (LO) phonon mode in pure CO2 ice and in CO2 ice mixtures with H2O, CO, and O2 components. We show that the LO phonon mode position is sensitive to the mixing ratio of various ice components of astronomical interest. In the era of the James Webb Space Telescope, this characteristic could be used to constrain interstellar ice compositions and morphologies. More immediately, LO phonon mode spectroscopy provides a sensitive probe of ice mixing in the laboratory and should thus enable diffusion measurements with higher precision than has been previously possible.

  10. Isentropic transport and the seasonal cycle amplitude of CO2

    NASA Astrophysics Data System (ADS)

    Barnes, Elizabeth A.; Parazoo, Nicholas; Orbe, Clara; Denning, A. Scott

    2016-07-01

    Carbon-concentration feedbacks and carbon-climate feedbacks constitute one of the largest sources of uncertainty in future climate. Since the beginning of the modern atmospheric CO2 record, seasonal variations in CO2 have been recognized as a signal of the metabolism of land ecosystems, and quantitative attribution of changes in the seasonal cycle amplitude (SCA) of CO2 to ecosystem processes is critical for understanding and projecting carbon-climate feedbacks far into the 21st Century. Here the impact of surface carbon fluxes on the SCA of CO2 throughout the Northern Hemisphere troposphere is investigated, paying particular attention to isentropic transport across latitudes. The analysis includes both a chemical transport model GOES-Chem and an idealized tracer in a gray-radiation aquaplanet. The results of the study can be summarized by two main conclusions: (1) the SCA of CO2 roughly follows surfaces of constant potential temperature, which can explain the observed increase in SCA with latitude along pressure surfaces and (2) increasing seasonal fluxes in lower latitudes have a larger impact on the SCA of CO2 throughout most of the troposphere compared to increasing seasonal fluxes in higher latitudes. These results provide strong evidence that recently observed changes in the SCA of CO2 at high northern latitudes (poleward of 60°N) are likely driven by changes in midlatitude surface fluxes, rather than changes in Arctic fluxes.

  11. Acidification of reverse micellar nanodroplets by atmospheric pressure CO2.

    PubMed

    Levinger, Nancy E; Rubenstrunk, Lauren C; Baruah, Bharat; Crans, Debbie C

    2011-05-11

    Water absorption of atmospheric carbon dioxide lowers the solution pH due to carbonic acid formation. Bulk water acidification by CO(2) is well documented, but significantly less is known about its effect on water in confined spaces. Considering its prominence as a greenhouse gas, the importance of aerosols in acid rain, and CO(2)-buffering in cellular systems, surprisingly little information exists about the absorption of CO(2) by nanosized water droplets. The fundamental interactions of CO(2) with water, particularly in nanosized structures, may influence a wide range of processes in our technological society. Here results from experiments investigating the uptake of gaseous CO(2) by water pools in reverse micelles are presented. Despite the small number of water molecules in each droplet, changes in vanadium probes within the water pools, measured using vanadium-51 NMR spectroscopy, indicate a significant drop in pH after CO(2) introduction. Collectively, the pH-dependent vanadium probes show CO(2) dissolves in the nanowater droplets, causing the reverse micelle acidity to increase. © 2011 American Chemical Society

  12. A Cationic MOF with High Uptake and Selectivity for CO2 due to Multiple CO2 -Philic Sites.

    PubMed

    Wang, Hai-Hua; Shi, Wen-Juan; Hou, Lei; Li, Gao-Peng; Zhu, Zhonghua; Wang, Yao-Yu

    2015-11-09

    The reaction of N-rich pyrazinyl triazolyl carboxyl ligand 3-(4-carboxylbenzene)-5-(2-pyrazinyl)-1H-1,2,4-triazole (H2 cbptz) with MnCl2 afforded 3D cationic metal-organic framework (MOF) [Mn2 (Hcbptz)2 (Cl)(H2 O)]Cl⋅DMF⋅0.5 CH3 CN (1), which has an unusual (3,4)-connected 3,4T1 topology and 1D channels composed of cavities. MOF 1 has a very polar framework that contains exposed metal sites, uncoordinated N atoms, narrow channels, and Cl(-) basic sites, which lead to not only high CO2 uptake, but also remarkably selective adsorption of CO2 over N2 and CH4 at 298-333 K. The multiple CO2 -philic sites were identified by grand canonical Monte Carlo simulations. Moreover, 1 shows excellent stability in natural air environment. These advantages make 1 a very promising candidate in post-combustion CO2 capture, natural-gas upgrading, and landfill gas-purification processes. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Field Tests of Real-time In-situ Dissolved CO2 Monitoring for CO2 Leakage Detection in Groundwater

    NASA Astrophysics Data System (ADS)

    Yang, C.; Zou, Y.; Delgado, J.; Guzman, N.; Pinedo, J.

    2016-12-01

    Groundwater monitoring for detecting CO2 leakage relies on groundwater sampling from water wells drilled into aquifers. Usually groundwater samples are required be collected periodically in field and analyzed in the laboratory. Obviously groundwater sampling is labor and cost-intensive for long-term monitoring of large areas. Potential damage and contamination of water samples during the sampling process can degrade accuracy, and intermittent monitoring may miss changes in the geochemical parameters of groundwater, and therefore signs of CO2 leakage. Real-time in-situ monitoring of geochemical parameters with chemical sensors may play an important role for CO2 leakage detection in groundwater at a geological carbon sequestration site. This study presents field demonstration of a real-time in situ monitoring system capable of covering large areas for detection of low levels of dissolved CO2 in groundwater and reliably differentiating natural variations of dissolved CO2 concentration from small changes resulting from leakage. The sand-alone system includes fully distributed fiber optic sensors for carbon dioxide detection with a unique sensor technology developed by Intelligent Optical Systems. The systems were deployed to the two research sites: the Brackenridge Field Laboratory where the aquifer is shallow at depths of 10-20 ft below surface and the Devine site where the aquifer is much deeper at depths of 140 to 150 ft. Groundwater samples were periodically collected from the water wells which were installed with the chemical sensors and further compared to the measurements of the chemical sensors. Our study shows that geochemical monitoring of dissolved CO2 with fiber optic sensors could provide reliable CO2 leakage signal detection in groundwater as long as CO2 leakage signals are stronger than background noises at the monitoring locations.

  14. The rise and fall of carbon dioxide: Why controlling CO2 may be necessary in greenhouses

    USDA-ARS?s Scientific Manuscript database

    In the winter production cycle, many of us focus on sealing up gaps in an effort to decrease air infiltration, and cut our heating bills substantially along the way. While making these changes or upgrades, we ignoring something the potential impact this has on carbon dioxide (CO2) and plant growth. ...

  15. Nutrient removal and biogas upgrading by integrating freshwater algae cultivation with piggery anaerobic digestate liquid treatment.

    PubMed

    Xu, Jie; Zhao, Yongjun; Zhao, Guohua; Zhang, Hui

    2015-08-01

    An integrated approach that combined freshwater microalgae Scenedesmus obliquus (FACHB-31) cultivation with piggery anaerobic digestate liquid treatment was investigated in this study. The characteristics of algal growth, biogas production, and nutrient removal were examined using photobioreactor bags (PBRbs) to cultivate S. obliquus (FACHB-31) in digestate with various digestate dilutions (the concentration levels of 3200, 2200, 1600, 1200, 800, and 400 mg L(-1) chemical oxygen demand (COD)) during 7-day period. The effects of the level of pollutants on nutrient removal efficiency and CO2 removal process were investigated to select the optimum system for effectively upgrade biogas and simultaneously reduce the nutrient content in digestate. The treatment performance displayed that average removal rates of COD, total nitrogen (TN), total phosphorous (TP), and CO2 were 61.58-75.29, 58.39-74.63, 70.09-88.79, and 54.26-73.81 %, respectively. All the strains grew well under any the dilution treatments. With increased initial nutrient concentration to a certain range, the CO4 content (v/v) of raw biogas increased. Differences in the biogas enrichment of S. obliquus (FACHB-31) in all treatments mainly resulted from variations in biomass productivity and CO2 uptake. Notably, the diluted digestate sample of 1600 mg L(-1) COD provided an optimal nutrient concentration for S. obliquus (FACHB-31) cultivation, where the advantageous nutrient and CO2 removals, as well as the highest productivities of biomass and biogas upgrading, were revealed. Results showed that microalgal biomass production offered real opportunities to address issues such as CO2 sequestration, wastewater treatment, and biogas production.

  16. CO2-induced changes in mineral stoichiometry of wheat grains

    NASA Astrophysics Data System (ADS)

    Broberg, Malin; Pleijel, Håkan; Högy, Petra

    2016-04-01

    positive environmental effect and possibly as a result of reduced transpiration under eCO2, since uptake and transport of Cd is known to be related to transpiration. For elements with substantial data the response in OTC and FACE exposure systems could be compared and no large differences were observed. Our study shows that eCO2 has a significant effect on the mineral composition of wheat grain. This has strong implications for human nutrition in a world of rising CO2 concentrations. An altered chemical composition of biomass under eCO2 is also of great importance for the biogeochemical cycling of elements in general.

  17. CO2 Utilization and Storage in Shale Gas Reservoirs

    NASA Astrophysics Data System (ADS)

    Schaef, T.; Glezakou, V.; Owen, T.; Miller, Q.; Loring, J.; Davidson, C.; McGrail, P.

    2013-12-01

    supercritical CO2. Additional experiments were conducted with pressurized attenuated total reflectance infrared spectroscopy technique that tracked clay hydration, gas adsorption, and water concentrations in the fluids during exposure to CO2 and CH4. These fundamental physico-chemical data are being collected into a database for parameterization of multiphase flow and reactive transport simulations of the CO2 injection, trapping, and secondary methane in fractured shales.

  18. A Critical Assessment of Microbiological Biogas to Biomethane Upgrading Systems.

    PubMed

    Rittmann, Simon K-M R

    2015-01-01

    Microbiological biogas upgrading could become a promising technology for production of methane (CH(4)). This is, storage of irregular generated electricity results in a need to store electricity generated at peak times for use at non-peak times, which could be achieved in an intermediate step by electrolysis of water to molecular hydrogen (H(2)). Microbiological biogas upgrading can be performed by contacting carbon dioxide (CO(2)), H(2) and hydrogenotrophic methanogenic Archaea either in situ in an anaerobic digester, or ex situ in a separate bioreactor. In situ microbiological biogas upgrading is indicated to require thorough bioprocess development, because only low volumetric CH(4) production rates and low CH(4) fermentation offgas content have been achieved. Higher volumetric production rates are shown for the ex situ microbiological biogas upgrading compared to in situ microbiological biogas upgrading. However, the ex situ microbiological biogas upgrading currently suffers from H(2) gas liquid mass transfer limitation, which results in low volumetric CH(4) productivity compared to pure H(2)/CO(2) conversion to CH(4). If waste gas utilization from biological and industrial sources can be shown without reduction in volumetric CH(4) productivity, as well as if the aim of a single stage conversion to a CH(4) fermentation offgas content exceeding 95 vol% can be demonstrated, ex situ microbiological biogas upgrading with pure or enrichment cultures of methanogens could become a promising future technology for almost CO(2)-neutral biomethane production.

  19. Integrated CO 2 Storage and Brine Extraction

    DOE PAGES

    Hunter, Kelsey; Bielicki, Jeffrey M.; Middleton, Richard; ...

    2017-08-18

    Carbon dioxide (CO2) capture, utilization, and storage (CCUS) can reduce CO2 emissions from fossil fuel power plants by injecting CO2 into deep saline aquifers for storage. CCUS typically increases reservoir pressure which increases costs, because less CO2 can be injected, and risks such as induced seismicity. Extracting brine with enhanced water recovery (EWR) from the CO2 storage reservoir can manage and reduce pressure in the formation, decrease the risks linked to reservoir overpressure (e.g., induced seismicity), increase CO2 storage capacity, and enable CO2 plume management. We modeled scenarios of CO2 injection with EWR into the Rock Springs Uplift (RSU) formationmore » in southwest Wyoming. The Finite Element Heat and Mass Transfer Code (FEHM) was used to model CO2 injection with brine extraction and the corresponding increase in pressure within the RSU. We analyzed the model for pressure management, CO2 storage, CO2 saturation, and brine extraction due to the quantity and location of brine extraction wells. The model limited CO2 injection to a constant pressure increase of two MPa at the injection well with and without extracting brine at hydrostatic pressure. Finally, we found that brine extraction can be used as a technical and cost-effective pressure management strategy to limit reservoir pressure buildup and increase CO2 storage associated with a single injection well.« less

  20. Passive CO2 concentration in higher plants.

    PubMed

    Sage, Rowan F; Khoshravesh, Roxana

    2016-06-01

    Photorespiratory limitations on C3 photosynthesis are substantial in warm, low CO2 conditions. To compensate, certain plants evolved mechanisms to actively concentrate CO2 around Rubisco using ATP-supported CO2 pumps such as C4 photosynthesis. Plants can also passively accumulate CO2 without additional ATP expenditure by localizing the release of photorespired and respired CO2 around Rubisco that is diffusively isolated from peripheral air spaces. Passive accumulation of photorespired CO2 occurs when glycine decarboxylase is localized to vascular sheath cells in what is termed C2 photosynthesis, and through forming sheaths of chloroplasts around the periphery of mesophyll cells. The peripheral sheaths require photorespired CO2 to re-enter chloroplasts where it can be refixed. Passive accumulation of respiratory CO2 is common in organs such as stems, fruits and flowers, due to abundant heterotrophic tissues and high diffusive resistance along the organ periphery. Chloroplasts within these organs are able to exploit this high CO2 to reduce photorespiration. CO2 concentration can also be enhanced passively by channeling respired CO2 from roots and rhizomes into photosynthetic cells of stems and leaves via lacunae, aerenchyma and the xylem stream. Through passive CO2 concentration, C3 species likely improved their carbon economy and maintained fitness during episodes of low atmospheric CO2. Copyright © 2016 Elsevier Ltd. All rights reserved.

  1. Lasers utilizing CO2 isotopes

    NASA Astrophysics Data System (ADS)

    Pechenin, Yu V.; Domanov, M. S.

    1980-08-01

    The lasing spectra and energy characteristics were investigated for lasers operating with the isotopes 12C16O2, 13C16O2, 12C18O2, and 12C16O18O. It was found that the output power of a laser utilizing the CO2 isotopes was determined by the content of a particular isotope in the carbon dioxide gas. For equal enrichments, all the isotopes investigated, with the exception of 12C16O18O, gave comparable output powers. The unsaturated gains were identical for the most intense transitions of the symmetric molecules; the gain was a factor of two less for the asymmetric molecule. The gain rose linearly with increasing enrichment. The ultimate specific power output, given by the product of the saturation power density and the gain, was practically independent of the enrichment.

  2. End Tidal CO2 Tension

    PubMed Central

    Pugh, Meredith E.; Newman, Alexander L.; Robbins, Ivan M.; Tolle, James; Austin, Eric D.; Newman, John H.

    2011-01-01

    Background: CO2 excretion is impaired in pulmonary arterial hypertension (PAH) due to underlying vascular obstruction and increased dead space. Our aim was to determine whether resting end tidal CO2 (Etco2) could differentiate patients with PAH from those with pulmonary venous hypertension (PVH) or patients without pulmonary hypertension (PH) and whether successful treatment of PAH resulted in higher Etco2 values. Methods: We performed Etco2 measurements for five breaths at rest and after a 6-min walk test (6MWT) in patients seen at our pulmonary vascular center. Mean Etco2 values were correlated with 6-min walk distance and right-sided heart catheterization data. Results: We enrolled 84 patients with PAH, 17 with PVH without left ventricular systolic dysfunction, and seven with no PH and no severe alterations in pulmonary function testing. Etco2 was significantly lower in patients with PAH than in those with no PH and PVH (P < .0001 PAH vs both groups). Etco2 correlated with the pulmonary artery diastolic pressure-to-pulmonary artery occlusion pressure gradient (r = −0.50, P = .0002) and pulmonary vascular resistance (r = −0.44, P = .002). Etco2 after 6MWT correlated with walk distance (r = 0.34, P = .003). In patients with prostaglandin therapy escalation, Etco2 increased in those who had clinical improvement, whereas in patients who did not improve clinically, Etco2 failed to rise (P = .04). Conclusions: Etco2 is a promising tool to differentiate patients with PAH from those with PVH or no PH, correlates with diagnostic and prognostic hemodynamic indicators, and may increase with successful treatment of PAH. PMID:21622547

  3. CO2 Sequestration and Recycle by Photosynthesis

    SciTech Connect

    Steven S.C. Chuang

    2004-02-01

    Visible light-photocatalysis could provide a cost-effective route to recycle CO2 to useful chemicals or fuels. Research is planned to study the reactivity of adsorbates, their role in the photosynthesis reaction, and their relation to the nature of surface sites during photosynthesis of methanol and hydrocarbons from CO{sub 2}/H{sub 2}O. The year two research focus catalyst screening and IR studies. Key research results show Pd/TiO2 exhibits the highest activity for hydrocarbon synthesis from photocatalytic reactions. The in situ IR could successfully monitor the adsorbate hydrocarbon species on Cu/TiO2. Year III research will focus on developing a better understanding of the key factors which control the catalyst activity.

  4. Sources/sinks analysis with satellite sensing for exploring global atmospheric CO2 distributions

    NASA Astrophysics Data System (ADS)

    Shim, C.; Nassar, R.; Kim, J.

    2010-12-01

    There is growing interest in CO2 budget analysis since space-borne measurements of global CO2 distribution have been conducted (e.g, GOSAT project). Here we simulated the global CO2 distribution to estimate individual source/sink contributions. The chemical transport model (GEOS-Chem) was used in order to simulate the global CO2 distribution with updated global sources/sinks with 2°x2.5° horizontal resolution. In addition, 3-D emissions from aviation and chemical oxidation of CO are implemented. The model simulated CO2 amounts were compared with the GOSAT column averaged CO2 column (SWIR L2 data) from April 2009 to May 2010. The seasonal cycles of CO2 concentration were compared and the regional patterns of CO2 distribution are explained by the model with a systemic difference by 1 ~ 2% in the CO2 concentration. In other work, the GEOS-Chem CO2 concentrations show reasonable agreement with GLOBALVIEW-CO2. We further estimated the sources/sinks contributions to the global CO2 budget through 9 tagged CO2 tracers (fossil fuels, ocean exchanges, biomass burning, biofuel burning, balanced biosphere, net terrestrial exchange, ship emissions, aviation emissions, and oxidation from carbon precursors) over the years 2005-2009. Global CO2 concentration shows an increase of 2.1 ppbv/year in which the human fossil fuel and cement emissions are the main driving force (5.0 ppbv/year) for the trend. Net terrestrial and oceanic exchange of CO2 are main sinks (-2.1 ppbv/year and -0.7 ppbv/year, respectively). Our model results will help to suggest the level of reduction in global human CO2 emissions which could control the global CO2 trends in 21th century.

  5. Direct capture of CO2 from ambient air

    DOE PAGES

    Sanz-Perez, Eloy S.; Murdock, Christopher R.; Didas, Stephanie A.; ...

    2016-08-25

    The increase in the global atmospheric CO2 concentration resulting from over a century of combustion of fossil fuels has been associated with significant global climate change. With the global population increase driving continued increases in fossil fuel use, humanity’s primary reliance on fossil energy for the next several decades is assured. Traditional modes of carbon capture such as precombustion and postcombustion CO2 capture from large point sources can help slow the rate of increase of the atmospheric CO2 concentration, but only the direct removal of CO2 from the air, or “direct air capture” (DAC), can actually reduce the global atmosphericmore » CO2 concentration. The past decade has seen a steep rise in the use of chemical sorbents that are cycled through sorption and desorption cycles for CO2 removal from ultradilute gases such as air. This Review provides a historical overview of the field of DAC, along with an exhaustive description of the use of chemical sorbents targeted at this application. Solvents and solid sorbents that interact strongly with CO2 are described, including basic solvents, supported amine and ammonium materials, and metal-organic frameworks (MOFs), as the primary classes of chemical sorbents. Hypothetical processes for the deployment of such sorbents are discussed, as well as the limited array of technoeconomic analyses published on DAC. Overall, it is concluded that there are many new materials that could play a role in emerging DAC technologies. Furthermore, these materials need to be further investigated and developed with a practical sorbent-air contacting process in mind if society is to make rapid progress in deploying DAC as a means of mitigating climate change.« less

  6. Direct Capture of CO2 from Ambient Air.

    PubMed

    Sanz-Pérez, Eloy S; Murdock, Christopher R; Didas, Stephanie A; Jones, Christopher W

    2016-10-12

    The increase in the global atmospheric CO2 concentration resulting from over a century of combustion of fossil fuels has been associated with significant global climate change. With the global population increase driving continued increases in fossil fuel use, humanity's primary reliance on fossil energy for the next several decades is assured. Traditional modes of carbon capture such as precombustion and postcombustion CO2 capture from large point sources can help slow the rate of increase of the atmospheric CO2 concentration, but only the direct removal of CO2 from the air, or "direct air capture" (DAC), can actually reduce the global atmospheric CO2 concentration. The past decade has seen a steep rise in the use of chemical sorbents that are cycled through sorption and desorption cycles for CO2 removal from ultradilute gases such as air. This Review provides a historical overview of the field of DAC, along with an exhaustive description of the use of chemical sorbents targeted at this application. Solvents and solid sorbents that interact strongly with CO2 are described, including basic solvents, supported amine and ammonium materials, and metal-organic frameworks (MOFs), as the primary classes of chemical sorbents. Hypothetical processes for the deployment of such sorbents are discussed, as well as the limited array of technoeconomic analyses published on DAC. Overall, it is concluded that there are many new materials that could play a role in emerging DAC technologies. However, these materials need to be further investigated and developed with a practical sorbent-air contacting process in mind if society is to make rapid progress in deploying DAC as a means of mitigating climate change.

  7. Circulation of waste materials, water, CO2, and O2, and production of food and animal feed within a closed and controlled system comprised of humans, goats, crops, and physical/chemical system

    NASA Astrophysics Data System (ADS)

    Tako, Yasuhiro; Tako, Yasuhiro; Tsuga, Shou-Ichi; Komatsubara, Osamu; Aibe, You-Ichi; Nozoe, Susumu; Arai, Ryuji; Tani, Takashi; Ishioka, Masanao; Masuda, Tsuyoshi; Abe, Koichi; Nakamura, Yuji

    Two humans and two goats inhabited and crops were cultivated within the Closed Ecology Experiment Facilities (CEEF). Circulation of waste in addition to circulation of water, O2 and CO2, and supply of food and animal feed from crops cultivated in the CEEF was conducted in the experiments. The two humans lived and worked in the Plant Module (PM) and the Animal and Human habitation Module (AHM) of the CEEF during 28 days at muximum continuously in 2007.

  8. Sequestration of CO2 by halotolerant algae

    PubMed Central

    2014-01-01

    The potential of halotolerant algae isolated from natural resources was used to study CO2 fixation and algal lipid production. Biological fixation of CO2 in photobioreactor in presence of salinity is exploited. The CO2 concentration 1060 ppm gave the highest biomass yield (700 mg dry wt/l), the highest total lipid content (10.33%) with 80% of CO2 removal. PMID:24847439

  9. Understanding chemical reactions of CO2 and its isoelectronic molecules with 1-butyl-3-methylimidazolium acetate by changing the nature of the cation: the case of CS2 in 1-butyl-1-methylpyrrolidinium acetate studied by NMR spectroscopy and density functional theory calculations.

    PubMed

    Cabaço, M Isabel; Besnard, Marcel; Chávez, Fabián Vaca; Pinaud, Noël; Sebastião, Pedro J; Coutinho, João A P; Danten, Yann

    2014-06-28

    NMR spectroscopy ((1)H, (13)C, (15)N) shows that carbon disulfide reacts spontaneously with 1-butyl-1-methylpyrrolidinium acetate ([BmPyrro][Ac]) in the liquid phase. It is found that the acetate anions play an important role in conditioning chemical reactions with CS2 leading, via coupled complex reactions, to the degradation of this molecule to form thioacetate anion (CH3COS(-)), CO2, OCS, and trithiocarbonate (CS3 (2-)). In marked contrast, the cation does not lead to the formation of any adducts allowing to conclude that, at most, its role consists in assisting indirectly these reactions. The choice of the [BmPyrro](+) cation in the present study allows disentangling the role of the anion and the cation in the reactions. As a consequence, the ensemble of results already reported on CS2-[Bmim][Ac] (1), OCS-[Bmim][Ac] (2), and CO2-[Bmim][Ac] (3) systems can be consistently rationalized. It is argued that in system (1) both anion and cation play a role. The CS2 reacts with the acetate anion leading to the formation of CH3COS(-), CO2, and OCS. After these reactions have proceeded the nascent CO2 and OCS interact with the cation to form imidazolium-carboxylate ([Bmim] CO2) and imidazolium-thiocarboxylate ([Bmim] COS). The same scenario also applies to system (2). In contrast, in the CO2-[Bmim] [Ac] system a concerted cooperative process between the cation, the anion, and the CO2 molecule takes place. A carbene issued from the cation reacts to form the [Bmim] CO2, whereas the proton released by the ring interacts with the anion to produce acetic acid. In all these systems, the formation of adduct resulting from the reaction between the solute molecule and the carbene species originating from the cation is expected. However, this species was only observed in systems (2) and (3). The absence of such an adduct in system (1) has been theoretically investigated using DFT calculations. The values of the energetic barrier of the reactions show that the formation of [Bmim

  10. Public Acceptance for Geological CO2-Storage

    NASA Astrophysics Data System (ADS)

    Schilling, F.; Ossing, F.; Würdemann, H.; Co2SINK Team

    2009-04-01

    for public, press, NGOs,…). - being open for visitors (first of all for the local!) often we informed the public together with the mining authorities - being open for podium discussions and presentation etc. - organized by NGOs, Student groups, press, politics, scientific meetings… Since people usually trust scientists more than politicians and companies, scientists have an enhanced responsibility while informing the public. Once again - always tell the truth and take care of your credibility! In this case, it was most helpful that the project was embedded in the broad scientific activity of research centre which seems to have given the project a positive neutral background. As many people have an undefined fear of all operations in the underground, we tried to address all issues related to storage. Ranging from the transport, injection facility, technical installation, safety of the storage site, the wells, hydraulic system, chemical reactions etc.. When addressing all major concerns before people ask, confidence to the scientists is kept high. We never said that there is absolutely no risk (by the way, nobody would believe that!) we weighted the risk with respect to health, safety and environmental HSE issues. We explained in detail the different trapping mechanisms of the storage operation. This has to be done according to the social groups involved. For the broad public common analogues were helpful: - Trapping in the pore space - a sponge - Trapping through a tight cap rock - a bottle of mineral water with a crown cap as seal - Chemical Trapping - opening of a bottle of mineral water - Well bore integrity - problem of retightening of a bottle with a crown cap - Sucking in of fluid -instead of releasing a sandstone sample standing partly in water - Injecting of CO2 - using a soda machine - Often the concern of burning gas is addressed - showing a CO2 fire extinguisher -CO is poisonous, CO2 not: - drinking soda or even better? champaigne Beyond information of

  11. Throwing new light on the reduction of CO2.

    PubMed

    Ozin, Geoffrey A

    2015-03-18

    While the chemical energy in fossil fuels has enabled the rapid rise of modern civilization, their utilization and accompanying anthropogenic CO2 emissions is occurring at a rate that is outpacing nature's carbon cycle. Its effect is now considered to be irreversible and this could lead to the demise of human society. This is a complex issue without a single solution, yet from the burgeoning global research activity and development in the field of CO2 capture and utilization, there is light at the end of the tunnel. In this article a couple of recent advances are illuminated. Attention is focused on the discovery of gas-phase, light-assisted heterogeneous catalytic materials and processes for CO2 photoreduction that operate at sufficiently high rates and conversion efficiencies, and under mild conditions, to open a new pathway for an energy transition from today's "fossil fuel economy" to a new and sustainable "CO2 economy". Whichever of the competing CO2 capture and utilization approaches proves to be the best way forward for the development of a future CO2-based solar fuels economy, hopefully this can occur in a period short enough to circumvent the predicted adverse consequences of greenhouse gas climate change.

  12. Sorbents for CO2 capture from high carbon fly ashes.

    PubMed

    Maroto-Valer, M Mercedes; Lu, Zhe; Zhang, Yinzhi; Tang, Zhong

    2008-11-01

    Fly ashes with high-unburned-carbon content, referred to as fly ash carbons, are an increasing problem for the utility industry, since they cannot be marketed as a cement extender and, therefore, have to be disposed. Previous work has explored the potential development of amine-enriched fly ash carbons for CO2 capture. However, their performance was lower than that of commercially available sorbents, probably because the samples investigated were not activated prior to impregnation and, therefore, had a very low surface area. Accordingly, the work described here focuses on the development of activated fly ash derived sorbents for CO2 capture. The samples were steam activated at 850 degrees C, resulting in a significant increase of the surface area (1075 m2/g). The activated samples were impregnated with different amine compounds, and the resultant samples were tested for CO2 capture at different temperatures. The CO2 adsorption of the parent and activated samples is typical of a physical adsorption process. The impregnation process results in a decrease of the surface areas, indicating a blocking of the porosity. The highest adsorption capacity at 30 and 70 degrees C for the amine impregnated activated carbons was probably due to a combination of physical adsorption inherent from the parent sample and chemical adsorption of the loaded amine groups. The CO2 adsorption capacities for the activated amine impregnated samples are higher than those previously published for fly ash carbons without activation (68.6 vs. 45 mg CO2/g sorbent).

  13. High-Density Nanosharp Microstructures Enable Efficient CO2 Electroreduction.

    PubMed

    Saberi Safaei, Tina; Mepham, Adam; Zheng, Xueli; Pang, Yuanjie; Dinh, Cao-Thang; Liu, Min; Sinton, David; Kelley, Shana O; Sargent, Edward H

    2016-11-09

    Conversion of CO2 to CO powered by renewable electricity not only reduces CO2 pollution but also is a means to store renewable energy via chemical production of fuels from CO. However, the kinetics of this reaction are slow due its large energetic barrier. We have recently reported CO2 reduction that is considerably enhanced via local electric field concentration at the tips of sharp gold nanostructures. The high local electric field enhances CO2 concentration at the catalytic active sites, lowering the activation barrier. Here we engineer the nucleation and growth of next-generation Au nanostructures. The electroplating overpotential was manipulated to generate an appreciably increased density of honed nanoneedles. Using this approach, we report the first application of sequential electrodeposition to increase the density of sharp tips in CO2 electroreduction. Selective regions of the primary nanoneedles are passivated using a thiol SAM (self-assembled monolayer), and then growth is concentrated atop the uncovered high-energy planes, providing new nucleation sites that ultimately lead to an increase in the density of the nanosharp structures. The two-step process leads to a new record in CO2 to CO reduction, with a geometric current density of 38 mA/cm(2) at -0.4 V (vs reversible hydrogen electrode), and a 15-fold improvement over the best prior reports of electrochemical surface area (ECSA) normalized current density.

  14. Solvation of Esters and Ketones in Supercritical CO2.

    PubMed

    Kajiya, Daisuke; Imanishi, Masayoshi; Saitow, Ken-ichi

    2016-02-04

    Vibrational Raman spectra for the C═O stretching modes of three esters with different functional groups (methyl, a single phenyl, and two phenyl groups) were measured in supercritical carbon dioxide (scCO2). The results were compared with Raman spectra for three ketones involving the same functional groups, measured at the same thermodynamic states in scCO2. The peak frequencies of the Raman spectra of these six solute molecules were analyzed by decomposition into the attractive and repulsive energy components, based on the perturbed hard-sphere theory. For all solute molecules, the attractive energy is greater than the repulsive energy. In particular, a significant difference in the attractive energies of the ester-CO2 and ketone-CO2 systems was observed when the methyl group is attached to the ester or ketone. This difference was significantly reduced in the solute systems with a single phenyl group and was completely absent in those with two phenyl groups. The optimized structures among the solutes and CO2 molecules based on quantum chemical calculations indicate that greater attractive energy is obtained for a system where the oxygen atom of the ester is solvated by CO2 molecules.

  15. Aminosilicone solvents for CO(2) capture.

    PubMed

    Perry, Robert J; Grocela-Rocha, Teresa A; O'Brien, Michael J; Genovese, Sarah; Wood, Benjamin R; Lewis, Larry N; Lam, Hubert; Soloveichik, Grigorii; Rubinsztajn, Malgorzata; Kniajanski, Sergei; Draper, Sam; Enick, Robert M; Johnson, J Karl; Xie, Hong-bin; Tapriyal, Deepak

    2010-08-23

    This work describes the first report of the use of an aminosilicone solvent mix for the capture of CO(2). To maintain a liquid state, a hydroxyether co-solvent was employed which allowed enhanced physisorption of CO(2) in the solvent mixture. Regeneration of the capture solvent system was demonstrated over 6 cycles and absorption isotherms indicate a 25-50 % increase in dynamic CO(2) capacity over 30 % MEA. In addition, proof of concept for continuous CO(2) absorption was verified. Additionally, modeling to predict heats of reaction of aminosilicone solvents with CO(2) was in good agreement with experimental results.

  16. Isotopic CO2 Instrumentation for UAV Measurements

    NASA Astrophysics Data System (ADS)

    Gomez, A.; Silver, J.

    2013-12-01

    Carbon dioxide is the largest component of anthroprogenic green house gas emissions. Knowing atmospheric 13CO2/12CO2 ratios precisely is important for understanding biogenic and anthroprogenic sources and sinks for carbon. Instrumentation mounted on UAV aircraft would enable important spatial isotopic CO2 information. However, current isotopic CO2 instrumentation have unfavorable attributes for UAV use, such as high power requirements, high cost, high weight, and large size. Here we present the early development of a compact isotopic CO2 instrument that is designed to nullify effects of pressure, temperature and moisture, and will ultimately be suitable for UAV deployment.

  17. Forest succession at elevated CO2

    SciTech Connect

    Clark, James S.; Schlesinger, William H.

    2002-02-01

    We tested hypotheses concerning the response of forest succession to elevated CO2 in the FACTS-1 site at the Duke Forest. We quantified growth and survival of naturally recruited seedlings, tree saplings, vines, and shrubs under ambient and elevated CO2. We planted seeds and seedlings to augment sample sites. We augmented CO2 treatments with estimates of shade tolerance and nutrient limitation while controlling for soil and light effects to place CO2 treatments within the context of natural variability at the site. Results are now being analyzed and used to parameterize forest models of CO2 response.

  18. Continental-scale variation in controls of summer CO2 in United States lakes

    NASA Astrophysics Data System (ADS)

    Lapierre, Jean-Francois; Seekell, David A.; Filstrup, Christopher T.; Collins, Sarah M.; Emi Fergus, C.; Soranno, Patricia A.; Cheruvelil, Kendra S.

    2017-04-01

    Understanding the broad-scale response of lake CO2 dynamics to global change is challenging because the relative importance of different controls of surface water CO2 is not known across broad geographic extents. Using geostatistical analyses of 1080 lakes in the conterminous United States, we found that lake partial pressure of CO2 (pCO2) was controlled by different chemical and biological factors related to inputs and losses of CO2 along climate, topography, geomorphology, and land use gradients. Despite weak spatial patterns in pCO2 across the study extent, there were strong regional patterns in the pCO2 driver-response relationships, i.e., in pCO2 "regulation." Because relationships between lake CO2 and its predictors varied spatially, global models performed poorly in explaining the variability in CO2 for U.S. lakes. The geographically varying driver-response relationships of lake pCO2 reflected major landscape gradients across the study extent and pointed to the importance of regional-scale variation in pCO2 regulation. These results indicate a higher level of organization for these physically disconnected systems than previously thought and suggest that changes in climate and land use could induce shifts in the main pathways that determine the role of lakes as sources and sinks of atmospheric CO2.

  19. Thermal injuries as a result of CO2 laser resurfacing.

    PubMed

    Grossman, A R; Majidian, A M; Grossman, P H

    1998-09-01

    CO2 laser resurfacing of the face for fine wrinkles has gained great popularity over a short period of time. The use of the CO2 laser has proven to be effective in reducing or eliminating fine wrinkles. This tool in the surgeon's armamentarium has been added to those of dermabrasion and chemical peel. The theoretical advantage of the use of the CO2 laser for resurfacing has been better accuracy and reportedly more control of the depth of penetration. The use of the CO2 laser has been welcomed by many cosmetic surgeons. Until now, there have been few reported cases of complications with the use of the CO2 laser. To many, this would sound too good to be true; unfortunately, that is the case. The CO2 laser is a high-energy machine that can indeed cause thermal injury. This thermal injury can result in deep burns to the skin and hypertrophic scarring. We feel this is more common than is currently being reported, and we share our experience as a burn and wound care referral service. During an 18-month period, 20 consecutive patients were referred to our practice who had received injuries from the CO2 laser resurfacing laser. We present here in this review a summary of those injuries. The CO2 resurfacing laser is a very effective tool for the treatment of fine wrinkles, but it is not without the potential for serious complications. We urge caution with the use of the laser and prompt recognition and treatment of thermal injury to the skin.

  20. Reversible Acid Gas Capture Using CO2-Binding Organic Liquids

    SciTech Connect

    Heldebrant, David J.; Koech, Phillip K.; Yonker, Clement R.; Rainbolt, James E.; Zheng, Feng

    2010-08-31

    Acid gas scrubbing technology is predominantly aqueous alkanolamine based. Of the acid gases, CO2, H2S and SO2 have been shown to be reversible, however there are serious disadvantages with corrosion and high regeneration costs. The primary scrubbing system composed of monoethanolamine is limited to 30% by weight because of the highly corrosive solution. This gravimetric limitation limits the CO2 volumetric (≤108 g/L) and gravimetric capacity (≤7 wt%) of the system. Furthermore the scrubbing system has a large energy penalty from pumping and heating the excess water required to dissolve the MEA bicarbonate salt. Considering the high specific heat of water (4 j/g-1K-1), low capacities and the high corrosion we set out to design a fully organic solvent that can chemically bind all acid gases i.e. CO2 as reversible alkylcarbonate ionic liquids or analogues thereof. Having a liquid acid gas carrier improves process economics because there is no need for excess solvent to pump and to heat. We have demonstrated illustrated in Figure 1, that CO2-binding organic liquids (CO2BOLs) have a high CO2 solubility paired with a much lower specific heat (<1.5 J/g-1K-1) than aqueous systems. CO2BOLs are a subsection of a larger class of materials known as Binding Organic Liquids (BOLs). Our BOLs have been shown to reversibly bind and release COS, CS2, and SO2, which we denote COSBOLS, CS2BOLs and SO2BOLs. Our BOLs are highly tunable and can be designed for post or pre-combustion gas capture. The design and testing of the next generation zwitterionic CO2BOLs and SO2BOLs are presented.

  1. Microbial Growth under Supercritical CO2

    PubMed Central

    Peet, Kyle C.; Freedman, Adam J. E.; Hernandez, Hector H.; Britto, Vanya; Boreham, Chris; Ajo-Franklin, Jonathan B.

    2015-01-01

    Growth of microorganisms in environments containing CO2 above its critical point is unexpected due to a combination of deleterious effects, including cytoplasmic acidification and membrane destabilization. Thus, supercritical CO2 (scCO2) is generally regarded as a sterilizing agent. We report isolation of bacteria from three sites targeted for geologic carbon dioxide sequestration (GCS) that are capable of growth in pressurized bioreactors containing scCO2. Analysis of 16S rRNA genes from scCO2 enrichment cultures revealed microbial assemblages of varied complexity, including representatives of the genus Bacillus. Propagation of enrichment cultures under scCO2 headspace led to isolation of six strains corresponding to Bacillus cereus, Bacillus subterraneus, Bacillus amyloliquefaciens, Bacillus safensis, and Bacillus megaterium. Isolates are spore-forming, facultative anaerobes and capable of germination and growth under an scCO2 headspace. In addition to these isolates, several Bacillus type strains grew under scCO2, suggesting that this may be a shared feature of spore-forming Bacillus spp. Our results provide direct evidence of microbial activity at the interface between scCO2 and an aqueous phase. Since microbial activity can influence the key mechanisms for permanent storage of sequestered CO2 (i.e., structural, residual, solubility, and mineral trapping), our work suggests that during GCS microorganisms may grow and catalyze biological reactions that influence the fate and transport of CO2 in the deep subsurface. PMID:25681188

  2. Microbial growth under supercritical CO2.

    PubMed

    Peet, Kyle C; Freedman, Adam J E; Hernandez, Hector H; Britto, Vanya; Boreham, Chris; Ajo-Franklin, Jonathan B; Thompson, Janelle R

    2015-04-01

    Growth of microorganisms in environments containing CO2 above its critical point is unexpected due to a combination of deleterious effects, including cytoplasmic acidification and membrane destabilization. Thus, supercritical CO2 (scCO2) is generally regarded as a sterilizing agent. We report isolation of bacteria from three sites targeted for geologic carbon dioxide sequestration (GCS) that are capable of growth in pressurized bioreactors containing scCO2. Analysis of 16S rRNA genes from scCO2 enrichment cultures revealed microbial assemblages of varied complexity, including representatives of the genus Bacillus. Propagation of enrichment cultures under scCO2 headspace led to isolation of six strains corresponding to Bacillus cereus, Bacillus subterraneus, Bacillus amyloliquefaciens, Bacillus safensis, and Bacillus megaterium. Isolates are spore-forming, facultative anaerobes and capable of germination and growth under an scCO2 headspace. In addition to these isolates, several Bacillus type strains grew under scCO2, suggesting that this may be a shared feature of spore-forming Bacillus spp. Our results provide direct evidence of microbial activity at the interface between scCO2 and an aqueous phase. Since microbial activity can influence the key mechanisms for permanent storage of sequestered CO2 (i.e., structural, residual, solubility, and mineral trapping), our work suggests that during GCS microorganisms may grow and catalyze biological reactions that influence the fate and transport of CO2 in the deep subsurface.

  3. Autotrophic and heterotrophic soil respiration determined with trenching, soil CO2 fluxes and 13CO2/12CO2 concentration gradients in a boreal forest ecosystem

    NASA Astrophysics Data System (ADS)

    Pumpanen, Jukka; Shurpali, Narasinha; Kulmala, Liisa; Kolari, Pasi; Heinonsalo, Jussi

    2017-04-01

    Soil CO2 efflux forms a substantial part of the ecosystem carbon balance, and it can contribute more than half of the annual ecosystem respiration. Recently assimilated carbon which has been fixed in photosynthesis during the previous days plays an important role in soil CO2 efflux, and its contribution is seasonally variable. Moreover, the recently assimilated C has been shown to stimulate the decomposition of recalcitrant C in soil and increase the mineralization of nitrogen, the most important macronutrient limiting gross primary productivity (GPP) in boreal ecosystems. Podzolic soils, typical in boreal zone, have distinctive layers with different biological and chemical properties. The biological activity in different soil layers has large seasonal variation due to vertical gradient in temperature, soil organic matter and root biomass. Thus, the source of CO2 and its components have a vertical gradient which is seasonally variable. The contribution of recently assimilated C and its seasonal as well as spatial variation in soil are difficult to assess without disturbing the system. The most common method of partitioning soil respiration into its components is trenching which entails the roots being cut or girdling where the flow of carbohydrates from the canopy to roots has been isolated by cutting of the phloem. Other methods for determining the contribution of autotrophic (Ra) and heterotrophic (Rh) respiration components in soil CO2 efflux are pulse labelling with 13CO2 or 14CO2 or the natural abundance of 13C and/or 14C isotopes. Also differences in seasonal and short-term temperature response of soil respiration have been used to separate Ra and Rh. We compared the seasonal variation in Ra and Rh using the trenching method and differences between seasonal and short-term temperature responses of soil respiration. I addition, we estimated the vertical variation in soil biological activity using soil CO2 concentration and the natural abundance of 13C and 12C

  4. Amine scrubbing for CO2 capture.

    PubMed

    Rochelle, Gary T

    2009-09-25

    Amine scrubbing has been used to separate carbon dioxide (CO2) from natural gas and hydrogen since 1930. It is a robust technology and is ready to be tested and used on a larger scale for CO2 capture from coal-fired power plants. The minimum work requirement to separate CO2 from coal-fired flue gas and compress CO2 to 150 bar is 0.11 megawatt-hours per metric ton of CO2. Process and solvent improvements should reduce the energy consumption to 0.2 megawatt-hour per ton of CO2. Other advanced technologies will not provide energy-efficient or timely solutions to CO2 emission from conventional coal-fired power plants.

  5. Heterogeneous catalytic conversion of CO2: a comprehensive theoretical review

    NASA Astrophysics Data System (ADS)

    Li, Yawei; Chan, Siew Hwa; Sun, Qiang

    2015-05-01

    The conversion of CO2 into fuels and useful chemicals has been intensively pursued for renewable, sustainable and green energy. However, due to the negative adiabatic electron affinity (EA) and large ionization potential (IP), the CO2 molecule is chemically inert, thus making the conversion difficult under normal conditions. Novel catalysts, which have high stability, superior efficiency and low cost, are urgently needed to facilitate the conversion. As the first step to design such catalysts, understanding the mechanisms involved in CO2 conversion is absolutely indispensable. In this review, we have summarized the recent theoretical progress in mechanistic studies based on density functional theory, kinetic Monte Carlo simulation, and microkinetics modeling. We focus on reaction channels, intermediate products, the key factors determining the conversion of CO2 in solid-gas interface thermocatalytic reduction and solid-liquid interface electrocatalytic reduction. Furthermore, we have proposed some possible strategies for improving CO2 electrocatalysis and also discussed the challenges in theory, model construction, and future research directions.

  6. CO2 Sequestration in Unmineable Coal Seams: Potential Environmental Impacts

    SciTech Connect

    Hedges, S.W.; Soong, Yee; McCarthy Jones, J.R.; Harrison, D.K.; Irdi, G.A.; Frommell, E.A.; Dilmore, R.M.; Pique, P.J.; Brown, T.D

    2005-09-01

    An initial investigation into the potential environmental impacts of CO2 sequestration in unmineable coal seams has been conducted, focusing on changes in the produced water during enhanced coalbed methane (ECBM) production using a CO2 injection process (CO2-ECBM). Two coals have been used in this study, the medium volatile bituminous Upper Freeport coal (APCS 1) of the Argonne Premium Coal Samples series, and an as-mined Pittsburgh #8 coal, which is a high volatile bituminous coal. Coal samples were reacted with either synthetic produced water or field collected produced water and gaseous carbon dioxide at 40 οC and 50 bar to evaluate the potential for mobilizing toxic metals during CO2-ECBM/sequestration. Microscopic and x-ray diffraction analysis of the post-reaction coal samples clearly show evidence of chemical reaction, and chemical analysis of the produced water shows substantial changes in composition. These results suggest that changes to the produced water chemistry and the potential for mobilizing toxic trace elements from coalbeds are important factors to be considered when evaluating deep, unmineable coal seams for CO2 sequestration.

  7. Eliminating Glutaraldehyde from Crosslinked Collagen Films using Supercritical CO2.

    PubMed

    Casali, Dominic M; Yost, Michael J; Matthews, Michael A

    2017-09-04

    Collagen has received considerable attention as a biomaterial for tissue engineering because of its low immunogenicity, controllable biodegradation, and ability to influence cell growth and proliferation. Frequently, collagen scaffolds require crosslinking to improve mechanical strength, requiring agents like glutaraldehyde that have high residual cytotoxicity. A novel method for extracting residual glutaraldehyde from crosslinked collagen films with supercritical carbon dioxide (CO2 ) is presented. CO2 is a non-toxic, non-flammable substance that is relatively inert and can be used to process biomaterials at mild pressures and physiologic temperatures. In this work, it was first determined that type I collagen is chemically compatible with both liquid and supercritical CO2 . Treated collagen showed minimal changes in physico-chemical properties as determined by differential scanning calorimetry, gel electrophoresis, and circular dichroism. CO2 was subsequently used to extract residual glutaraldehyde from crosslinked collagen films. Glutaraldehyde concentration was reduced by over 95%, from over 20 ppm before treatment to about 1 ppm, in only 1 hour. CO2 treatment caused negligible alteration of thermal stability, but did significantly increase film stiffness and tensile strength. However, these changes were minor compared to heat-based removal of glutaraldehyde. This article is protected by copyright. All rights reserved. © 2017 Wiley Periodicals, Inc.

  8. Water-CO2 Mixtures Under Extreme Conditions

    NASA Astrophysics Data System (ADS)

    Plattner, D. L.; Somayazulu, M.

    2010-12-01

    In situ high pressure-temperature Raman spectroscopy was used to investigate the formation of clathrates in water-CO2 mixtures and to study the chemical interactions between water and CO2 at supercritical conditions. Diamond anvil cell’s (DAC) were loaded with ruby, water, CO2, and a gold plated gasket. Quartz was later added to the cell as a pressure sensor for supercritical phase analysis. At 25 °C and within the pressure range of 0.8 to 2.6 GPa, no clathrate was observed. Our results confirm recent findings which also dispute claims of clathrate existence at our conditions. A decrease in the temperature required to reach the supercritical phase of water-CO2 mixtures was observed from 0.35 GPa to 4.5 GPa. Furthermore, at 4.4 GPa and 290 °C, a chemical reaction between CO2 and water occurred. The resulting compound has a Raman peak with a frequency shift of 1000 cm-1. This reaction and the compound it produces are of great interest and are currently being investigated.

  9. CO2 Annual and Semiannual Cycles from Satellite Retrievals and Models

    NASA Astrophysics Data System (ADS)

    Jiang, X.; Crisp, D.; Olsen, E. T.; Kulawik, S. S.; Miller, C. E.; Pagano, T. S.; Yung, Y. L.

    2014-12-01

    We have compared satellite CO2 retrievals from the Greenhouse gases Observing SATellite (GOSAT), Atmospheric Infrared Sounder (AIRS), and Tropospheric Emission Spectrometer (TES) with in-situ measurements from the Earth System Research Laboratory (NOAA-ESRL) Surface CO2 and Total Carbon Column Observing Network (TCCON), and utilized zonal means to characterize variability and distribution of CO2. In general, zonally averaged CO2 from the three satellite data sets are consistent with the surface and TCCON XCO2 data. Retrievals of CO2 from the three satellites show more (less) CO2 in the northern hemisphere than that in the southern hemisphere in the northern hemispheric winter (summer) season. The difference between the three satellite CO2 retrievals might be related to the different averaging kernels in the satellites CO2 retrievals. A multiple regression method was used to calculate the CO2 annual cycle and semiannual cycle amplitudes from different satellite CO2 retrievals. The CO2 annual cycle and semiannual cycle amplitudes are largest at the surface, as seen in the NOAA-ESRL CO2 data sets. The CO2 annual cycle and semiannual cycle amplitudes in the GOSAT XCO2, AIRS mid-tropospheric CO2, and TES mid-tropospheric CO2 are smaller compared with those from the surface CO2. Similar regression analysis was applied to the Model for OZone And Related chemical Tracers-2 (MOZART-2) and CarbonTracker model CO2. The convolved model CO2 annual cycle and semiannual cycle amplitudes are similar to those from the satellite CO2 retrievals, although the model tends to under-estimate the CO2 seasonal cycle amplitudes in the northern hemisphere mid-latitudes from the comparison with GOSAT and TES CO2 and underestimate the CO2 semi-annual cycle amplitudes in the high latitudes from the comparison with AIRS CO2. The difference between model and satellite CO2 can be used to identify possible deficiency in the model and improve the model in the future.

  10. CO2 Sparging Phase 3 Full Scale Implementation and Monitoring Report

    EPA Pesticide Factsheets

    In-situ carbon dioxide (CO2) sparging was designed and implemented to treat a subsurface causticbrine pool (CBP) formed as a result of releases from historical production of industrial chemicals at theLCP Chemicals Site, Brunswick, GA (Site).

  11. Fourier Transform Microwave Spectra of CO{2}-ETHYLENE Sulfide, CO{2}-ETHYLENE Oxide and CO{2}-PROPYLENE Oxide Complexes

    NASA Astrophysics Data System (ADS)

    Orita, Yukari; Kawashima, Yoshiyuki; Hirota, Eizi

    2010-06-01

    We have previously examined the difference in roles of O and S in structure and dynamics of the CO-ethylene oxide (EO) and CO-ethylene sulfide (ES) complexes. We have extended the investigation to CO{2}-EO and CO{2}-ES for comparison. We have also observed the CO{2}-propylene oxide (PO) complex, which is an important intermediate in the reaction of PO with CO{2} leading to polycarbonate. Both a-type and b-type transitions were observed for the CO{2}-EO and CO{2}-ES, but no c-type transitions were observed at all. We also detected the {34}S and {13}C isotopic species in natural abundance and the species containing {18}OCO and C{18}O% {2}, which were synthesized by burning paper in an {18}O{2} and{% 16}O{2} mixture. By analyzing the observed spectra we concluded the CO{2} moiety of CO{2}-EO and CO{2}-ES located in a plane % prependicular to the three-membered ring and bisecting the COC or CSC angle of EO or ES, respectively, as in the case of CO-EO and CO-ES complexes. An % ab initio MO calculation at the level of MP2/6-311G(d, p) yielded an optimized structure in good agreement with the experimental result. We have derived from the observed spectra the distance, the stretching force constant, and the binding energy of the bonds between the constituents of the CO{2}-EO and CO{2}-ES complexes and have found that the distances of the two complexes were shorter by 0.2Å than those in CO-EO and CO-ES, respectively, and that the intermolecular bonds were two times stronger in the CO{2} complexes than in the corresponding CO complexes. We have concluded from the observed spectra that the CO{2} moiety in CO{2}-PO is located on the PO three-membered ring plane opposite to the methyl group. The constituents in CO{2}-PO were more weakly bound than those in CO{2}-EO and CO{2}-ES. S. Sato, Y. Kawashima, Y. Tatamitani, and E. Hirota, 63rd International Symposium on Molecular Spectroscopy, WF05 (2008).

  12. Geophysical Implications of Enceladus' CO2 Frost

    NASA Astrophysics Data System (ADS)

    Matson, D.; Davies, A. G.; Johnson, T. V.; Castillo, J. C.; Lunine, J. I.

    2013-12-01

    CO2 frost has been reported on the surface of Enceladus [1]. We suggest that the frost originated from shallow gas pockets below the surface. These pockets are a natural consequence of the ocean water circulation hypothesis [2]. They are different from the plume chambers [3] and would constitute a previously unrecognized structure in the surface. The oceanic circulation uses gas bubbles to make seawater buoyant and bring up water, chemicals, and heat from a warm ocean at depth [2]. The ocean water rises through the icy crust and near the surface it spreads out laterally beneath a relatively thin ice cap, following the pattern indicated by the thermal anomalies identified in Cassini data [4,5]. Topography on the bottom of this cap ice is conducive to the formation of gas pockets. As the ocean water flows horizontally, the gas bubbles in it continue to rise vertically. Even though their vertical migration may be slow and even if the flow is relatively turbulent, some bubbles reach recesses in the bottom of the ice cap and, over time, pop and form gas pockets. The gas pockets are envisioned as being ruptured by the regular fissuring of ice in the South Polar Region. Hurford et al. [6] have modelled the tidally controlled openings of rifts in the SPR. If one of these rifts reaches a gas pocket, CO2 gas may come to the surface. The tortuosity and other properties of its route will determine if it vents as a seep or a jet. If enough gas is vented and the molecules in the transient cloud have many collisions, some of them will be scattered to the surface and freeze. It was noted by Brown, et al. [1] that the frost deposits may not be permanent and that an active replenishment processes might be necessary. Studies of CO2 frost on Iapetus suggest that migration can be significant [7]. This work was performed at the Jet Propulsion Laboratory, California Institute of Technology, under contract to NASA. al., Science 311, 1425-1428, 2006. [2] Matson D. L. et al., Icarus 221, 53

  13. Simulation of CO 2 concentrations at Tsukuba tall tower using WRF-CO 2 tracer transport model

    NASA Astrophysics Data System (ADS)

    Ballav, Srabanti; Patra, Prabir K.; Sawa, Yousuke; Matsueda, Hidekazu; Adachi, Ahoro; Onogi, Shigeru; Takigawa, Masayuki; de, Utpal K.

    2016-02-01

    Simulation of carbon dioxide (CO2) at hourly/weekly intervals and fine vertical resolution at the continental or coastal sites is challenging because of coarse horizontal resolution of global transport models. Here the regional Weather Research and Forecasting (WRF) model coupled with atmospheric chemistry is adopted for simulating atmospheric CO2 (hereinafter WRF-CO2) in nonreactive chemical tracer mode. Model results at horizontal resolution of 27 × 27 km and 31 vertical levels are compared with hourly CO2 measurements from Tsukuba, Japan (36.05°N, 140.13 oE) at tower heights of 25 and 200 m for the entire year 2002. Using the wind rose analysis, we find that the fossil fuel emission signal from the megacity Tokyo dominates the diurnal, synoptic and seasonal variations observed at Tsukuba. Contribution of terrestrial biosphere fluxes is of secondary importance for CO2 concentration variability. The phase of synoptic scale variability in CO2 at both heights are remarkably well simulated the observed data (correlation coefficient >0.70) for the entire year. The simulations of monthly mean diurnal cycles are in better agreement with the measurements at lower height compared to that at the upper height. The modelled vertical CO2 gradients are generally greater than the observed vertical gradient. Sensitivity studies show that the simulation of observed vertical gradient can be improved by increasing the number of vertical levels from 31 in the model WRF to 37 (4 below 200 m) and using the Mellor-Yamada-Janjic planetary boundary scheme. These results have large implications for improving transport model simulation of CO2 over the continental sites.

  14. Variability in soil CO2 production and surface CO2 efflux across riparian-hillslope transitions

    Treesearch

    Vincent Jerald. Pacific

    2007-01-01

    The spatial and temporal controls on soil CO2 production and surface CO2 efflux have been identified as an outstanding gap in our understanding of carbon cycling. I investigated both the spatial and temporal variability of soil CO2 concentrations and surface CO2 efflux across eight topographically distinct riparian-hillslope transitions in the ~300 ha subalpine upper-...

  15. CO2 transport over complex terrain

    USGS Publications Warehouse

    Sun, Jielun; Burns, Sean P.; Delany, A.C.; Oncley, S.P.; Turnipseed, A.A.; Stephens, B.B.; Lenschow, D.H.; LeMone, M.A.; Monson, Russell K.; Anderson, D.E.

    2007-01-01

    CO2 transport processes relevant for estimating net ecosystem exchange (NEE) at the Niwot Ridge AmeriFlux site in the front range of the Rocky Mountains, Colorado, USA, were investigated during a pilot experiment. We found that cold, moist, and CO2-rich air was transported downslope at night and upslope in the early morning at this forest site situated on a ???5% east-facing slope. We found that CO2 advection dominated the total CO2 transport in the NEE estimate at night although there are large uncertainties because of partial cancellation of horizontal and vertical advection. The horizontal CO2 advection captured not only the CO2 loss at night, but also the CO2 uptake during daytime. We found that horizontal CO2 advection was significant even during daytime especially when turbulent mixing was not significant, such as in early morning and evening transition periods and within the canopy. Similar processes can occur anywhere regardless of whether flow is generated by orography, synoptic pressure gradients, or surface heterogeneity as long as CO2 concentration is not well mixed by turbulence. The long-term net effect of all the CO2 budget terms on estimates of NEE needs to be investigated. ?? 2007 Elsevier B.V. All rights reserved.

  16. Covalent Organic Frameworks for CO2 Capture.

    PubMed

    Zeng, Yongfei; Zou, Ruqiang; Zhao, Yanli

    2016-04-20

    As an emerging class of porous crystalline materials, covalent organic frameworks (COFs) are excellent candidates for various applications. In particular, they can serve as ideal platforms for capturing CO2 to mitigate the dilemma caused by the greenhouse effect. Recent research achievements using COFs for CO2 capture are highlighted. A background overview is provided, consisting of a brief statement on the current CO2 issue, a summary of representative materials utilized for CO2 capture, and an introduction to COFs. Research progresses on: i) experimental CO2 capture using different COFs synthesized based on different covalent bond formations, and ii) computational simulation results of such porous materials on CO2 capture are summarized. Based on these experimental and theoretical studies, careful analyses and discussions in terms of the COF stability, low- and high-pressure CO2 uptake, CO2 selectivity, breakthrough performance, and CO2 capture conditions are provided. Finally, a perspective and conclusion section of COFs for CO2 capture is presented. Recent advancements in the field are highlighted and the strategies and principals involved are discussed.

  17. CO2 flux from Javanese mud volcanism.

    PubMed

    Queißer, M; Burton, M R; Arzilli, F; Chiarugi, A; Marliyani, G I; Anggara, F; Harijoko, A

    2017-06-01

    Studying the quantity and origin of CO2 emitted by back-arc mud volcanoes is critical to correctly model fluid-dynamical, thermodynamical, and geochemical processes that drive their activity and to constrain their role in the global geochemical carbon cycle. We measured CO2 fluxes of the Bledug Kuwu mud volcano on the Kendeng Fold and thrust belt in the back arc of Central Java, Indonesia, using scanning remote sensing absorption spectroscopy. The data show that the expelled gas is rich in CO2 with a volume fraction of at least 16 vol %. A lower limit CO2 flux of 1.4 kg s(-1) (117 t d(-1)) was determined, in line with the CO2 flux from the Javanese mud volcano LUSI. Extrapolating these results to mud volcanism from the whole of Java suggests an order of magnitude total CO2 flux of 3 kt d(-1), comparable with the expected back-arc efflux of magmatic CO2. After discussing geochemical, geological, and geophysical evidence we conclude that the source of CO2 observed at Bledug Kuwu is likely a mixture of thermogenic, biogenic, and magmatic CO2, with faulting controlling potential pathways for magmatic fluids. This study further demonstrates the merit of man-portable active remote sensing instruments for probing natural gas releases, enabling bottom-up quantification of CO2 fluxes.

  18. Earth's Atmospheric CO2 Saturated IR Absorption

    NASA Astrophysics Data System (ADS)

    Wall, Ernst

    2008-10-01

    Using the on-line SpectraCalc IR absorption simulator, the amount of IR absorption by the 15 μ line of the current atmospheric CO2 was obtained and compared with that of twice the amount of CO2. The simulation required a fixed density equivalent for the atmospheric path length. This was obtained by numerically integrating the NOAA Standard Atmospheric model. While the current line is saturated, doubling the CO2 will cause a slight width increase. Using this and the blackbody radiation curve plus considering the effects of water vapor, the temperature rise of the Earth will be less than 2.5 deg. C. Integrating a NASA Martian atmospheric model, we find that the Martian atmosphere has 45 times more CO2 to penetrate than Earth, and yet, the Martian diurnal temperature swings exceed those of the Sahara desert. I.e., large amounts of CO2 alone do not necessarily cause planetary warming. As the oceans warm from any cause, more CO2 is boiled out, but if they cool, they will absorb more CO2 just as a carbonated drink does, so that temperature and CO2 density will correlate. It is to be noted that the Earth's known petroleum reserves contain only enough CO2 to increase the atmospheric CO2 by some 15%.

  19. CO2 flux from Javanese mud volcanism

    NASA Astrophysics Data System (ADS)

    Queißer, M.; Burton, M. R.; Arzilli, F.; Chiarugi, A.; Marliyani, G. I.; Anggara, F.; Harijoko, A.

    2017-06-01

    Studying the quantity and origin of CO2 emitted by back-arc mud volcanoes is critical to correctly model fluid-dynamical, thermodynamical, and geochemical processes that drive their activity and to constrain their role in the global geochemical carbon cycle. We measured CO2 fluxes of the Bledug Kuwu mud volcano on the Kendeng Fold and thrust belt in the back arc of Central Java, Indonesia, using scanning remote sensing absorption spectroscopy. The data show that the expelled gas is rich in CO2 with a volume fraction of at least 16 vol %. A lower limit CO2 flux of 1.4 kg s-1 (117 t d-1) was determined, in line with the CO2 flux from the Javanese mud volcano LUSI. Extrapolating these results to mud volcanism from the whole of Java suggests an order of magnitude total CO2 flux of 3 kt d-1, comparable with the expected back-arc efflux of magmatic CO2. After discussing geochemical, geological, and geophysical evidence we conclude that the source of CO2 observed at Bledug Kuwu is likely a mixture of thermogenic, biogenic, and magmatic CO2, with faulting controlling potential pathways for magmatic fluids. This study further demonstrates the merit of man-portable active remote sensing instruments for probing natural gas releases, enabling bottom-up quantification of CO2 fluxes.

  20. CO2 flux from Javanese mud volcanism

    PubMed Central

    Burton, M. R.; Arzilli, F.; Chiarugi, A.; Marliyani, G. I.; Anggara, F.; Harijoko, A.

    2017-01-01

    Abstract Studying the quantity and origin of CO2 emitted by back‐arc mud volcanoes is critical to correctly model fluid‐dynamical, thermodynamical, and geochemical processes that drive their activity and to constrain their role in the global geochemical carbon cycle. We measured CO2 fluxes of the Bledug Kuwu mud volcano on the Kendeng Fold and thrust belt in the back arc of Central Java, Indonesia, using scanning remote sensing absorption spectroscopy. The data show that the expelled gas is rich in CO2 with a volume fraction of at least 16 vol %. A lower limit CO2 flux of 1.4 kg s−1 (117 t d−1) was determined, in line with the CO2 flux from the Javanese mud volcano LUSI. Extrapolating these results to mud volcanism from the whole of Java suggests an order of magnitude total CO2 flux of 3 kt d−1, comparable with the expected back‐arc efflux of magmatic CO2. After discussing geochemical, geological, and geophysical evidence we conclude that the source of CO2 observed at Bledug Kuwu is likely a mixture of thermogenic, biogenic, and magmatic CO2, with faulting controlling potential pathways for magmatic fluids. This study further demonstrates the merit of man‐portable active remote sensing instruments for probing natural gas releases, enabling bottom‐up quantification of CO2 fluxes. PMID:28944134

  1. Exogenously produced CO2 doubles the CO2 efflux from three north temperate lakes

    NASA Astrophysics Data System (ADS)

    Wilkinson, Grace M.; Buelo, Cal D.; Cole, Jonathan J.; Pace, Michael L.

    2016-03-01

    It is well established that lakes are typically sources of CO2 to the atmosphere. However, it remains unclear what portion of CO2 efflux is from endogenously processed organic carbon or from exogenously produced CO2 transported into lakes. We estimated high-frequency CO2 and O2 efflux from three north temperate lakes in summer to determine the proportion of the total CO2 efflux that was exogenously produced. Two of the lakes were amended with nutrients to experimentally enhance endogenous CO2 uptake. In the unfertilized lake, 50% of CO2 efflux was from exogenous sources and hydrology had a large influence on efflux. In the fertilized lakes, endogenous CO2 efflux was negative (into the lake) yet exogenous CO2 made the lakes net sources of CO2 to the atmosphere. Shifts in hydrologic regimes and nutrient loading have the potential to change whether small lakes act primarily as reactors or vents in the watershed.

  2. Energyless CO2 Absorption, Generation, and Fixation Using Atmospheric CO2.

    PubMed

    Inagaki, Fuyuhiko; Okada, Yasuhiko; Matsumoto, Chiaki; Yamada, Masayuki; Nakazawa, Kenta; Mukai, Chisato

    2016-01-01

    From an economic and ecological perspective, the efficient utilization of atmospheric CO2 as a carbon resource should be a much more important goal than reducing CO2 emissions. However, no strategy to harvest CO2 using atmospheric CO2 at room temperature currently exists, which is presumably due to the extremely low concentration of CO2 in ambient air (approximately 400 ppm=0.04 vol%). We discovered that monoethanolamine (MEA) and its derivatives efficiently absorbed atmospheric CO2 without requiring an energy source. We also found that the absorbed CO2 could be easily liberated with acid. Furthermore, a novel CO2 generator enabled us to synthesize a high value-added material (i.e., 2-oxazolidinone derivatives based on the metal catalyzed CO2-fixation at room temperature) from atmospheric CO2.

  3. Stabilities and structures of the Li-CO 2 and Na-CO 2 complexes

    NASA Astrophysics Data System (ADS)

    Yoshioka, Y.; Jordan, K. D.

    1981-12-01

    The geometries and stabilities of the Li-CO 2 and Na-CO 2 complexes are calculated using thc self-consistent-field-XXX-Fock method. The minimum energy. C 2v structures of Li-CO 2 and Na-CO 2 are found to be stable by 0.85 and 0.34 eV, respectively, with respect to dissociation to CO 2 + alkali atom.

  4. Lidar measurements of the column CO2 mixing ratio made by NASA Goddard's CO2 Sounder during the NASA ASCENDS 2014 Airborne campaign.

    NASA Astrophysics Data System (ADS)

    Ramanathan, A. K.; Mao, J.; Abshire, J. B.; Kawa, S. R.

    2015-12-01

    Remote sensing measurements of CO2 from space can help improve our understanding of the carbon cycle and help constrain the global carbon budget. However, such measurements need to be sufficiently accurate to detect small (1 ppm) changes in the CO2 mixing ratio (XCO2) against a large background (~ 400 ppm). Satellite measurements of XCO2 using passive spectrometers, such as those from the Japanese GOSAT (Greenhouse gas Observing Satellite) and the NASA OCO-2 (Orbiting Carbon Observatory-2) are limited to daytime sunlit portions of the Earth and are susceptible to biases from clouds and aerosols. For this reason, NASA commissioned the formulation study of ASCENDS a space-based lidar mission. NASA Goddard Space Flight Center's CO2 Sounder lidar is one candidate approach for the ASCENDS mission. The NASA GSFC CO2 Sounder measures the CO2 mixing ratio using a pulsed multi-wavelength integrated path differential absorption (IPDA) approach. The CO2 Sounder has flown in the 2011, 2013 and 2014 ASCENDS airborne campaigns over the continental US, and has produced measurements in close agreement with in situ measurements of the CO2 column. In 2014, the CO2 Sounder upgraded its laser with a precision step-locked diode laser source to improve the lidar wavelength position accuracy. It also improved its optical receiver with a low-noise, high efficiency, HgCdTe avalanche photo diode detector. The combination of these two technologies enabled lidar XCO2 measurements with unprecedented accuracy. In this presentation, we show analysis from the ASCENDS 2014 field campaign, exploring: (1) Horizontal XCO2 gradients measured by the lidar, (2) Comparisons of lidar XCO2 measurements against the Parameterized Chemistry Transport Model (PCTM), and (3) Lidar column water vapor measurements using a HDO absorption line that occurs next to the CO2 absorption line. This can reduce the uncertainty in the dry air column used in XCO2 retrievals.

  5. Performance of photoperiod and light intensity on biogas upgrade and biogas effluent nutrient reduction by the microalgae Chlorella sp.

    PubMed

    Yan, Cheng; Zheng, Zheng

    2013-07-01

    Biogas is an environment-friendly fuel but that must be upgraded before being utilized. The method about removing CO2 from biogas by microalgal culturing using biogas effluent as nutrient medium in this study could effectively upgrade biogas and simultaneously reduce the biogas effluent nutrient. Results showed that the optimum parameters for microalgal growth and biogas effluent nutrient reduction was moderate light intensity with middle photoperiod. While low light intensity with long photoperiod and moderate light intensity with middle photoperiod obtained the best biogas CO2 removal and biogas upgrade effects. Therefore, the optimal parameters were moderate light intensity 350 μmol m(-2)s(-1) with middle photoperiod 14 h light:10h dark. Under this condition, the microalgal dry weight, CH4 concentration, reduction efficiency of chemical oxygen demand, total nitrogen, and total phosphorus was 615.84 ± 33.07 mg L(-1), 92.16 ± 2.83% (v/v), 88.74 ± 3.45%, 83.94 ± 3.51%, and 80.43 ± 4.17%, respectively.

  6. CO2 sequestration: Storage capacity guideline needed

    USGS Publications Warehouse

    Frailey, S.M.; Finley, R.J.; Hickman, T.S.

    2006-01-01

    Petroleum reserves are classified for the assessment of available supplies by governmental agencies, management of business processes for achieving exploration and production efficiency, and documentation of the value of reserves and resources in financial statements. Up to the present however, the storage capacity determinations made by some organizations in the initial CO2 resource assessment are incorrect technically. New publications should thus cover differences in mineral adsorption of CO2 and dissolution of CO2 in various brine waters.

  7. Production of solar fuels by CO2 plasmolysis

    NASA Astrophysics Data System (ADS)

    Goede, Adelbert P. H.; Bongers, Waldo A.; Graswinckel, Martijn F.; M. C. M van de Sanden, Richard; Leins, Martina; Kopecki, Jochen; Schulz, Andreas; Walker, Mathias

    2014-12-01

    A storage scheme for Renewable Energy (RE) based on the plasmolysis of CO2into CO and O2 has been experimentally investigated, demonstrating high energy efficiency (>50%) combined with high energy density, rapid start-stop and no use of scarce materials. The key parameter controlling energy efficiency has been identified as the reduced electric field. Basic plasma parameters including density and temperature are derived from a simple particle and energy balance model, allowing parameter specification of an upscale 100 kW reactor. With RE powered plasmolysis as the critical element, a CO2 neutral energy system becomes feasible when complemented by effective capture of CO2 at the input and separation of CO from the output gas stream followed by downstream chemical processing into hydrocarbon fuels.

  8. Electric field effects in electrochemical CO2 reduction

    DOE PAGES

    Chen, Leanne D.; Urushihara, Makoto; Chan, Karen; ...

    2016-09-22

    Electrochemical reduction of CO2 has the potential to reduce greenhouse gas emissions while providing energy storage and producing chemical feedstocks. A mechanistic understanding of the process is crucial to the discovery of efficient catalysts, and an atomistic description of the electrochemical interface is a major challenge due to its complexity. Here, we examine the CO2 → CO electrocatalytic pathway on Ag(111) using density functional theory (DFT) calculations and an explicit model of the electrochemical interface. We show that the electric field from solvated cations in the double layer and their corresponding image charges on the metal surface significantly stabilizes keymore » intermediates—*CO2 and *COOH. At the field-stabilized sites, the formation of *CO is rate-determining. We present a microkinetic model that incorporates field effects and electrochemical barriers from ab initio calculations. As a result, the computed polarization curves show reasonable agreement with experiment without fitting any parameters.« less

  9. Chances and challenges of forest scale CO2 enrichment

    NASA Astrophysics Data System (ADS)

    Körner, Christian

    2016-04-01

    Rising CO2 is changing the biosphere's diet. As with any dietary change, both amount and quality of food matter. Atmospheric CO2 enrichment is clearly providing a rather one-sided, C-rich diet. Hence, the reaiistic experimental simulation of its effect on the single biggest C reservoir of the biosphere, that is forest, requires experimental conditions that resemble exactly that situation. In the past, trees where most commonly exposed to elevated CO2 while provided with ample other constituents of a plant's diet (soil nutrients), yielding exaggerated growth stimulation, unlikely to reflect real world responses. So, by either selecting fertile soils, disturbing the system by fire or planting activities, offering ample soil space to isolated individuals or even adding fertilizer, almost any CO2-response can be 'designed'. The 'art' of designing future Free Air CO2 Enrichment (FACE) experiments will be to avoid exactly these pitfalls. Plants can incorporate additional C only to the extent the provision of chemical elements other than C will permit, given the stoichiometry of life. Site selection (soil fertility), degree of canopy closure, recent disturbance regime or successional stage will influence CO2 effects. It is the fundamental dilemma in CO2-enrichment research that simple, homogenous, artificial test systems offer statistical power, while systems that account for 'naturalness' and species diversity do not. Any new FACE program needs to handle that tradeoff between precision and relevance. In this presentation I will advocate a pragmatic approach that will inevitably have to lean on individual tree responses, across a wide as possible range of neighborhoods, age and growth conditions, with the statistical power depending in obtaining the best possible pre-treatment traits and responses. By illustrating the results of 15 years of FACE with 30-40 m tall forest trees, I will caution against over-optimistic ecosystem scale approaches with just ONE technology

  10. A review of mineral carbonation technologies to sequester CO2.

    PubMed

    Sanna, A; Uibu, M; Caramanna, G; Kuusik, R; Maroto-Valer, M M

    2014-12-07

    Carbon dioxide (CO2) capture and sequestration includes a portfolio of technologies that can potentially sequester billions of tonnes of CO2 per year. Mineral carbonation (MC) is emerging as a potential CCS technology solution to sequester CO2 from smaller/medium emitters, where geological sequestration is not a viable option. In MC processes, CO2 is chemically reacted with calcium- and/or magnesium-containing materials to form stable carbonates. This work investigates the current advancement in the proposed MC technologies and the role they can play in decreasing the overall cost of this CO2 sequestration route. In situ mineral carbonation is a very promising option in terms of resources available and enhanced security, but the technology is still in its infancy and transport and storage costs are still higher than geological storage in sedimentary basins ($17 instead of $8 per tCO2). Ex situ mineral carbonation has been demonstrated on pilot and demonstration scales. However, its application is currently limited by its high costs, which range from $50 to $300 per tCO2 sequestered. Energy use, the reaction rate and material handling are the key factors hindering the success of this technology. The value of the products seems central to render MC economically viable in the same way as conventional CCS seems profitable only when combined with EOR. Large scale projects such as the Skyonic process can help in reducing the knowledge gaps on MC fundamentals and provide accurate costing and data on processes integration and comparison. The literature to date indicates that in the coming decades MC can play an important role in decarbonising the power and industrial sector.

  11. R&D100: CO2 Memzyme

    ScienceCinema

    Rempe, Susan; Brinker, Jeff; Jiang, Ying-Bing; Vanegas, Juan

    2016-07-12

    By combining a water droplet loaded with CO2 enzymes in an ultrathin nanopore on a flexible substrate, researchers at Sandia National Laboratories realized the first technology that meets and exceeds DOE targets for cost-effective CO2 capture. When compared with the nearest membrane competitor, this technology delivers a three times permeation rate, twenty times higher selectivity, and ten time lower fabrication cost. The CO2 Memzyme has the potential to remove 90% of CO2 emissions and is forecasted to save the U.S. coal industry $90 billion a year compared to conventional technology.

  12. R&D100: CO2 Memzyme

    SciTech Connect

    Rempe, Susan; Brinker, Jeff; Jiang, Ying-Bing; Vanegas, Juan

    2015-11-19

    By combining a water droplet loaded with CO2 enzymes in an ultrathin nanopore on a flexible substrate, researchers at Sandia National Laboratories realized the first technology that meets and exceeds DOE targets for cost-effective CO2 capture. When compared with the nearest membrane competitor, this technology delivers a three times permeation rate, twenty times higher selectivity, and ten time lower fabrication cost. The CO2 Memzyme has the potential to remove 90% of CO2 emissions and is forecasted to save the U.S. coal industry $90 billion a year compared to conventional technology.

  13. CO2 MITIGATION VIA ACCELERATED LIMESTONE WEATHERING

    SciTech Connect

    Rau, G H; Knauss, K G; Langer, W H; Caldeira, K G

    2004-02-27

    The climate and environmental impacts of our current, carbon-intensive energy usage demands that effective and practical energy alternatives and CO2 mitigation strategies be found. As part of this effort, various means of capturing and storing CO2 generated from fossil-fuel-based energy production are being investigated. One of the proposed methods involves a geochemistry-based capture and sequestration process that hydrates point-source, waste CO2 with water to produce a carbonic acid solution. This in turn is reacted and neutralized with limestone, thus converting the original CO2 gas to calcium bicarbonate in solution, the overall reaction being:

  14. A novel CO 2 gas analyzer based on IR absorption

    NASA Astrophysics Data System (ADS)

    Zhang, Guangjun; Wu, Xiaoli

    2004-08-01

    Carbon dioxide (CO 2) gas analyzer can be widely used in many fields. A novel CO 2 gas analyzer based on infrared ray (IR) absorption is presented sufficiently in this paper. Applying Lambert-Beer Law, a novel space-double-beam optical structure is established successfully. The optical structure includes an IR source, a gas cell, a bandpass filter with a transmission wavelength at 4.26 μm, another bandpass filter with a transmission wavelength at 3.9 μm, and two IR detectors. Based on Redial Basic Function (RBF) artificial neural network, the measuring model of IR CO 2 analyzer is established with a high accuracy. A dynamic compensation filter is effectively designed to improve the dynamic characteristic of the IR CO 2 analyzer without gas pump. The IR CO 2 analyzer possesses the advantages of high accuracy and mechanical reliability with small volume, lightweight, and low-power consumption. Therefore, it can be used in such relevant fields as environmental protection, processing control, chemical analysis, medical diagnosis, and space environmental and control systems.

  15. Pentaethylenehexamine-Loaded Hierarchically Porous Silica for CO2 Adsorption

    PubMed Central

    Ji, Changchun; Huang, Xin; Li, Lei; Xiao, Fukui; Zhao, Ning; Wei, Wei

    2016-01-01

    Recently, amine-functionalized materials as a prospective chemical sorbent for post combustion CO2 capture have gained great interest. However, the amine grafting for the traditional MCM-41, SBA-15, pore-expanded MCM-41 or SBA-15 supports can cause the pore volume and specific surface area of sorbents to decrease, significantly affecting the CO2 adsorption-desorption dynamics. To overcome this issue, hierarchical porous silica with interparticle macropores and long-range ordering mesopores was prepared and impregnated with pentaethylenehexamine. The pore structure and amino functional group content of the modified silicas were analyzed by scanning electron microscope, transmission electron microscope, N2 adsorption, X-ray powder diffraction, and Fourier transform infrared spectra. Moreover, the effects of the pore structure as well as the amount of PEHA loading of the samples on the CO2 adsorption capacity were investigated in a fixed-bed adsorption system. The CO2 adsorption capacity reached 4.5 mmol CO2/(g of adsorbent) for HPS−PEHA-70 at 75 °C. Further, the adsorption capacity for HPS-PEHA-70 was steady after a total of 15 adsorption-desorption cycles. PMID:28773956

  16. Role of CO2 in the formation of gold deposits.

    PubMed

    Phillips, G N; Evans, K A

    2004-06-24

    Much of global gold production has come from deposits with uneconomic concentrations of base metals, such as copper, lead and zinc. These 'gold-only' deposits are thought to have formed from hot, aqueous fluids rich in carbon dioxide, but only minor significance has been attached to the role of the CO2 in the process of gold transport. This is because chemical bonding between gold ions and CO2 species is not strong, and so it is unlikely that CO2 has a direct role in gold transport. An alternative indirect role for CO2 as a weak acid that buffers pH has also appeared unlikely, because previously inferred pH values for such gold-bearing fluids are variable. Here we show that such calculated pH values are unlikely to record conditions of gold transport, and propose that CO2 may play a critical role during gold transport by buffering the fluid in a pH range where elevated gold concentration can be maintained by complexation with reduced sulphur. Our conclusions, which are supported by geochemical modelling, may provide a platform for new gold exploration methods.

  17. Binding energies of CO2 with some ionic liquids

    NASA Astrophysics Data System (ADS)

    Eucker, William; Bendler, John

    2007-03-01

    Room temperature ionic liquids (RTILs), a novel class of materials with negligible vapor pressures and potentiality as benign solvents, may be an ideal chemical for carbon dioxide (CO2) gas sequestration. Ab initio computational modeling was used to investigate the molecular interactions of simple RTIL anions hexafluorophosphate (PF6^-) and tetrafluoroborate (BF4^-) with CO2. Electronic potential energy surface (PES) scans of a comprehensive sampling of 1:1 anion-CO2 orientations were computed using Spartan '02 with Dunning's correlation consistent basis sets. Qualitatively, the PES scans yielded deeper, more numerous and radially closer active sites surrounding BF4^- anion as compared with the PF6^- anion. Quantitatively, the binding energies of 17.87 kJ/mol and 25.24 kJ/mol were extracted from the identified global energy minima for the PF6^- and BF4^- systems, respectively. The smaller BF4^- anion was concluded to bind more strongly to the CO2. However, literature-reported experimental Henry's law constants for CO2 dissolved in imidizolium based RTILs show greater gas solvation in the PF6^- system. The discrepancy between the energetics calculation results and the experimental solvation data will be discussed.

  18. Materials for Hydrogen Production with Integrated CO2 Capture

    NASA Astrophysics Data System (ADS)

    van den Brink, Ruud W.; de Bruijn, Frank A.

    2009-09-01

    Palladium-based membrane reactors and sorption-enhanced water-gas shift are two promising technologies for efficient production of hydrogen with integrated CO2 capture. This paper discusses material issues of the two crucial materials of these technologies: the membrane and the CO2 sorbent. For Pd and Pd-alloy membranes the major issues concern the stability of the membrane and the poisoning of the membrane surface by compound such as sulfur and carbon monoxide. Both issues are addressed by research into novel Pd-alloys. For the potassium-promoted hydrotalcite CO2 sorbents used in sorption-enhanced water gas shift, the main challenges are a high CO2 adsorption capacity, chemical and mechanical stability, and low steam use for sorbent regeneration. Promising results have recently been reported for several of these challenges. For both hydrogen-selective membranes and CO2 sorbents, the interaction of the materials with sulfur is an import issue to enable their use in the production of hydrogen from coal.

  19. Climate balance of biogas upgrading systems.

    PubMed

    Pertl, A; Mostbauer, P; Obersteiner, G

    2010-01-01

    One of the numerous applications of renewable energy is represented by the use of upgraded biogas where needed by feeding into the gas grid. The aim of the present study was to identify an upgrading scenario featuring minimum overall GHG emissions. The study was based on a life-cycle approach taking into account also GHG emissions resulting from plant cultivation to the process of energy conversion. For anaerobic digestion two substrates have been taken into account: (1) agricultural resources and (2) municipal organic waste. The study provides results for four different upgrading technologies including the BABIU (Bottom Ash for Biogas Upgrading) method. As the transport of bottom ash is a critical factor implicated in the BABIU-method, different transport distances and means of conveyance (lorry, train) have been considered. Furthermore, aspects including biogas compression and energy conversion in a combined heat and power plant were assessed. GHG emissions from a conventional energy supply system (natural gas) have been estimated as reference scenario. The main findings obtained underlined how the overall reduction of GHG emissions may be rather limited, for example for an agricultural context in which PSA-scenarios emit only 10% less greenhouse gases than the reference scenario. The BABIU-method constitutes an efficient upgrading method capable of attaining a high reduction of GHG emission by sequestration of CO(2).

  20. CO2 Interaction with Geomaterials (Invited)

    NASA Astrophysics Data System (ADS)

    Romanov, V.; Howard, B. H.; Lynn, R. J.; Warzinski, R. P.; Hur, T.; Myshakin, E. M.; Lopano, C. L.; Voora, V. K.; Al-Saidi, W. A.; Jordan, K. D.; Cygan, R. T.; Guthrie, G. D.

    2010-12-01

    This work compares the sorption and swelling processes associated with CO2-coal and CO2-clay interactions. We investigated the mechanisms of interaction related to CO2 adsortion in micropores, intercalation into sub-micropores, dissolution in solid matrix, the role of water, and the associated changes in reservoir permeability, for applications in CO2 sequestration and enhanced coal bed methane recovery. The structural changes caused by CO2 have been investigated. A high-pressure micro-dilatometer was equipped to investigate the effect of CO2 pressure on the thermoplastic properties of coal. Using an identical dilatometer, Rashid Khan (1985) performed experiments with CO2 that revealed a dramatic reduction in the softening temperature of coal when exposed to high-pressure CO2. A set of experiments was designed for -20+45-mesh samples of Argonne Premium Pocahontas #3 coal, which is similar in proximate and ultimate analysis to the Lower Kittanning seam coal that Khan used in his experiments. No dramatic decrease in coal softening temperature has been observed in high-pressure CO2 that would corroborate the prior work of Khan. Thus, conventional polymer (or “geopolymer”) theories may not be directly applicable to CO2 interaction with coals. Clays are similar to coals in that they represent abundant geomaterials with well-developed microporous structure. We evaluated the CO2 sequestration potential of clays relative to coals and investigated the factors that affect the sorption capacity, rates, and permanence of CO2 trapping. For the geomaterials comparison studies, we used source clay samples from The Clay Minerals Society. Preliminary results showed that expandable clays have CO2 sorption capacities comparable to those of coal. We analyzed sorption isotherms, XRD, DRIFTS (infrared reflectance spectra at non-ambient conditions), and TGA-MS (thermal gravimetric analysis) data to compare the effects of various factors on CO2 trapping. In montmorillonite, CO2

  1. Mechanism of acid reduction at low and high overpotential metal electrodes in the presence and absence of CO2: Implications for CO2 reduction by N-heterocycles

    NASA Astrophysics Data System (ADS)

    Zeitler, Elizabeth L.

    Carbon dioxide reduction is of public interest to synthesize useful materials from CO2 and for storage of renewable energy in a carbon-constrained world. Scientifically, CO2 reduction is of fundamental interest to understand the activation of small molecules and stable chemical bonds. Pyridinium catalysts have been observed to lower the overpotential for reduction of CO2 to methanol at platinum and p-GaP electrodes. In this study, the reduction of pyridinium at a variety of metal electrode surfaces was explored along with its interaction with CO2. The reduction of any weak acid analyte on platinum was found to proceed via a one-electron, proton-coupled process forming H2. The reduction potential could be predicted entirely by acid pKa. Equilibrium and kinetic isotope effects supported this assignment. A prepeak feature observed for acid reductions was examined. Reduction forming a pi-radical was observed for 4,4'-bipyridinium at platinum, gold and glassy carbon via spectroelectrochemistry. Only a small increase in radical decay was observed in the presence of CO 2. Pyridinium reduction at gold was found to occur via proton reduction. Protonated and unprotonated N-heterocycle reductions on glassy carbon can best be explained via pi-reduction. The interaction of CO2 with pyridine was examined. Current in the presence of CO2 was enhanced at slow scan rates due to the slow hydration of CO2 into carbonic acid, leading to pyridinium protonation and is not diagnostic of CO2 reduction. A variety of weak acid analytes showed current enhancement, with greater pKa values leading to greater enhancement. Solution buffering at the electrode interface by CO2 was examined. Current enhancement of pyridinium under CO2 was greater than the sum of the currents for background CO2 reduction and pyridinium reduction, indicating pyridine enhanced CO2 hydration.

  2. CO2 generation rate in Chinese people.

    PubMed

    Qi, M W; Li, X F; Weschler, L B; Sundell, J

    2014-12-01

    Carbon dioxide (CO2 ) metabolically produced by humans has been widely used as a tracer gas for determining ventilation rates in occupied rooms. Among other necessities, the method requires good estimates of human CO2 generation rates. An empirically derived equation is widely used to calculate the CO2 generation rate. However, there are indications that this equation is not valid for young Chinese people. In this study, we measured the CO2 generation rate of 44 young Chinese people at two typical activity levels, quiet sitting and relaxed standing. We found that the commonly used empirical equation overpredicted CO2 generation rates, but could be corrected with a factor of 0.75 for Chinese females and of 0.85 for Chinese males. The variance for measured CO2 sitting was much smaller than for standing, and hence, we concluded that sitting yields more precise CO2 generation estimates. The relative contributions of sex, height, weight, and metabolic rate were analyzed. We concluded that the error in estimating metabolic rate is responsible for most of the difference in measured generation of CO2 from the empirical equation's predictions. The tracer gas method using CO2 generated by people is widely used to calculate ventilation rate. However, the empirically derived equation that is normally used to estimate CO2 generation rate is not suitable for young Chinese people at rest. To estimate the CO2 generation rate in Chinese people under low-activity conditions, the empirical equation should be multiplied by correction factors of 0.75 and 0.85 for females and males, respectively. © 2014 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

  3. An emerging understanding of mechanisms governing insect herbivory under elevated CO2.

    PubMed

    Zavala, Jorge A; Nabity, Paul D; DeLucia, Evan H

    2013-01-01

    By changing the chemical composition of foliage, the increase in atmospheric CO(2) is fundamentally altering insect herbivory. The responses of folivorous insects to these changes is, however, highly variable. In this review we highlight emerging mechanisms by which increasing CO(2) alters the defense chemistry and signaling of plants. The response of allelochemicals affecting insect performance varies under elevated CO(2), and results suggest this is driven by changes in plant hormones. Increasing CO(2) suppresses the production of jasmonates and ethylene and increases the production of salicylic acid, and these differential responses of plant hormones affect specific secondary chemical pathways. In addition to changes in secondary chemistry, elevated CO(2) decreases rates of water loss from leaves, increases temperature and feeding rates, and alters nutritional content. New insights into the mechanistic responses of secondary chemistry to elevated CO(2) increase our ability to predict the ecological and evolutionary responses of plants attacked by insects.

  4. Detection of CO2 leaks from carbon capture and storage sites to the atmosphere with combined CO2 and O2 measurements

    NASA Astrophysics Data System (ADS)

    van Leeuwen, Charlotte; Meijer, Harro A. J.

    2015-04-01

    One of the main issues in carbon capture and storage (CCS) is the possibility of leakage of CO2 from the storage reservoir to the atmosphere, both from a public health and a climate change combat perspective. Detecting these leaks in the atmosphere is difficult due to the rapid mixing of the emitted CO2 with the surrounding air masses and the high natural variability of the atmospheric CO2 concentration. Instead of measuring only the CO2 concentration of the atmosphere, its isotopes or chemical tracers that are released together with the CO2, our method uses O2 measurements in addition to CO2 measurements to detect a leak from a CCS site. CO2 and O2 are coupled in most processes on earth. In photosynthesis, plants take up CO2 and release O2 at the same time. In respiration and fossil fuel burning, O2 is consumed while CO2 is released. In case of a leak from a CCS site, however, there is no relationship between CO2 and O2. A CO2 leak can therefore be distinguished from other sources of CO2 by looking at the atmospheric CO2-O2 ratio. A natural increase of the CO2 concentration is accompanied by a drop in the O2 concentration, while an increase in the CO2 concentration caused by a leak from a CCS site does not have any effect on the O2 concentration. To demonstrate this leak detection strategy we designed and built a transportable CO2 and O2 measurement system, that is capable of measuring the relatively minute (ppm's variations on a 21% concentration) changes in the O2 concentration. The system comprises of three cases that contain the instrumentation and gas handling equipment, the gas cylinders used as reference and calibration gases and a drying system, respectively. Air is pumped to the system from an air inlet that is placed in a small tower in the field. At the conference, we will demonstrate the success of leak detection with our system by showing measurements of several CO2 release experiments, where CO2 was released at a small distance from the air inlet of

  5. Characterization of CO2 leakage into the freshwater body

    NASA Astrophysics Data System (ADS)

    Singh, Ashok; Delfs, Jens-Olaf; Shao, Habing; Kolditz, Olaf

    2013-04-01

    Current research into Carbon dioxide Capture and Storage (CCS) is dominated by improving the CO2 storage capacity. However, potential leakage of CO2 can cause environmental problems, particularly if freshwater resources are nearby. In this regards, it is important to understand the chemistry of CO2 and the water system. CO2 leakage across the fluid interface (CO2 and water) is controlled by the difference in the partial pressure of CO2 in the storage and in the freshwater body. Once the CO2 is in solution, it equilibrates with the bicarbonate and carbonate ions. According to Millero (1994)such a system can be characterized by two parameters out of the four: total alkalinity (TA), total carbonate (TCO2), fugacity of CO2(fCO2) and pH. In the present modeling study, we are interested in the (i) CO2 leakage into a freshwater body (while injecting CO2 for storage) through an inclined fracture and (ii) characterization of the system by measuring fugacity of CO2 and pH. According to work presented by Singh et al. (2012), about 31% of injected CO2 leaks into the freshwater body. Solubility of CO2 in water follows Henry's law, while the Henry constant, K0 is calculated by an empirical relation developed by Murray and Riley (1971), which is a function of salinity and temperature. According to our results, pH and fugacity both appear to be a linear function of temperature. To simulate the discussed problem, a corresponding numerical module has been developed for multi-component fluid flow coupled with heat and mass transport processes. Governing equations and Volume Translated Peng-Robinson equations of state are implemented within the object-oriented finite element code OpenGeoSys (Kolditz et al., 2012; www.opengeosys.org). Primary variables are pressure, temperature and salinity which are obtained by solving the governing equations in a monolithic way The governing equations are discretized spatially within the context of a Galerkin approach, whereas the temporal

  6. TLRS-3 system upgrades

    NASA Technical Reports Server (NTRS)

    Eichinger, Richard; Cheng, Grace; Crawford, William; Cresswell, Don; Crooks, Henry A.; Donovan, Howard; Edge, David R.; Emenheiser, Kenneth S.; Hanrahan, William P., III; Heinick, J. Michael

    1993-01-01

    This presentation describes the upgrades to the Transportable Laser Ranging Systems serial number three (TLRS-3), and the impact that these upgrades will have on the TLRS-3 performance in the field. The four major areas of system upgrades are the HP-380 computer, the Optical Attenuation Mechanism (OAM), the upgraded spatial, spectral and temporal filtering for improved daylight ranging capability, and the software upgrade to enable the system to track the Etalon satellites. The TLRS-3 was returned to the Goddard Geophysical and Astronomical Observatory (GGAO) in December 1991 for system upgrades in preparation of the TOPEX/POSEIDON campaign scheduled to begin in the summer of 1992. Many system upgrades were incorporated into the system while interleaving planned facility maintenance making TLRS-3 a more versatile and more dependable laser ranging system. The TLRS-3 was initially baselined with the MOBLAS-7 via simultaneous satellite ranging on the LAGEOS, Ajisai, Starlette, and ERS-I satellites. During the upgrades and following completion of the system upgrades intercomparisons with the MOBLAS-7 were made to verify the integrity and accuracy of the system changes. Several other groups of personnel participated in the TLRS-3 upgrade and they are: the Survey Section, the Precision Measurement Equipment Laboratory, the Architectural and Engineering Services Department, the Precision Timing Section, and the station personnel at TLRS-3 and MOBLAS-7.

  7. Choosing amine-based absorbents for CO2 capture.

    PubMed

    Gomes, João; Santos, Samuel; Bordado, João

    2015-01-01

    CO2 capture from gaseous effluents is one of the great challenges faced by chemical and environmental engineers, as the increase in CO2 levels in the Earth atmosphere might be responsible for dramatic climate changes. From the existing capture technologies, the only proven and mature technology is chemical absorption using aqueous amine solutions. However, bearing in mind that this process is somewhat expensive, it is important to choose the most efficient and, at the same time, the least expensive solvents. For this purpose, a pilot test facility was assembled and includes an absorption column, as well as a stripping column, a heat exchanger between the two columns, a reboiler for the stripping column, pumping systems, surge tanks and all necessary instrumentation and control systems. Some different aquous amine solutions were tested on this facility and it was found that, from a set of six tested amines, diethanol amine is the one that turned out to be the most economical choice, as it showed a higher CO2 loading capacity (0.982 mol of CO2 per mol of amine) and the lowest price per litre (25.70 €/L), even when compared with monoethanolamine, the benchmark solvent, exhibiting a price per litre of 30.50 €/L.

  8. CO2 Capture with Enzyme Synthetic Analogue

    SciTech Connect

    Cordatos, Harry

    2010-11-08

    Overview of an ongoing, 2 year research project partially funded by APRA-E to create a novel, synthetic analogue of carbonic anhydrase and incorporate it into a membrane for removal of CO2 from flue gas in coal power plants. Mechanism background, preliminary feasibility study results, molecular modeling of analogue-CO2 interaction, and program timeline are provided.

  9. CO2 Capture with Enzyme Synthetic Analogue

    SciTech Connect

    Cordatos, Harry

    2010-03-01

    Project overview provides background on carbonic anhydrase transport mechanism for CO2 in the human body and proposed approach for ARPA-E project to create a synthetic enzyme analogue and utilize it in a membrane for CO2 capture from flue gas.

  10. Capturing CO2 via reactions in nanopores.

    SciTech Connect

    Leung, Kevin; Nenoff, Tina Maria; Criscenti, Louise Jacqueline; Tang, Z; Dong, J. H.

    2008-10-01

    This one-year exploratory LDRD aims to provide fundamental understanding of the mechanism of CO2 scrubbing platforms that will reduce green house gas emission and mitigate the effect of climate change. The project builds on the team members expertise developed in previous LDRD projects to study the capture or preferential retention of CO2 in nanoporous membranes and on metal oxide surfaces. We apply Density Functional Theory and ab initio molecular dynamics techniques to model the binding of CO2 on MgO and CaO (100) surfaces and inside water-filled, amine group functionalized silica nanopores. The results elucidate the mechanisms of CO2 trapping and clarify some confusion in the literature. Our work identifies key future calculations that will have the greatest impact on CO2 capture technologies, and provides guidance to science-based design of platforms that can separate the green house gas CO2 from power plant exhaust or even from the atmosphere. Experimentally, we modify commercial MFI zeolite membranes and find that they preferentially transmit H2 over CO2 by a factor of 34. Since zeolite has potential catalytic capability to crack hydrocarbons into CO2 and H2, this finding paves the way for zeolite membranes that can convert biofuel into H2 and separate the products all in one step.

  11. CO2 annual and semiannual cycles from multiple satellite retrievals and models

    NASA Astrophysics Data System (ADS)

    Jiang, Xun; Crisp, David; Olsen, Edward T.; Kulawik, Susan S.; Miller, Charles E.; Pagano, Thomas S.; Liang, Maochang; Yung, Yuk L.

    2016-02-01

    Satellite CO2 retrievals from the Greenhouse gases Observing SATellite (GOSAT), Atmospheric Infrared Sounder (AIRS), and Tropospheric Emission Spectrometer (TES) and in situ measurements from the National Oceanic and Atmospheric Administration - Earth System Research Laboratory (NOAA-ESRL) Surface CO2 and Total Carbon Column Observing Network (TCCON) are utilized to explore the CO2 variability at different altitudes. A multiple regression method is used to calculate the CO2 annual cycle and semiannual cycle amplitudes from different data sets. The CO2 annual cycle and semiannual cycle amplitudes for GOSAT XCO2 and TCCON XCO2 are consistent but smaller than those seen in the NOAA-ESRL surface data. The CO2 annual and semiannual cycles are smallest in the AIRS midtropospheric CO2 compared with other data sets in the Northern Hemisphere. The amplitudes for the CO2 annual cycle and semiannual cycle from GOSAT, TES, and AIRS CO2 are small and comparable to each other in the Southern Hemisphere. Similar regression analysis is applied to the Model for OZone And Related chemical Tracers-2 and CarbonTracker model CO2. The convolved model CO2 annual cycle and semiannual cycle amplitudes are similar to those from the satellite CO2 retrievals, although the models tend to underestimate the CO2 seasonal cycle amplitudes in the Northern Hemisphere midlatitudes and underestimate the CO2 semiannual cycle amplitudes in the high latitudes. These results can be used to better understand the vertical structures for the CO2 annual cycle and semiannual cycle and help identify deficiencies in the models, which are very important for the carbon budget study.

  12. Improved Criteria for Increasing CO2 Storage Potential with CO2 Enhanced Oil Recovery

    NASA Astrophysics Data System (ADS)

    Bauman, J.; Pawar, R.

    2013-12-01

    In recent years it has been found that deployment of CO2 capture and storage technology at large scales will be difficult without significant incentives. One of the technologies that has been a focus in recent years is CO2 enhanced oil/gas recovery, where additional hydrocarbon recovery provides an economic incentive for deployment. The way CO2 EOR is currently deployed, maximization of additional oil production does not necessarily lead to maximization of stored CO2, though significant amounts of CO2 are stored regardless of the objective. To determine the potential of large-scale CO2 storage through CO2 EOR, it is necessary to determine the feasibility of deploying this technology over a wide range of oil/gas field characteristics. In addition it is also necessary to accurately estimate the ultimate CO2 storage potential and develop approaches that optimize oil recovery along with long-term CO2 storage. This study uses compositional reservoir simulations to further develop technical screening criteria that not only improve oil recovery, but maximize CO2 storage during enhanced oil recovery operations. Minimum miscibility pressure, maximum oil/ CO2 contact without the need of significant waterflooding, and CO2 breakthrough prevention are a few key parameters specific to the technical aspects of CO2 enhanced oil recovery that maximize CO2 storage. We have developed reduced order models based on simulation results to determine the ultimate oil recovery and CO2 storage potential in these formations. Our goal is to develop and demonstrate a methodology that can be used to determine feasibility and long-term CO2 storage potential of CO2 EOR technology.

  13. Zinc depolarized electrochemical CO2 concentration

    NASA Technical Reports Server (NTRS)

    Woods, R. R.; Marshall, R. D.; Schubert, F. H.

    1975-01-01

    Two zinc depolarized electrochemical carbon dioxide concentrator concepts were analytically and experimentally evaluated for portable life support system carbon dioxide (CO2) removal application. The first concept, referred to as the zinc hydrogen generator electrochemical depolarized CO2 concentrator, uses a ZHG to generate hydrogen for direct use in an EDC. The second concept, referred to as the zinc/electrochemical depolarized concentrator, uses a standard EDC cell construction modified for use with the Zn anode. The Zn anode is consumed and subsequently regenerated, thereby eliminating the need to supply H2 to the EDC for the CO2 removal process. The evaluation was based primarily on an analytical evaluation of the two ZnDCs at projected end item performance and hardware design levels. Both ZnDC concepts for PLSS CO2 removal application were found to be noncompetitive in both total equivalent launch weight and individual extravehicular activity mission volume when compared to other candidate regenerable PLSS CO2 scrubbers.

  14. Geophysical monitoring technology for CO2 sequestration

    NASA Astrophysics Data System (ADS)

    Ma, Jin-Feng; Li, Lin; Wang, Hao-Fan; Tan, Ming-You; Cui, Shi-Ling; Zhang, Yun-Yin; Qu, Zhi-Peng; Jia, Ling-Yun; Zhang, Shu-Hai

    2016-06-01

    Geophysical techniques play key roles in the measuring, monitoring, and verifying the safety of CO2 sequestration and in identifying the efficiency of CO2-enhanced oil recovery. Although geophysical monitoring techniques for CO2 sequestration have grown out of conventional oil and gas geophysical exploration techniques, it takes a long time to conduct geophysical monitoring, and there are many barriers and challenges. In this paper, with the initial objective of performing CO2 sequestration, we studied the geophysical tasks associated with evaluating geological storage sites and monitoring CO2 sequestration. Based on our review of the scope of geophysical monitoring techniques and our experience in domestic and international carbon capture and sequestration projects, we analyzed the inherent difficulties and our experiences in geophysical monitoring techniques, especially, with respect to 4D seismic acquisition, processing, and interpretation.

  15. Ab initio Quantum Chemical Studies of Reactions in Astrophysical Ices. Reactions Involving CH3OH, CO2, CO, HNCO in H2CO/NH3/H2O Ices

    NASA Technical Reports Server (NTRS)

    Woon, David E.

    2006-01-01

    While reactions between closed shell molecules generally involve prohibitive barriers in the gas phase, prior experimental and theoretical studies have demonstrated that some of these reactions are significantly enhanced when confined within an icy grain mantle and can occur efficiently at temperatures below 100 K with no additional energy processing. The archetypal case is the reaction of formaldehyde (H2CO) and ammonia (NH3) to yield hydroxymethylamine (NH2CH2OH). In the present work we have characterized reactions involving methanol (CH3OH), carbon dioxide (CO2), carbon monoxide (CO), and isocyanic acid (HNCO) in search of other favorable cases. Most of the emphasis is on CH3OH, which was investigated in the two-body reaction with one H2CO and the three-body reaction with two H2CO molecules. The addition of a second H2CO to the product of the reaction between CH3OH and H2CO was also considered as an alternative route to longer polyoxymethylene polymers of the -CH2O- form. The reaction between HNCO and NH3 was studied to determine if it can compete against the barrierless charge transfer process that yields OCN(-) and NH4(+). Finally, the H2CO + NH3 reaction was revisited with additional benchmark calculations that confirm that little or no barrier is present when it occurs in ice.

  16. Ab Initio Quantum Chemical Studies of Reactions in Astrophysical Ices - Reactions Involving CH3OH, CO2, CO, and HNCO in H2CO/NH3/H2O Ices

    NASA Astrophysics Data System (ADS)

    Woon, David E.

    2006-09-01

    While reactions between closed shell molecules generally involve prohibitive barriers in the gas phase, prior experimental and theoretical studies have demonstrated that some of these reactions are significantly enhanced when confined within an icy grain mantle and can occur efficiently at temperatures below 100 K with no additional energy processing. The archetypal case is the reaction of formaldehyde (H2CO) and ammonia (NH3) to yield hydroxymethylamine (NH2CH2OH). In the present work we have characterized reactions involving methanol (CH3OH), carbon dioxide (CO2), carbon monoxide (CO), and isocyanic acid (HNCO) in search of other favorable cases. Most of the emphasis is on CH3OH, which was investigated in the two-body reaction with one H2CO and the three-body reaction with two H2CO molecules. The addition of a second H2CO to the product of the reaction between CH3OH and H2CO was also considered as an alternative route to longer polyoxymethylene polymers of the -CH2O- form. The reaction between HNCO and NH3 was studied to determine if it can compete against the barrierless charge transfer process that yields OCN- and NH4+. Finally, the H2CO + NH3 reaction was revisited with additional benchmark calculations that confirm that little or no barrier is present when it occurs in ice.

  17. A model for the evolution of CO2 on Mars.

    PubMed

    Haberle, R M; Tyler, D; McKay, C P; Davis, W L

    1994-05-01

    We have constructed a model that predicts the evolution of CO2 on Mars from the end of the heavy bombardment period to the present. The model draws on published estimates of the main processes believed to affect the fate of CO2 during this period: chemical weathering, regolith uptake, polar cap formation, and atmospheric escape. Except for escape, the rate at which these processes act is controlled by surface temperatures which we calculate using a modified version of the Gierasch and Toon energy balance model (1973, J. Atmos. Sci. 30, 1502-1508). The modifications account for the change in solar luminosity with time, the greenhouse effect, and a polar and solar equatorial energy budget. Using published estimates for the main parameters, we find no evolutionary scenario in which CO2 is capable of producing a warm (global mean temperatures>250 K) and wet (surface pressures>30 mbar) early climate, and then evolves to present conditions with approximately 7 mbar in the atmosphere, <300 mbar in the regolith, and <5 mbar in the caps. Such scenarios would only exist if the early sun were brighter than standard solar models suggest, if greenhouse gases other than CO2 were present in the early atmosphere, or if the polar albedo were significantly lower than 0.75. However, these scenarios generally require the storage of large amounts of CO2 (>1 bar) in the carbonate reservoir. If the warm and wet early Mars constraint is relaxed, then we find best overall agreement with present day reservoirs for initial CO2 inventories of 0.5-1.0 bar. We also find that the polar caps can a profound effect on how the system evolves. If the initial amount of CO2 is less than some critical value, then there is not enough heating of the poles to prevent permanent caps from forming. Once formed, these caps control how the system evolves, because they set the surface pressure and, hence, the thermal environment. If the initial amount of CO2 is greater than this critical value, then caps do not

  18. The ins and outs of CO2

    PubMed Central

    Raven, John A.; Beardall, John

    2016-01-01

    It is difficult to distinguish influx and efflux of inorganic C in photosynthesizing tissues; this article examines what is known and where there are gaps in knowledge. Irreversible decarboxylases produce CO2, and CO2 is the substrate/product of enzymes that act as carboxylases and decarboxylases. Some irreversible carboxylases use CO2; others use HCO3 –. The relative role of permeation through the lipid bilayer versus movement through CO2-selective membrane proteins in the downhill, non-energized, movement of CO2 is not clear. Passive permeation explains most CO2 entry, including terrestrial and aquatic organisms with C3 physiology and biochemistry, terrestrial C4 plants and all crassulacean acid metabolism (CAM) plants, as well as being part of some mechanisms of HCO3 – use in CO2 concentrating mechanism (CCM) function, although further work is needed to test the mechanism in some cases. However, there is some evidence of active CO2 influx at the plasmalemma of algae. HCO3 – active influx at the plasmalemma underlies all cyanobacterial and some algal CCMs. HCO3 – can also enter some algal chloroplasts, probably as part of a CCM. The high intracellular CO2 and HCO3 – pools consequent upon CCMs result in leakage involving CO2, and occasionally HCO3 –. Leakage from cyanobacterial and microalgal CCMs involves up to half, but sometimes more, of the gross inorganic C entering in the CCM; leakage from terrestrial C4 plants is lower in most environments. Little is known of leakage from other organisms with CCMs, though given the leakage better-examined organisms, leakage occurs and increases the energetic cost of net carbon assimilation. PMID:26466660

  19. The ins and outs of CO2.

    PubMed

    Raven, John A; Beardall, John

    2016-01-01

    It is difficult to distinguish influx and efflux of inorganic C in photosynthesizing tissues; this article examines what is known and where there are gaps in knowledge. Irreversible decarboxylases produce CO2, and CO2 is the substrate/product of enzymes that act as carboxylases and decarboxylases. Some irreversible carboxylases use CO2; others use HCO3(-). The relative role of permeation through the lipid bilayer versus movement through CO2-selective membrane proteins in the downhill, non-energized, movement of CO2 is not clear. Passive permeation explains most CO2 entry, including terrestrial and aquatic organisms with C3 physiology and biochemistry, terrestrial C4 plants and all crassulacean acid metabolism (CAM) plants, as well as being part of some mechanisms of HCO3(-) use in CO2 concentrating mechanism (CCM) function, although further work is needed to test the mechanism in some cases. However, there is some evidence of active CO2 influx at the plasmalemma of algae. HCO3(-) active influx at the plasmalemma underlies all cyanobacterial and some algal CCMs. HCO3(-) can also enter some algal chloroplasts, probably as part of a CCM. The high intracellular CO2 and HCO3(-) pools consequent upon CCMs result in leakage involving CO2, and occasionally HCO3(-). Leakage from cyanobacterial and microalgal CCMs involves up to half, but sometimes more, of the gross inorganic C entering in the CCM; leakage from terrestrial C4 plants is lower in most environments. Little is known of leakage from other organisms with CCMs, though given the leakage better-examined organisms, leakage occurs and increases the energetic cost of net carbon assimilation. © The Author 2015. Published by Oxford University Press on behalf of the Society for Experimental Biology.

  20. Rate of CO2 attack on hydrated Class H well cement under geologic sequestration conditions.

    PubMed

    Kutchko, Barbara G; Strazisar, Brian R; Lowry, Gregory V; Dzombak, David A; Thaulow, Niels

    2008-08-15

    Experiments were conducted to study the degradation of hardened cement paste due to exposure to CO2 and brine under geologic sequestration conditions (T = 50 degrees C and 30.3 MPa). The goal was to determine the rate of reaction of hydrated cement exposed to supercritical CO2 and to CO2-saturated brine to assess the potential impact of degradation in existing wells on CO2 storage integrity. Two different forms of chemical alteration were observed. The supercritical CO2 alteration of cement was similar in process to cement in contact with atmospheric CO2 (ordinary carbonation), while alteration of cement exposed to CO2-saturated brine was typical of acid attack on cement. Extrapolation of the hydrated cement alteration rate measured for 1 year indicates a penetration depth range of 1.00 +/- 0.07 mm for the CO2-saturated brine and 1.68 +/- 0.24 mm for the supercritical CO2 after 30 years. These penetration depths are consistent with observations of field samples from an enhanced oil recovery site after 30 years of exposure to CO2-saturated brine under similar temperature and pressure conditions. These results suggest that significant degradation due to matrix diffusion of CO2 in intact Class H neat hydrated cement is unlikely on time scales of decades.

  1. CO2 (dry ice) cleaning system

    NASA Astrophysics Data System (ADS)

    Barnett, Donald M.

    1995-03-01

    Tomco Equipment Company has participated in the dry ice (solid carbon dioxide, CO2) cleaning industry for over ten years as a pioneer in the manufacturer of high density, dry ice cleaning pellet production equipment. For over four years Tomco high density pelletizers have been available to the dry ice cleaning industry. Approximately one year ago Tomco introduced the DI-250, a new dry ice blast unit making Tomco a single source supplier for sublimable media, particle blast, cleaning systems. This new blast unit is an all pneumatic, single discharge hose device. It meters the insertion of 1/8 inch diameter (or smaller), high density, dry ice pellets into a high pressure, propellant gas stream. The dry ice and propellant streams are controlled and mixed from the blast cabinet. From there the mixture is transported to the nozzle where the pellets are accelerated to an appropriate blasting velocity. When directed to impact upon a target area, these dry ice pellets have sufficient energy to effectively remove most surface coatings through dry, abrasive contact. The meta-stable, dry ice pellets used for CO2 cleaning, while labeled 'high density,' are less dense than alternate, abrasive, particle blast media. In addition, after contacting the target surface, they return to their equilibrium condition: a superheated gas state. Most currently used grit blasting media are silicon dioxide based, which possess a sharp tetrahedral molecular structure. Silicon dioxide crystal structures will always produce smaller sharp-edged replicas of the original crystal upon fracture. Larger, softer dry ice pellets do not share the same sharp-edged crystalline structures as their non-sublimable counterparts when broken. In fact, upon contact with the target surface, dry ice pellets will plastically deform and break apart. As such, dry ice cleaning is less harmful to sensitive substrates, workers and the environment than chemical or abrasive cleaning systems. Dry ice cleaning system

  2. CO2 (dry ice) cleaning system

    NASA Technical Reports Server (NTRS)

    Barnett, Donald M.

    1995-01-01

    Tomco Equipment Company has participated in the dry ice (solid carbon dioxide, CO2) cleaning industry for over ten years as a pioneer in the manufacturer of high density, dry ice cleaning pellet production equipment. For over four years Tomco high density pelletizers have been available to the dry ice cleaning industry. Approximately one year ago Tomco introduced the DI-250, a new dry ice blast unit making Tomco a single source supplier for sublimable media, particle blast, cleaning systems. This new blast unit is an all pneumatic, single discharge hose device. It meters the insertion of 1/8 inch diameter (or smaller), high density, dry ice pellets into a high pressure, propellant gas stream. The dry ice and propellant streams are controlled and mixed from the blast cabinet. From there the mixture is transported to the nozzle where the pellets are accelerated to an appropriate blasting velocity. When directed to impact upon a target area, these dry ice pellets have sufficient energy to effectively remove most surface coatings through dry, abrasive contact. The meta-stable, dry ice pellets used for CO2 cleaning, while labeled 'high density,' are less dense than alternate, abrasive, particle blast media. In addition, after contacting the target surface, they return to their equilibrium condition: a superheated gas state. Most currently used grit blasting media are silicon dioxide based, which possess a sharp tetrahedral molecular structure. Silicon dioxide crystal structures will always produce smaller sharp-edged replicas of the original crystal upon fracture. Larger, softer dry ice pellets do not share the same sharp-edged crystalline structures as their non-sublimable counterparts when broken. In fact, upon contact with the target surface, dry ice pellets will plastically deform and break apart. As such, dry ice cleaning is less harmful to sensitive substrates, workers and the environment than chemical or abrasive cleaning systems. Dry ice cleaning system

  3. Dynamics of CO2 fluxes and concentrations during a shallow subsurface CO2 release

    SciTech Connect

    Lewicki, J.L.; Hilley, G.E.; Dobeck, L.; Spangler, L.

    2009-09-01

    A field facility located in Bozeman, Montana provides the opportunity to test methods to detect, locate, and quantify potential CO2 leakage from geologic storage sites. From 9 July to 7 August 2008, 0.3 t CO2 d{sup -1} were injected from a 100-m long, {approx}2.5 m deep horizontal well. Repeated measurements of soil CO2 fluxes on a grid characterized the spatio-temporal evolution of the surface leakage signal and quantified the surface leakage rate. Infrared CO2 concentration sensors installed in the soil at 30 cm depth at 0 to 10 m from the well and at 4 cm above the ground at 0 and 5 m from the well recorded surface breakthrough of CO2 leakage and migration of CO2 leakage through the soil. Temporal variations in CO2 concentrations were correlated with atmospheric and soil temperature, wind speed, atmospheric pressure, rainfall, and CO2 injection rate.

  4. A usage of CO2 hydrate: convenient method to increase CO2 concentration in culturing algae.

    PubMed

    Nakano, Sho; Chang, Kwang-Hyeon; Shijima, Atsushi; Miyamoto, Hiroyuki; Sato, Yukio; Noto, Yuji; Ha, Jin-Yong; Sakamoto, Masaki

    2014-11-01

    The addition of CO2 to algal culture systems can increase algal biomass effectively. Generally, gas bubbling is used to increase CO2 levels in culture systems; however, it is difficult to quantitatively operate to control the concentration using this method. In this study, we tested the usability of CO2 hydrate for phytoplankton culture. Specifically, green algae Pseudokirchneriella subcapitata were cultured in COMBO medium that contained dissolved CO2 hydrate, after which its effects were evaluated. The experiment was conducted according to a general bioassay procedure (OECD TG201). CO2 promoted algae growth effectively (about 2-fold relative to the control), and the decrease in pH due to dissolution of the CO2 in water recovered soon because of photosynthesis. Since the CO2 hydrate method can control a CO2 concentration easily and quantitatively, it is expected to be useful in future applications.

  5. Experimental multi-phase H2O-CO2 brine interactions at elevated temperature and pressure: Implications for CO2 sequestration in deep-saline aquifers

    USGS Publications Warehouse

    Rosenbauer, R.; Koksalan, T.

    2004-01-01

    The burning of fossil fuel and other anthropogenic activities have caused a continuous and dramatic 30% increase of atmospheric CO2 over the past 150 yr. CO2 sequestration is increasingly being viewed as a tool for managing these anthropogenic CO2 emissions to the atmosphere. CO2-saturated brine-rock experiments were carried out to evaluate the effects of multiphase H2O-CO2 fluids on mineral equilibria and the potential for CO2 sequestration in mineral phases within deep-saline aquifers. Experimental results were generally consistent with theoretical thermodynamic calculations. The solubility of CO2 was enhanced in brines in the presence of both limestone and sandstone relative to brines alone. Reactions between CO2 saturated brines and arkosic sandstones were characterized by desiccation of the brine and changes in the chemical composition of the brine suggesting fixation of CO2 in mineral phases. These reactions were occurring on a measurable but kinetically slow time scale at 120??C.

  6. Stomatal proxy record of CO2 concentrations from the last termination suggests an important role for CO2 at climate change transitions

    NASA Astrophysics Data System (ADS)

    Steinthorsdottir, Margret; Wohlfarth, Barbara; Kylander, Malin E.; Blaauw, Maarten; Reimer, Paula J.

    2013-05-01

    A new stomatal proxy-based record of CO2 concentrations ([CO2]), based on Betula nana (dwarf birch) leaves from the Hässeldala Port sedimentary sequence in south-eastern Sweden, is presented. The record is of high chronological resolution and spans most of Greenland Interstadial 1 (GI-1a to 1c, Allerød pollen zone), Greenland Stadial 1 (GS-1, Younger Dryas pollen zone) and the very beginning of the Holocene (Preboreal pollen zone). The record clearly demonstrates that i) [CO2] were significantly higher than usually reported for the Last Termination and ii) the overall pattern of CO2 evolution through the studied time period is fairly dynamic, with significant abrupt fluctuations in [CO2] when the climate moved from interstadial to stadial state and vice versa. A new loss-on-ignition chemical record (used here as a proxy for temperature) lends independent support to the Hässeldala Port [CO2] record. The large-amplitude fluctuations around the climate change transitions may indicate unstable climates and that “tipping-point” situations were involved in Last Termination climate evolution. The scenario presented here is in contrast to [CO2] records reconstructed from air bubbles trapped in ice, which indicate lower concentrations and a gradual, linear increase of [CO2] through time. The prevalent explanation for the main climate forcer during the Last Termination being ocean circulation patterns needs to re-examined, and a larger role for atmospheric [CO2] considered.

  7. A simulation study on the abatement of CO2 emissions by de-absorption with monoethanolamine.

    PubMed

    Greer, T; Bedelbayev, A; Igreja, J M; Gomes, J F; Lie, B

    2010-01-01

    Because of the adverse effect of CO2 from fossil fuel combustion on the earth's ecosystems, the most cost-effective method for CO2 capture is an important area of research. The predominant process for CO2 capture currently employed by industry is chemical absorption in amine solutions. A dynamic model for the de-absorption process was developed with monoethanolamine (MEA) solution. Henry's law was used for modelling the vapour phase equilibrium of the CO2, and fugacity ratios calculated by the Peng-Robinson equation of state (EOS) were used for H2O, MEA, N2 and O2. Chemical reactions between CO2 and MEA were included in the model along with the enhancement factor for chemical absorption. Liquid and vapour energy balances were developed to calculate the liquid and vapour temperature, respectively.

  8. Screening of microalgae for integral biogas slurry nutrient removal and biogas upgrading by different microalgae cultivation technology.

    PubMed

    Wang, Xue; Bao, Keting; Cao, Weixing; Zhao, Yongjun; Hu, Chang Wei

    2017-07-14

    The microalgae-based technology has been developed to reduce biogas slurry nutrients and upgrade biogas simultaneously. In this work, five microalgal strains named Chlorella vulgaris, Scenedesmus obliquus, Selenastrum capricornutum, Nitzschia palea, and Anabaena spiroides under mono- and co-cultivation were used for biogas upgrading. Optimum biogas slurry nutrient reduction could be achieved by co-cultivating microalgae (Chlorella vulgaris, Scenedesmus obliquus, and Nitzschia palea) with fungi using the pelletization technology. In addition, the effects of different ratio of mixed LED light wavelengths applying mixed light-emitting diode during algae strains and fungi co-cultivation on CO2 and biogas slurry nutrient removal efficiency were also investigated. The results showed that the COD (chemical oxygen demand), TN (total nitrogen), and TP (total phosphorus) removal efficiency were 85.82 ± 5.37%, 83.31 ± 4.72%, and 84.26 ± 5.58%, respectively at red: blue = 5:5 under the co-cultivation of S. obliquus and fungi. In terms of biogas upgrading, CH4 contents were higher than 90% (v/v) for all strains, except the co-cultivation with S. obliquus and fungi at red: blue = 3:7. The results indicated that co-cultivation of microalgae with fungi under mixed light wavelengths treatments was most successful in nutrient removal from wastewater and biogas upgrading.

  9. Investigation of Wyoming Bentonite Hydration in Dry to Water-Saturated Supercritical CH4 and CH4/CO2 Mixtures: Implications for CO2-Enhanced Gas Production

    NASA Astrophysics Data System (ADS)

    Loring, J.

    2015-12-01

    Injection of CO2 into low permeability shale formations leads to additional gas recovery and reduces the flux of CO2 into the atmosphere, thus combining a strong economic incentive with a permanent storage option for CO2. Reduced formation transmissivity due to clay swelling is a concern in CO2-enhanced gas production. Clay minerals partly determine the physical (i.e. permeability, brittleness) and certain chemical properties (i.e. wetting ability, gas adsorption) of shales, and montmorillonites are of particular interest because they swell by the uptake of species in their interlayer. In this study, the hydration and expansion of Na-, Cs-, and NH4+-saturated montmorillonite (Na-, Cs-, and NH4-SWy-2) in high-pressure (90 bar) and moderate temperature (50 °C) methane, carbon dioxide, and CO2/CH4 mixtures (3 and 25 mole% CO2) were investigated using in situ IR spectroscopic titrations, in situ XRD, in situ MAS-NMR, and ab initio electronic structure calculations. The overarching goal was to better understand the hydration/expansion behavior of Na-SWy-2 in CO2/CH4 fluid mixtures by comparison to Cs-, and NH4+-saturated clays. Specific aims were to (1) determine if CH4 intercalates the clays, (2) probe the effects of increasing dissolved CO2 and H2O concentrations, and (3) understand the role of cation solvation by H2O and/or CO2. In pure CH4, no evidence of CH4 intercalation was detected by IR for any of the clays. Similarly, no measurable changes to the basal spacing were observed by XRD in the presence of pure CH4. However, when dry Cs- and NH4-SWy-2 were exposed to dry fluids containing CO2, IR showed maximum CO2 penetrated the interlayer, XRD indicated the clays expanded, and NMR showed evidence for cation solvation by CO2, in line with theoretical predictions. IR titration of these clays with water showed sorbed H2O concentrations decreased with increasing dissolved CO2, suggesting competition for interlayer residency by CO2 and H2O. For Na-SWy-2, on the other

  10. CIUDENs Pilot Project for CO2 Biomonitoring Tools (PISCO2)

    NASA Astrophysics Data System (ADS)

    García, D.; Bruno, J.; Credoz, A.; Grandia, F.; Fuentes, J.; Calabuig, E.; Montoto, M.; Ciuden's Co2 Geological Storage Programme

    2011-12-01

    This paper describes CIUDENs Pilot Project for CO2 Biomonitoring Tools (PISCO2) in NW Spain; focusing on the development of biomonitoring of potential CO2 leakages through testing biogeochemical effects of CO2 injection in soils. CIUDEN is a Spanish National foundation created in 2006 dedicated to different projects related to energy and environment. One of the main activities is the construction and operation of various facilities for Research and Development in CCS. The PISCO2 installation consists of 18 cells excavated in the ground and isolated by concrete. Each cell has a 40 m3. The cells will be filled with different soils from various sites in Spain including the Hontomín site in Burgos, where CIUDENs CO2 Storage Technological Development Plant is under construction. The cells are be equipped with systems for (i) controlled CO2 injection at different depths, (ii) control of irrigation and drainage in the unsaturated soil, (iii) sampling of groundwater and gases, and (iv) monitoring of different parameters; such as water content, pH, CO2 flux, microbiological, botanical, and biogeochemical alterations and the chemical composition of water. The main objectives are: the detection of potential diffuse leakage during/after the injection operations; the use of native species as bio-indicators of early leakage; the calibration and optimization of monitoring sensors & methodologies; the optimization of existing multiphase reactive transport models and the comprehension improvement of the biogeochemical processes. The facility is planned to be fully operational in November 2011. Its configuration makes it unique and suitable for international R&D programs. CIUDEN is open for cooperative research projects with institutions all over the world. Results are expected to significantly contribute to the development of new, useful, economical and ecological biomonitoring tools for wide areas. The paper will focus on the presentation of the technical caracteristics and the

  11. The D0 Upgrade

    SciTech Connect

    Abachi, S.; D0 Collaboration

    1995-07-01

    In this paper we describe the approved DO Upgrade detector, and its physics capabilities. The DO Upgrade is under construction and will run during the next Fermilab collider running period in early 1999 (Run II). The upgrade is designed to work at the higher luminosities and shorter bunch spacings expected during this run. The major elements of t he upgrade are: a new tracking system with a silicon tracker, scintillating fiber tracker, a 2T solenoid, and a central preshower detector; new calorimeter electronics; new muon trigger and tracking detectors with new muon system electronics; a forward preshower detector; new trigger electronics and DAQ improvements to handle the higher rates.

  12. EPIC Computer Upgrade

    NASA Image and Video Library

    Expedition 30 Commander Dan Burbank and Flight Engineer Don Pettit work on installing hardware for the Enhanced Processor and Integrated Communications (EPIC) upgrade of the International Space Sta...

  13. CO2 deserts: implications of existing CO2 supply limitations for carbon management.

    PubMed

    Middleton, Richard S; Clarens, Andres F; Liu, Xiaowei; Bielicki, Jeffrey M; Levine, Jonathan S

    2014-10-07

    Efforts to mitigate the impacts of climate change will require deep reductions in anthropogenic CO2 emissions on the scale of gigatonnes per year. CO2 capture and utilization and/or storage technologies are a class of approaches that can substantially reduce CO2 emissions. Even though examples of this approach, such as CO2-enhanced oil recovery, are already being practiced on a scale >0.05 Gt/year, little attention has been focused on the supply of CO2 for these projects. Here, facility-scale data newly collected by the U.S. Environmental Protection Agency was processed to produce the first comprehensive map of CO2 sources from industrial sectors currently supplying CO2 in the United States. Collectively these sources produce 0.16 Gt/year, but the data reveal the presence of large areas without access to CO2 at an industrially relevant scale (>25 kt/year). Even though some facilities with the capability to capture CO2 are not doing so and in some regions pipeline networks are being built to link CO2 sources and sinks, much of the country exists in "CO2 deserts". A life cycle analysis of the sources reveals that the predominant source of CO2, dedicated wells, has the largest carbon footprint further confounding prospects for rational carbon management strategies.

  14. CO2 Accounting and Risk Analysis for CO2 Sequestration at Enhanced Oil Recovery Sites.

    PubMed

    Dai, Zhenxue; Viswanathan, Hari; Middleton, Richard; Pan, Feng; Ampomah, William; Yang, Changbing; Jia, Wei; Xiao, Ting; Lee, Si-Yong; McPherson, Brian; Balch, Robert; Grigg, Reid; White, Mark

    2016-07-19

    Using CO2 in enhanced oil recovery (CO2-EOR) is a promising technology for emissions management because CO2-EOR can dramatically reduce sequestration costs in the absence of emissions policies that include incentives for carbon capture and storage. This study develops a multiscale statistical framework to perform CO2 accounting and risk analysis in an EOR environment at the Farnsworth Unit (FWU), Texas. A set of geostatistical-based Monte Carlo simulations of CO2-oil/gas-water flow and transport in the Morrow formation are conducted for global sensitivity and statistical analysis of the major risk metrics: CO2/water injection/production rates, cumulative net CO2 storage, cumulative oil/gas productions, and CO2 breakthrough time. The median and confidence intervals are estimated for quantifying uncertainty ranges of the risk metrics. A response-surface-based economic model has been derived to calculate the CO2-EOR profitability for the FWU site with a current oil price, which suggests that approximately 31% of the 1000 realizations can be profitable. If government carbon-tax credits are available, or the oil price goes up or CO2 capture and operating expenses reduce, more realizations would be profitable. The results from this study provide valuable insights for understanding CO2 storage potential and the corresponding environmental and economic risks of commercial-scale CO2-sequestration in depleted reservoirs.

  15. Effects of CO2 leakage on soil bacterial communities from simulated CO2-EOR areas.

    PubMed

    Chen, Fu; Yang, Yongjun; Ma, Yanjun; Hou, Huping; Zhang, Shaoliang; Ma, Jing

    2016-05-18

    CO2-EOR (enhanced oil recovery) has been proposed as a viable option for flooding oil and reducing anthropogenic CO2 contribution to the atmospheric pool. However, the potential risk of CO2 leakage from the process poses a threat to the ecological system. High-throughput sequencing was used to investigate the effects of CO2 emission on the composition and structure of soil bacterial communities. The diversity of bacterial communities notably decreased with increasing CO2 flux. The composition of bacterial communities varied along the CO2 flux, with increasing CO2 flux accompanied by increases in the relative abundance of Bacteroidetes and Firmicutes phyla, but decreases in the relative abundance of Acidobacteria and Chloroflexi phyla. Within the Firmicutes phylum, the genus Lactobacillus increased sharply when the CO2 flux was at its highest point. Alpha and beta diversity analysis revealed that differences in bacterial communities were best explained by CO2 flux. The redundancy analysis (RDA) revealed that differences in bacterial communities were best explained by soil pH values which related to CO2 flux. These results could be useful for evaluating the risk of potential CO2 leakages on the ecosystems associated with CO2-EOR processes.

  16. Glacial CO2 Cycles: A Composite Scenario

    NASA Astrophysics Data System (ADS)

    Broecker, W. S.

    2015-12-01

    There are three main contributors to the glacial drawdown of atmospheric CO2 content: starvation of the supply of carbon to the ocean-atmosphere reservoir, excess CO2 storage in the deep sea, and surface-ocean cooling. In this talk, I explore a scenario in which all three play significant roles. Key to this scenario is the assumption that deep ocean storage is related to the extent of nutrient stratification of the deep Atlantic. The stronger this stratification, the larger the storage of respiration CO2. Further, it is my contention that the link between Milankovitch insolation cycles and climate is reorganizations of the ocean's thermohaline circulation leading to changes in the deep ocean's CO2 storage. If this is the case, the deep Atlantic d13C record kept in benthic foraminifera shells tells us that deep ocean CO2 storage follows Northern Hemisphere summer insolation cycles and thus lacks the downward ramp so prominent in the records of sea level, benthic 18O and CO2. Rather, the ramp is created by the damping of planetary CO2 emissions during glacial time intervals. As it is premature to present a specific scenario, I provide an example as to how these three contributors might be combined. As their magnitudes and shapes remain largely unconstrained, the intent of this exercise is to provoke creative thinking.

  17. CO2 mitigation via accelerated limestone weathering

    USGS Publications Warehouse

    Rau, Greg H.; Knauss, Kevin G.; Langer, William H.; Caldeira,

    2004-01-01

    We evaluate accelerated weathering of limestone (AWL: CO2 + CaCO3 + H2O=> Ca2+ + 2HCO3-) as a low-tech, inexpensive, high-capacity, environmentally-friendly CO2 capture and sequestration technology. With access to seawater and limestone being essential to this approach, significant limestone resources are close to most CO2-emitting power plants along the coastal US. Waste fines, representing more than 20% of current US crushed limestone production (>109 tonnes/yr), could be used as an inexpensive source of AWL carbonate. Under such circumstances CO2 mitigation cost could be as low as $3-$4/tonne. More broadly, 10-20% of US point-source CO2 emissions could be treated at $20-$30/tonne CO2. AWL end-solution disposal in the ocean would significantly reduce effects on ocean pH and carbonate chemistry relative to those caused by direct atmospheric or ocean CO2 disposal. Indeed, the increase in ocean Ca2+ and bicarbonate offered by AWL should enhance growth of corals and other calcifying marine organisms.

  18. Elevated CO2 and Soil Nitrogen Cycling

    NASA Astrophysics Data System (ADS)

    Hofmockel, K.; Schlesinger, W.

    2002-12-01

    Although forests can be large terrestrial carbon sinks, soil fertility can limit carbon sequestration in response to increased atmospheric CO2. During five years of CO2 fertilization (ambient + 200ppm) at the Duke Free-Air CO2 Enrichment (FACE) site, net primary production increased significantly by an average of 25% in treatment plots. Total nitrogen in the foliar canopy increased by 16%, requiring an additional 1.3 g N m-2yr-1 to be taken up from soils under elevated CO2. Mechanisms supporting increased nitrogen acquisition have not been identified. Here we report on biological N-fixation rates, using the acetylene reduction assay, in litter and mineral soil during three years of the CO2 enrichment experiment. Lack of a significant CO2 treatment effect on acetylene reduction indicates that carbon is not directly limiting biological N fixation. Nutrient addition experiments using a complete block design with glucose, Fe, Mo and P indicate biological N fixation is co-limited by molybdenum and carbon. These results suggest even if elevated atmospheric CO2 enhances below-ground carbon availability via root exudation, biological nitrogen fixation may not be stimulated due to micronutrient limitations. Assessment of future carbon sequestration by forest stands must consider limitations imposed by site fertility, including micronutrients.

  19. Advances in post AFM repair cleaning of photomask with CO2 cryogenic aerosol technology

    NASA Astrophysics Data System (ADS)

    Bowers, Charles; Varghese, Ivin; Balooch, Mehdi; Brandt, Werner

    2009-04-01

    As the mask technology matures, critical printing features and sub-resolution assist features (SRAF) shrink below 100 nm, forcing critical cleaning processes to face significant challenges. These challenges include use of new materials, oxidation, chemical contamination sensitivity, proportionally decreasing printable defect size, and a requirement for a damage-free clean. CO2 cryogenic aerosol cleaning has the potential to offer a wide process window for meeting these new challenges, if residue adder issues and damage can be eliminated. Some key differentiations of CO2 cryogenic aerosol cleaning are the non-oxidizing and non-etching properties compared to conventional chemical wet clean processes with or without megasonics. In prior work, the feasibility of CO2 cryogenic aerosol in post AFM repair photomask cleaning was demonstrated. In this paper, recent advancements of CO2 cryogenic aerosol cleaning technology are presented, focusing on the traditional problem areas of particle adders, electrostatic discharge (ESD), and mask damage mitigation. Key aspects of successful CO2 cryogenic aerosol cleaning include the spray nozzle design, CO2 liquid purity, and system design. The design of the nozzle directly controls the size, density, and velocity of the CO2 snow particles. Methodology and measurements of the solid CO2 particle size and velocity distributions will be presented, and their responses to various control parameters will be discussed. Adder control can be achieved only through use of highly purified CO2 and careful materials selection. Recent advances in CO2 purity will be discussed and data shown. The mask cleaning efficiency by CO2 cryogenic aerosol and damage control is essentially an optimization of the momentum of the solid CO2 particles and elimination of adders. The previous damage threshold of 150 nm SRAF structures has been reduced to 70nm and data will be shown indicating 60 nm is possible in the near future. Data on CO2 tribocharge mitigation

  20. Fate of H2S during the cultivation of Chlorella sp. deployed for biogas upgrading.

    PubMed

    González-Sánchez, Armando; Posten, Clemens

    2017-04-15

    The H2S may play a key role in the sulfur cycle among the biogas production by the anaerobic digestion of wastes and the biogas upgrading by a microalgae based technology. The biogas is upgraded by contacting with slightly alkaline aqueous microalgae culture, then CO2 and H2S are absorbed. The dissolved H2S could limit or inhibit the microalgae growth. This paper evaluated the role of dissolved H2S and other sulfured byproducts under prevailing biogas upgrading conditions using a microalgal technology. At initial stages of batch cultivation the growth of Chlorella sp. was presumably inhibited by dissolved H2S. After 2 days, the sulfides were oxidized mainly by oxic chemical reactions to sulfate, which was later rapidly assimilated by Chlorella sp., allowing high growing rates. The fate of H2S during the microalgae cultivation at pH > 8.5 was assessed by a mathematical model where the pentasulfide, thiosulfate and sulfite were firstly produced and converted finally to sulfate for posterior assimilation. Copyright © 2017 Elsevier Ltd. All rights reserved.

  1. Life cycle assessment of biogas upgrading technologies.

    PubMed

    Starr, Katherine; Gabarrell, Xavier; Villalba, Gara; Talens, Laura; Lombardi, Lidia

    2012-05-01

    This article evaluates the life cycle assessment (LCA) of three biogas upgrading technologies. An in-depth study and evaluation was conducted on high pressure water scrubbing (HPWS), as well as alkaline with regeneration (AwR) and bottom ash upgrading (BABIU), which additionally offer carbon storage. AwR and BABIU are two novel technologies that utilize waste from municipal solid waste incinerators - namely bottom ash (BA) and air pollution control residues (APC) - and are able to store CO(2) from biogas through accelerated carbonation processes. These are compared to high pressure water scrubbing (HPWS) which is a widely used technology in Europe. The AwR uses an alkaline solution to remove the CO(2) and then the solution - rich in carbonate and bicarbonate ions - is regenerated through carbonation of APC. The BABIU process directly exposes the gas to the BA to remove and immediately store the CO(2), again by carbonation. It was determined that the AwR process had an 84% higher impact in all LCA categories largely due to the energy intensive production of the alkaline reactants. The BABIU process had the lowest impact in most categories even when compared to five other CO(2) capture technologies on the market. AwR and BABIU have a particularly low impact in the global warming potential category as a result of the immediate storage of the CO(2). For AwR, it was determined that using NaOH instead of KOH improves its environmental performance by 34%. For the BABIU process the use of renewable energies would improve its impact since accounts for 55% of the impact. Copyright © 2011 Elsevier Ltd. All rights reserved.

  2. Core Ion Structures and Solvation Effects in Gas Phase [Sn(CO_{2})_{n}]^{-} Clusters

    NASA Astrophysics Data System (ADS)

    Thompson, Michael C.; Weber, J. Mathias

    2017-06-01

    We report infrared photodissociation spectra of [Sn(CO_{2})_{n}] (n=2-6) clusters. We explore core ion geometries through quantum chemical calculations and assign our experimental spectra through comparison with calculated vibrational frequencies. We discuss our results in the context of heterogeneous catalytic reduction of CO_{2}, and compare our results with previous work on other post-transition metal species.

  3. CO2 enrichment increases element concentrations in grass mixtures by changing species abundances

    USDA-ARS?s Scientific Manuscript database

    The continuing rise in atmospheric carbon dioxide (CO2) concentration may increase plant growth relatively more than the uptake of soil-derived chemical elements that are essential for herbivores. Rising CO2 also may alter the nutritional quality of forage or fodder derived from multi-species veget...

  4. Effects of Breathing Resistance on Resting Ventilatory Sensitivity to CO2

    DTIC Science & Technology

    2014-08-12

    through the same mechanism. It is possible that hyperbaric hyperoxia further decreases chemical sensitivity to CO2. Read’s rebreathing method...retention with inhaled CO2 and breathing resistance,” Undersea and Hyperbaric Medicine, Vol. 39, No. 4, pp. 815–828, 2012. 4.Naval Sea Systems Command

  5. Geological factors affecting CO2 plume distribution

    USGS Publications Warehouse

    Frailey, S.M.; Leetaru, H.

    2009-01-01

    Understanding the lateral extent of a CO2 plume has important implications with regards to buying/leasing pore volume rights, defining the area of review for an injection permit, determining the extent of an MMV plan, and managing basin-scale sequestration from multiple injection sites. The vertical and lateral distribution of CO2 has implications with regards to estimating CO2 storage volume at a specific site and the pore pressure below the caprock. Geologic and flow characteristics such as effective permeability and porosity, capillary pressure, lateral and vertical permeability anisotropy, geologic structure, and thickness all influence and affect the plume distribution to varying degrees. Depending on the variations in these parameters one may dominate the shape and size of the plume. Additionally, these parameters do not necessarily act independently. A comparison of viscous and gravity forces will determine the degree of vertical and lateral flow. However, this is dependent on formation thickness. For example in a thick zone with injection near the base, the CO2 moves radially from the well but will slow at greater radii and vertical movement will dominate. Generally the CO2 plume will not appreciably move laterally until the caprock or a relatively low permeability interval is contacted by the CO2. Conversely, in a relatively thin zone with the injection interval over nearly the entire zone, near the wellbore the CO2 will be distributed over the entire vertical component and will move laterally much further with minimal vertical movement. Assuming no geologic structure, injecting into a thin zone or into a thick zone immediately under a caprock will result in a larger plume size. With a geologic structure such as an anticline, CO2 plume size may be restricted and injection immediately below the caprock may have less lateral plume growth because the structure will induce downward vertical movement of the CO2 until the outer edge of the plume reaches a spill

  6. Can increasing CO2 cool Antarctica?

    NASA Astrophysics Data System (ADS)

    Schmithuesen, Holger; Notholt, Justus; König-Langlo, Gert; Lemke, Peter

    2014-05-01

    CO2 is the strongest anthropogenic forcing agent for climate change since pre-industrial times. Like other greenhouse gases, CO2 absorbs terrestrial surface radiation and causes emission from the atmosphere to space. As the surface is generally warmer than the atmosphere, the total long-wave emission to space is commonly less than the surface emission. However, this does not hold true for the high elevated areas of central Antarctica. Our investigations show, that for the high elevated areas of Antarctica the greenhouse effect (GHE) of CO2 is commonly around zero or even negative. This is based on the quantification of GHE as the difference between long-wave surface emission and top of atmosphere emission. We demonstrate this behaviour with the help of three models: a simple two-layer model, line-by-line calculations, and an ECMWF experiment. Additionally, in this region an increase in CO2 concentration leads to an instantaneous increased long-wave energy loss to space, which is a cooling effect on the earth-atmosphere system. However, short-wave warming by the weak absorption of solar radiation by CO2 are not taken into account here. The reason for this counter-intuitive behaviour is the fact that in the interior of Antarctica the surface is often colder than the stratosphere above. Radiation from the surface in the atmospheric window emitted to space is then relatively lower compared to radiation in the main CO2 band around 15 microns, which originates mostly from the stratosphere. Increasing CO2 concentration leads to increasing emission from the atmosphere to space, while blocking additional portions of surface emission. If the surface is colder than the stratosphere, this leads to additional long-wave energy loss to space for increasing CO2. Our findings for central Antarctica are in strong contrast to the generally known effect that increasing CO2 has on the long-wave emission to space, and hence on the Antarctic climate.

  7. Detecting small scale CO2 emission structures using OCO-2

    NASA Astrophysics Data System (ADS)

    Schwandner, Florian M.; Eldering, Annmarie; Verhulst, Kristal R.; Miller, Charles E.; Nguyen, Hai M.; Oda, Tomohiro; O'Dell, Christopher; Rao, Preeti; Kahn, Brian; Crisp, David; Gunson, Michael R.; Sanchez, Robert M.; Ashok, Manasa; Pieri, David; Linick, Justin P.; Yuen, Karen

    201