Canada
Decarbonization of Cement Production in a Hydrogen Economy
Apr 2022
Publication
The transition to net-zero emission energy systems creates synergistic opportunities across sectors. For example fuel hydrogen production from water electrolysis generates by-product oxygen that could be used to reduce the cost of carbon capture and storage (CCS) essential in the decarbonization of clinker production in cement making. To assess this opportunity a techno-economic assessment was carried out for the production of clinker using oxy-combustion in a natural gas-fueled plant coupled to CCS. Material and energy flows were assessed in a reference case for clinker production (oxygen from air no CCS) and compared to oxy-combustion clinker production from either an air separation unit (ASU 95% O2) or water electrolysis (100% O2) both coupled to CCS. Compared to the reference air-combusted clinker plant oxy-combustion increases thermal energy demand by 7% and electricity demand by 137% for ASU and 67% for electrolytic oxygen. The levelized cost of oxygen supply ranges from $49/tO2 for an on-site ASU to pipelined electrolytic O2 at $35/tO2 (200 km) or $13/t O2 (20 km). The cost of clinker for the reference plant without CCS increases linearly from $84/t clinker to $193/t clinker at a carbon price of $0/tCO2 to $150/tCO2 respectively. With oxy-combustion and CCS the clinker production cost ranges from $119 to $122/t clinker reflecting a breakeven carbon price of $39 to $53/tCO2 compared to the reference case. The lower cost for the electrolytic supply of by-product oxygen compared to ASU oxygen must be balanced against the reliability of supply the pipeline transport distance and the charges that may be added by the hydrogen producer.
A Comparative Study of Detonability and Propensity to Sustain High-speed Turbulent Deflagrations in Hydrogen and Methane Mixtures
Sep 2013
Publication
We’ve studied the conditions enabling a detonation to be quenched when interacting with an obstruction and the propensity for establishing subsequent fast-flame. Oxy-hydrogen detonations were found quench more easily than oxy-methane detonations when comparing the ratio of gap size and the detonation cell size. High-speed turbulent deflagrations that re-accelerate back to a detonation were only observed in methane-oxygen mixtures. Separate hot-spot ignition calculations revealed that the higher detonability of methane correlates with its stronger propensity to develop localized hot-spots. The results suggest that fast-flames are more difficult to form in hydrogen than in methane mixtures.
Kinetic Modeling and Quantum Yields: Hydrogen Production via Pd‐TiO2 Photocatalytic Water Splitting under Near‐UV and Visible Light
Jan 2022
Publication
A palladium (Pd) doped mesoporous titanium dioxide (TiO2) photocatalyst was used to produce hydrogen (H2) via water splitting under both near‐UV and visible light. Experiments were carried out in the Photo‐CREC Water‐II Reactor (PCW‐II) using a 0.25 wt% Pd‐TiO2 photocatalyst initial pH = 4 and 2.0 v/v% ethanol as an organic scavenger. After 6 h of near‐UV irradiation this photocatalyst yielded 113 cm3 STP of hydrogen (H2). Furthermore after 1 h of near‐UV photoreduc‐ tion followed by 5 h of visible light the 0.25 wt% Pd‐TiO2 photocatalyst yielded 5.25 cm3 STP of H2. The same photocatalyst photoreduced for 24 h under near‐UV and subsequently exposed to 5 h of visible light yielded 29 cm3 STP of H2. It was observed that the promoted redox reactions led to the production of hydrogen and by‐products such as methane ethane ethylene acetaldehyde carbon monoxide carbon dioxide and hydrogen peroxide. These redox reactions could be modeled using an “in series‐parallel” reaction network and Langmuir Hinshelwood based kinetics. The proposed rate equations were validated using statistical analysis for the experimental data and calculated kinetic parameters. Furthermore Quantum yields (QYୌ%) based on the H produced were also established at promising levels: (a) 34.8% under near‐UV light and 1.00 g L−1 photocatalyst concen‐ tration; (b) 8.8% under visible light and 0.15 g L−1. photocatalyst concentration following 24 h of near‐UV.
A Large-Scale Study on the Effect of Ambient Conditions on Hydrogen Recombiner Induced Ignition
Sep 2019
Publication
Hydrogen recombiners (known in the nuclear industry as passive autocatalytic recombiners-PARs) in general can be utilized for mitigation of hydrogen in controlled areas where there is potential for hydrogen release and ventilation is not practical. Recombiners are widely implemented in the nuclear industry however there are other applications of recombiners outside the nuclear industry that have not yet been explored practically. The most notable benefit of recombiners over conventional hydrogen mitigation measures is their passive capability where power or operator actions are not needed for the equipment to remove hydrogen when it is present.
One of most significant concerns regarding the use of hydrogen recombiners in industry is their potential to ignite hydrogen at elevated concentrations (>6 vol%). The catalyst heated by the exothermal H2–O2 reaction is known to be a potential ignition source to cause hydrogen burns. An experimental program utilizing a full-size PAR at the Large-Scale Vented Combustion Test Facility (LSVCTF) has been carried out by Canadian Nuclear Laboratories (CNL) to investigate and understand the behaviour of hydrogen combustion induced by a PAR on a large-scale basis. A number of parameters external to the PAR have been explored including the effect of ambient humidity (steam) and temperature. The various aspects of this investigation will be discussed in this paper and examples of results are provided.
One of most significant concerns regarding the use of hydrogen recombiners in industry is their potential to ignite hydrogen at elevated concentrations (>6 vol%). The catalyst heated by the exothermal H2–O2 reaction is known to be a potential ignition source to cause hydrogen burns. An experimental program utilizing a full-size PAR at the Large-Scale Vented Combustion Test Facility (LSVCTF) has been carried out by Canadian Nuclear Laboratories (CNL) to investigate and understand the behaviour of hydrogen combustion induced by a PAR on a large-scale basis. A number of parameters external to the PAR have been explored including the effect of ambient humidity (steam) and temperature. The various aspects of this investigation will be discussed in this paper and examples of results are provided.
Compliance Measurements of Fuel Cell Electric Vehicle Exhaust
Sep 2019
Publication
The NREL Sensor Laboratory has been developing an analyzer that can verify compliance to the international United Nations Global Technical Regulation number 13 (GTR 13--Global Technical Regulation on Hydrogen and Fuel Cell Vehicles) prescriptive requirements pertaining to allowable hydrogen levels in the exhaust of fuel cell electric vehicles (FCEV) [1]. GTR 13 prescribes that the FCEV exhaust shall remain below 4 vol% H2 over a 3-second moving average and shall not at any time exceed 8 vol% H2 as verified with an analyzer with a response time (t90) of 300 ms or faster. GTR 13 has been implemented and is to serve as the basis for national regulations pertaining to hydrogen powered vehicle safety in the United States Canada Japan and the European Union. In the U.S. vehicle safety is overseen by the Department of Transportation (DOT) through the Federal Motor Vehicle Safety Standards (FMVSS) and in Canada by Transport Canada through the Canadian Motor Vehicle Safety Standard (CMVSS). The NREL FCEV exhaust analyzer is based upon a low-cost commercial hydrogen sensor with a response time (t90) of less than 250 ms. A prototype analyzer and gas probe assembly have been constructed and tested that can interface to the gas sampling system used by Environment and Climate Change Canada’s (ECCC) Emission Research and Measurement Section (ERMS) for the exhaust gas analysis. Through a partnership with Transport Canada ECCC will analyze the hydrogen level in the exhaust of a commercial FCEV. ECCC will use the NREL FCEV Exhaust Gas analyzer to perform these measurements. The analyzer was demonstrated on a FCEV operating under simulated road conditions using a chassis dynamometer at a private facility.
Recovery Through Reform: Assessing the climate compatibility of Canada’s COVID-19 response in 2020
Feb 2021
Publication
Governments around the world are leveraging unprecedented amounts of capital to respond to the pandemic and bailing out struggling industries. Trends in energy-related spending indicate that despite the green push the world’s largest economies have still favoured fossil energy over clean energy.<br/><br/>We evaluate energy-related spending in Canada in 2020 (since the onset of COVID-19) using data from the Energy Policy Tracker. Trends in Canada are then compared to flagship policies in key jurisdictions with recent progressive climate policy announcements including France Germany and the United Kingdom. The brief ends with broad recommendations on how Canada can better align its recovery funding with climate action and fossil fuel subsidy reform.<br/><br/>This brief is one of three International Institute for Sustainable Development (IISD) policy briefs in its Recovery Through Reform series which assesses how efforts to achieve a green recovery from COVID-19 in Canada rely on—and can contribute to—fossil fuel subsidy reform.
Experimental Study on Accumulation of Helium Released into a Semi-confined Enclosure without Ventilation
Sep 2019
Publication
This paper examines the helium dispersion behaviour in a 16.6 m3 enclosure with a small opening in the floor and distributed leaks along the edges. Helium a simulant for hydrogen was injected near the center of the floor with an injection rate ranging from 2 to 50 standard liters per minute (Richardson number of 0.3–134) through an upward-facing nozzle. In a short-term transient the helium distribution predicted with the models of Baines & Turner (1969) and Worster & Huppert (1983) matched the measured distributions reasonably well. In a long-term transient the vertical helium profile always reached a steady state which consisted of a homogenous layer at the top overlaying a stratified layer at the bottom. The helium transients in the uniform layer predicted with the models of Lowesmith (2009) and Prasad & Yang (2010) assuming a vent was located in the ceiling were in good agreement with the measured transients.
Simulation of Shock-Initiated Ignition
Sep 2009
Publication
The scenario of detonative ignition in shocked mixture is significant because it is a contributor to deflagration to detonation transition for example following shock reflections. However even in one dimension simulation of ignition between a contact surface or a flame and a shock moving into a combustible mixture is difficult because of the singular nature of the initial conditions. Initially as the shock starts moving into reactive mixture the region filled with reactive mixture has zero thickness. On a fixed grid the number of grid points between the shock and the contact surface increases as the shock moves away from the latter. Due to initial lack of resolution in the region of interest staircasing may occur whereby the resulting plots consist of jumps between few values a few grid points and these numerical artifacts are amplified by the chemistry which is very sensitive to temperature leading to unreliable results. The formulation is transformed replacing time and space by time and space over time as the independent variables. This frame of reference corresponds to the self-similar formulation in which the non-reactive problem remains stationary and the initial conditions are well-resolved. Additionally a solution obtained from short time perturbation is used as initial condition at a time still short enough for the perturbation to be very accurate but long enough so that there is sufficient resolution. The numerical solution to the transformed problem is obtained using an essentially non-oscillatory algorithm which is adequate not only for the early part of the process but also for the latter part when chemistry leads to appearance of a shock and eventually a detonation wave is formed. A validation study was performed and the results were compared with the literature for single step Arrhenius chemistry. The method and its implementation were found to be effective. Results are presented for values of activation energy ranging from mild to stiff.
The Hydrogen Executive Leadership Panel (HELP) Initiative for Emergency Responder Training
Sep 2007
Publication
In close cooperation with their Canadian counterparts United States public safety authorities are taking the first steps towards creating a proper infrastructure to ensure the safe use of the new hydrogen fuel cells now being introduced commercially. Currently public safety officials are being asked to permit hydrogen fuel cells for stationary power and as emergency power backups for the telecommunications towers that exist everywhere. Consistent application of the safety codes is difficult – in part because it is new – yet it is far more complex to train emergency responders to deal safely with the inevitable hydrogen incidents. The US and Canadian building and fire codes and standards are similar but not identical. The US and Canadian rules are unlikely to be useful to other nations without modification to suit different regulatory systems. However emergency responder safety training is potentially more universal. The risks strategies and tactics are unlikely to differ much by region. The Hydrogen Executive Leadership Panel (HELP) made emergency responder safety training its first priority because the transition to hydrogen depends on keeping incidents small and inoffensive and the public and responders safe from harm. One might think that advising 1.2 million firefighters and 800000 law enforcement officers about hydrogen risks is no more complicated than adding guidance to a website. One would be wrong. The term “training” has specific legal implications which may vary by state. For hazardous materials federal requirements apply. Insurance companies place training requirements on the policies they sell to fire departments including the thousands of small all-volunteer departments which may operate as private corporations. Union contracts may define training and promotions may be based on satisfactorily completed certain levels of training. Emergency responders could no sooner learn how to extinguish a<br/>hydrogen fire by reading a webpage than a person could learn to ride a bicycle by reading a book. Procedures must be learned by listening reading and then doing. Regular practice is necessary. As new hydrogen applications are commercialized additional responder training may be necessary. This highlights another obstacle emergency responders’ ability to travel distances and take the time to undergo training. Historically fire academies established adjunct instructor programs and satellite academies to bring the training to firefighters. The large well-equipped academies are typically used for specialized training. States rarely have enough instructors and instructors often must take the time to create a course outline research each point and produce a program that is informative useful and holds the attention of responders. The challenge of training emergency responders seems next to impossible but public safety authorities are asked to tackle the impossible every day and a model exists to move forward in the U.S. Over the past few years the National Association of State Fire Marshals and U.S. Department of Transportation enlisted the help of emergency responders and industry to create a standardized approach to train emergency responders to deal with pipeline incidents. A curriculum and training materials were created and more than 26000 sets have been distributed for free to public safety agencies nationwide. More than 8000 instructors have been trained to use these materials that are now part of the regular training in 23 states. Using this model HELP intends to ensure that all emergency responders are trained to address hydrogen risks. The model and the rigorous scenario analysis and review used to developing the operational and technical training is addressed in this paper.
Synthesis and Performance of Photocatalysts for Photocatalytic Hydrogen Production: Future Perspectives
Dec 2021
Publication
Photocatalysis for “green” hydrogen production is a technology of increasing importance that has been studied using both TiO2–based and heterojunction composite-based semiconductors. Different irradiation sources and reactor units can be considered for the enhancement of photocatalysis. Current approaches also consider the use of electron/hole scavengers organic species such as ethanol that are “available” in agricultural waste in communities around the world. Alternatively organic pollutants present in wastewaters can be used as organic scavengers reducing health and environmental concerns for plants animals and humans. Thus photocatalysis may help reduce the carbon footprint of energy production by generating H2 a friendly energy carrier and by minimizing water contamination. This review discusses the most up-to-date and important information on photocatalysis for hydrogen production providing a critical evaluation of: (1) The synthesis and characterization of semiconductor materials; (2) The design of photocatalytic reactors; (3) The reaction engineering of photocatalysis; (4) Photocatalysis energy efficiencies; and (5) The future opportunities for photocatalysis using artificial intelligence. Overall this review describes the state-of-the-art of TiO2–based and heterojunction composite-based semiconductors that produce H2 from aqueous systems demonstrating the viability of photocatalysis for “green” hydrogen production.
Enhancing the Efficiency of Power- and Biomass-to-liquid Fuel Processes Using Fuel-assisted Solid Oxide Electrolysis Cells
Apr 2022
Publication
Power- and biomass-to-liquid fuel processes (PBtL) can utilize renewable energy and residual forestry waste to produce liquid synthetic fuels which have the potential to mitigate the climate impacts of the current transportation infrastructure including the long-haul aviation sector. In a previous study we demonstrated that implementing a solid oxide electrolysis cell (SOEC) in the PBtL process can significantly increase the energy efficiency of fuel production by supplying the produced hydrogen to a reverse water gas shift (RWGS) reactor to generate syngas which is then fed downstream to a Fischer–Tropsch (FT) reactor. The tail gas emitted from the FT reactor consists primarily of a mixture of hydrogen carbon monoxide and methane and is often recycled to the entrained flow gasifier located at the beginning of the process. In this analysis we investigate the efficiency gains of the PBtL process as a result of redirecting the tail gas of the FT reactor to the anode of an SOEC to serve as fuel. Supplying fuel to an SOEC can lower the electrical work input required to facilitate steam electrolysis when reacting electrochemically with oxide ions in the anode which in turn can reduce oxygen partial pressures and thus alleviate material degradation. Accordingly we develop a thermodynamic framework to reveal the performance limits of fuel-assisted SOECs (FASOECs) and provide strategies to minimize oxygen partial pressures in the SOEC anode. Additionally we elucidate how much fuel is required to match the heating demands of a cell when steam is supplied to the cathode over a broad range of inlet temperatures and demonstrate the influence of a set of reaction pathways of the supplied fuel on the operating potential of an FASOEC and the corresponding efficiency gain of the PBtL process. Based on preliminary calculations we estimate that implementing an FASOEC in the PBtL process can increase the energy efficiency of fuel production to more than 90% depending on the amount of FT tail gas available to the system.
Experimental Investigation of Spherical-flame Acceleration in Lean Hydrogen-air Mixtures
Oct 2015
Publication
Large-scale experiments examining spherical-flame acceleration in lean hydrogen-air mixtures were performed in a 64 m3 constant-pressure enclosure. Equivalence ratios ranging from 0.33 to 0.57 were examined using detailed front tracking for flame diameters up to 1.2 m through the use of a Background Oriented Schlieren (BOS) technique. From these measurements the critical radii for onset of instability for these mixtures on the order of 2–3 cm were obtained. In addition the laminar burning velocity and rate of flame acceleration as a function of radius were also measured.
Heat Transfer Analysis for Fast Filling of On-board Hydrogen Tank
Mar 2019
Publication
The heat transfer analysis in the filling process of compressed on-board hydrogen storage tank has been the focus of hydrogen storage research. The initial conditions mass flow rate and heat transfer coefficient have certain influence on the hydrogen filling performance. In this paper the effects of mass flow rate and heat transfer coefficient on hydrogen filling performance are mainly studied. A thermodynamic model of the compressed hydrogen storage tank was established by Matlab/Simulink. This 0D model is utilized to predict the hydrogen temperature hydrogen pressure tank wall temperature and SOC (State of Charge) during filling process. Comparing the simulated results with the experimental data the practicability of the model can be verified. The simulated results have certain meaning for improving the hydrogenation parameters in real filling process. And the model has a great significance to the study of hydrogen filling and purification.
CFD Based Simulation of Hydrogen Release Through Elliptical Orifices
Sep 2013
Publication
Computational Fluid Dynamics (CFD) is applied to investigate the near exit jet behavior of high pressure hydrogen release into quiescent ambient air through different types of orifices. The size and geometry of the release hole can affect the possibility of auto-ignition. Therefore the effect of release geometry on the behavior and development of hydrogen jet issuing from non-axisymmetric (elliptical) and expanding orifices is investigated and compared with their equivalent circular orifices. A three-dimensional in-house code is developed using the MPI library for parallel computing to simulate the flow based on an inviscid approximation. Convection dominates viscous effects in strongly underexpanded supersonic jets in the vicinity of release exit justifying the use of the Euler equations. The transport (advection) equation is applied to calculate the concentration of hydrogen-air mixture. The Abel-Nobel equation of state is used because high pressure hydrogen flow deviates from the ideal gas assumption. This work effort is conducted to fulfill two objectives. First two types of circular and elliptic orifices with the same cross sectional area are simulated and the flow behavior of each case is studied and compared during the initial stage of release. Second the comparative study between expanding circular exit and its fixed counterpart is carried out. This evaluation is conducted for different sizes of nozzle with different aspect ratios.
Ignition Experiments of Hydrogen Mixtures by Different Methods and Description of the DRDC Test Facilities
Sep 2009
Publication
The paper will present results of hydrogen/oxygen mixtures ignited by using electric sparks electrostatic discharges a heating element and a flame. Measurements of the lower flammability limit (LFL) was done for each ignition method. The hydrogen mixtures of different concentrations were ignited at the bottom of a combustion chamber leading to an upward propagation of the resulting flame. At some level of concentration the combustion was partial due to the limited upward propagation. The complete combustion of the whole mixture was observed at concentration limits higher than the known LFL of 4% vol. for hydrogen in air. The paper will describe the test facilities and the resulting ignition probabilities for different ignition methods.
Estimation of Final Hydrogen Temperature From Refueling Parameters
Oct 2015
Publication
Compressed hydrogen storage is currently widely used in fuel cell vehicles due to its simplicity in tank structure and refuelling process. For safety reason the final gas temperature in the hydrogen tank during vehicle refuelling must be maintained under a certain limit e.g. 85 °C. Many experiments have been performed to find the relations between the final gas temperature in the hydrogen tank and refueling conditions. The analytical solution of the hydrogen temperature in the tank can be obtained from the simplified thermodynamic model of a compressed hydrogen storage tank and it serves as function formula to fit experimental temperatures. From the analytical solution the final hydrogen temperature can be expressed as a weighted average form of initial temperature inflow temperature and ambient temperature inspired by the rule of mixtures. The weighted factors are related to other refuelling parameters such as initial mass initial pressure refuelling time refuelling mass rate average pressure ramp rate (APRR) final mass final pressure etc. The function formula coming from the analytical solution of the thermodynamic model is more meaningful physically and more efficient mathematically in fitting experimental temperatures. The simple uniform formula inspired by the concept of the rule of mixture and its weighted factors obtained from the analytical solution of lumped parameter thermodynamics model is representatively used to fit the experimental and simulated results in publication. Estimation of final hydrogen temperature from refuelling parameters based on the rule of mixtures is simple and practical for controlling the maximum temperature and for ensuring hydrogen safety during fast filling process.
CFD Simulations of the Effect of Ventilation on Hydrogen Release Behavior and Combustion in an Underground Mining Environment
Sep 2013
Publication
CFD simulations investigating the effect of ventilation airflow on hydrogen release behaviour in an underground mining tunnel were performed using FLACS hydrogen. Both dispersion and combustion scenarios of a hydrogen release coming from a severed distribution pipeline were investigated. Effects on the hydrogen dispersion such as ventilation strength and the mechanism of air flow supply (a pull or push fan) and mine opening surface roughness surface cavities and obstructions were explored. Results showing the effect of changing the position of the leak adding a cavity on the ceiling of the tunnel and changing the roughness of the walls are given. Overpressure sensitivity to the ignition delay was also considered. From the results for the varied ventilation regimes and spatial scenarios it is difficult to identify the optimal ventilation strategy giving the safest conditions for hydrogen distribution and refuelling in an underground mine.
Implementation of Large Scale Shadowgraphy in Hydrogen Safety Phenomena
Sep 2013
Publication
We have implemented a portable large-scale shadowgraph system for use in flow visualization relating to hydrogen safety. Previous large-scale shadowgraph and schlieren implementations have often been limited to background- oriented techniques which are subject to noise. The system built is based on a large-scale shadowgraph technique developed by Settles which allows for high-quality visualization. We have applied the shadowgraph system to complex phenomena and current issues in hydrogen safety including DDT in long channels jet releases and unconfined deflagrations. Shadowgrams taken are compared to a Z-schlieren system. This shadowgraph system allows analysis of these phenomena at longer length scales.
Measurements of Flow Velocity and Scalar Concentration in Turbulent Multi-component Jets
Sep 2017
Publication
Buoyancy effects and nozzle geometry can have a significant impact on turbulent jet dispersion. This work was motivated by applications involving hydrogen. Using helium as an experimental proxy buoyant horizontal jets issuing from a round orifice on the side wall of a circular tube were analyzed experimentally using particle image velocimetry (PIV) and planar laser-induced fluorescence (PLIF) techniques simultaneously to provide instantaneous and time-averaged flow fields of velocity and concentration. Effects of buoyancy and asymmetry on the resulting flow structure were studied over a range of Reynolds numbers and gas densities. Significant differences were found between the centreline trajectory spreading rate and velocity decay of conventional horizontal round axisymmetric jets issuing through flat plates and the pipeline leak-representative jets considered in the present study. The realistic pipeline jets were always asymmetric and found to deflect about the jet axis in the near field. In the far field it was found that the realistic pipeline leak geometry causes buoyancy effects to dominate much sooner than expected compared to horizontal round jets issuing through flat plates.
Hydrogen Fueling Standardization: Enabling ZEVs with "Same as Today" Fueling and FCEV Range and Safety
Oct 2015
Publication
Zero Emission Vehicles (ZEVs) are necessary to help reduce the emissions in the transportation sector which is responsible for 40% of overall greenhouse gas emissions. There are two types of ZEVs Battery Electric Vehicles (BEVs) and Fuel Cell Electric Vehicles (FCEVs) Commercial Success of BEVs has been challenging thus far also due to limited range and very long charging duration. FCEVs using H2 infrastructure with SAE J2601 and J2799 standards can be consistently fuelled in a safe manner fast and resulting in a range similar to conventional vehicles. Specifically fuelling with SAE J2601 with the SAE J2799 enables FCEVs to fill with hydrogen in 3-5 minutes and to achieve a high State of Charge (SOC) resulting in 300+ mile range without exceeding the safety storage limits. Standardized H2 therefore gives an advantage to the customer over electric charging. SAE created this H2 fuelling protocol based on modelling laboratory and field tests. These SAE standards enable the first generation of commercial FCEVs and H2 stations to achieve a customer acceptable fueling similar to today's experience. This report details the advantages of hydrogen and the validation of H2 fuelling for the SAE standards.
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