Italy
A Preliminary Assessment of the Potential of Low Percentage Green Hydrogen Blending in the Italian Natural Gas Network
Oct 2020
Publication
The growing rate of electricity generation from renewables is leading to new operational and management issues on the power grid because the electricity generated exceeds local requirements and the transportation or storage capacities are inadequate. An interesting option that is under investigation by several years is the opportunity to use the renewable electricity surplus to power electrolyzers that split water into its component parts with the hydrogen being directly injected into natural gas pipelines for both storage and transportation. This innovative approach merges together the concepts of (i) renewable power-to-hydrogen (P2H) and of (ii) hydrogen blending into natural gas networks. The combination of renewable P2H and hydrogen blending into natural gas networks has a huge potential in terms of environmental and social benefits but it is still facing several barriers that are technological economic legislative. In the framework of the new hydrogen strategy for a climate-neutral Europe Member States should design a roadmap moving towards a hydrogen ecosystem by 2050. The blending of “green hydrogen” that is hydrogen produced by renewable sources in the natural gas network at a limited percentage is a key element to enable hydrogen production in a preliminary and transitional phase. Therefore it is urgent to evaluate at the same time (i) the potential of green hydrogen blending at low percentage (up to 10%) and (ii) the maximum P2H capacity compatible with low percentage blending. The paper aims to preliminary assess the green hydrogen blending potential into the Italian natural gas network as a tool for policy makers grid and networks managers and energy planners.
Optimisation-based System Designs for Deep Offshore Wind Farms including Power to Gas Technologies
Feb 2022
Publication
A large deployment of energy storage solutions will be required by the stochastic and non-controllable nature of most renewable energy sources when planning for higher penetration of renewable electricity into the energy mix. Various solutions have been suggested for dealing with medium- and long-term energy storage. Hydrogen and ammonia are two of the most frequently discussed as they are both carbon-free fuels. In this paper the authors analyse the energy and cost efficiency of hydrogen and ammonia-based pathways for the storage transportation and final use of excess electricity from an offshore wind farm. The problem is solved as a linear programming problem simultaneously optimising the size of each problem unit and the respective time-dependent operational conditions. As a case study we consider an offshore wind farm of 1.5 GW size located in a reference location North of Scotland. The energy efficiency and cost of the whole chain are evaluated and compared with competitive alternatives namely batteries and liquid hydrogen storage. The results show that hydrogen and ammonia storage can be part of the optimal solution. Moreover their use for long-term energy storage can provide a significant cost-effective contribution to an extensive penetration of renewable energy sources in national energy systems.
Photoelectrochemical Hydrogen Production by Screen-Printed Copper Oxide Electrodes
May 2021
Publication
In this work copper oxides-based photocathodes for photoelectrochemical cells (PEC) were produced for the first time by screen printing. A total 7 × 10−3 g/m2 glycerine trioleate was found as optimum deflocculant amount to assure stable and homogeneous inks based on CuO nano-powder. The inks were formulated considering different binder amounts and deposited producing films with homogenous thickness microstructure and roughness. The as-produced films were thermally treated to obtain Cu2O- and Cu2O/CuO-based electrodes. The increased porosity obtained by adding higher amounts of binder in the ink positively affected the electron transfer from the surface of the electrode to the electrolyte thus increasing the corresponding photocurrent values. Moreover the Cu2O/CuO system showed a higher charge carrier and photocurrent density than the Cu2O-based one. The mixed Cu2O/CuO films allowed the most significant hydrogen production especially in slightly acid reaction conditions.
Different Scenarios of Electric Mobility: Current Situation and Possible Future Developments of Fuel Cell Vehicles in Italy
Jan 2020
Publication
The diffusion of electric vehicles in Italy has started but some complications weight its spread. At present hybrid technology is the most followed by users due particularly to socioeconomic factors such as cost of investment and range anxiety. After a deep discussion of the Italian scenario the aim of the paper is to recognize whether fuel cell technology may be an enabling solution to overcome pollution problems and respect for the environment. The opportunity to use fuel cells to store electric energy is quite fascinating—the charging times will be shortened and heavy passenger transport should be effortless challenged. On the basis of the present history and by investigating the available information this work reports the current e-mobility state in Italy and forecasts the cities in which a fuel cell charging infrastructure should be more profitable with the intention of granting a measured outlook on the plausible development of this actual niche market.
Hydrogen and Oxygen Production via Water Splitting in a Solar-Powered Membrane Reactor—A Conceptual Study
Jan 2021
Publication
Among the processes for producing hydrogen and oxygen from water via the use of solar energy water splitting has the advantage of being carried out in onestep. According to thermodynamics this process exhibits conversions of practical interest at very high temperatures and needs efficient separation systems in order to separate the reaction products hydrogen and oxygen. In this conceptual work the behaviour of a membrane reactor that uses two membranes perm-selective to hydrogen and oxygen is investigated in the temperature range 2000–2500 °C of interest for coupling this device with solar receivers. The effect of the reaction pressure has been evaluated at 0.5 and 1 bar while the permeate pressure has been fixed at 100 Pa. As a first result the use of the membrane perm-selective to oxygen in addition to the hydrogen one has improved significantly the reaction conversion that for instance at 0.5 bar and 2000 °C moves from 9.8% up to 18.8%. Based on these critical data a preliminary design of a membrane reactor consisting of a Ta tubular membrane separating the hydrogen and a hafnia camera separating the oxygen is presented: optimaloperating temperature of the reactor results in being around 2500 °C a value making impracticable its coupling with solar receivers even in view of an optimistic development of this technology. The study has verified that at 2000 °C with a water feed flow rate of 1000 kg h−1 about 200 and 100 m3 h−1 of hydrogen and oxygen are produced. In this case a surface of the hafnia membrane of the order of hundreds m2 is required: the design of such a membrane device may be feasible when considering special reactor configurations.
Delivering Net-zero Carbon Heat: Technoeconomic and Whole-system Comparisons of Domestic Electricity- and Hydrogen-driven Technologies in the UK
Apr 2022
Publication
Proposed sustainable transition pathways for moving away from natural gas in domestic heating focus on two main energy vectors: electricity and hydrogen. Electrification would be implemented by using vapourcompression heat pumps which are currently experiencing market growth in many countries. On the other hand hydrogen could substitute natural gas in boilers or be used in thermally–driven absorption heat pumps. In this paper a consistent thermodynamic and economic methodology is developed to assess the competitiveness of these options. The three technologies along with the option of district heating are for the first time compared for different weather/ambient conditions and fuel-price scenarios first from a homeowner’s and then from a wholeenergy system perspective. For the former two-dimensional decision maps are generated to identify the most cost-effective technologies for different combinations of fuel prices. It is shown that in the UK hydrogen technologies are economically favourable if hydrogen is supplied to domestic end-users at a price below half of the electricity price. Otherwise electrification and the use of conventional electric heat pumps will be preferred. From a whole-energy system perspective the total system cost per household (which accounts for upstream generation and storage as well as technology investment installation and maintenance) associated with electric heat pumps varies between 790 and 880 £/year for different scenarios making it the least-cost decarbonisation pathway. If hydrogen is produced by electrolysis the total system cost associated with hydrogen technologies is notably higher varying between 1410 and 1880 £/year. However this total system cost drops to 1150 £/year with hydrogen produced cost-effectively by methane reforming and carbon capture and storage thus reducing the gap between electricity- and hydrogen-driven technologies.
Hydrogen Embrittlement Evaluation of Micro Alloyed Steels by Means of J-Integral Curve
Jun 2019
Publication
The aim of this work is the evaluation of the hydrogen effect on the J-integral parameter. It is well-known that the micro alloyed steels are affected by Hydrogen Embrittlement phenomena only when they are subjected at the same time to plastic deformation and hydrogen evolution at their surface. Previous works have pointed out the absence of Hydrogen Embrittlement effects on pipeline steels cathodically protected under static load conditions. On the contrary in slow strain rate tests it is possible to observe the effect of the imposed potential and the strain rate on the hydrogen embrittlement steel behavior only after the necking of the specimens. J vs. Δa curves were measured on different pipeline steels in air and in aerated NaCl 3.5 g/L solution at free corrosion potential or under cathodic polarization at −1.05 and −2 V vs. SCE. The area under the J vs. Δa curves and the maximum crack propagation rate were taken into account. These parameters were compared with the ratio between the reduction of area in environment and in air obtained by slow strain rate test in the same environmental conditions and used to rank the different steels.
Integration of Chemical Looping Combustion for Cost-effective CO2 Capture from State-of-the-art Natural Gas Combined Cycles
May 2020
Publication
Chemical looping combustion (CLC) is a promising method for power production with integrated CO2 capture with almost no direct energy penalty. When integrated into a natural gas combined cycle (NGCC) plant however CLC imposes a large indirect energy penalty because the maximum achievable reactor temperature is far below the firing temperature of state-of-the-art gas turbines. This study presents a techno-economic assessment of a CLC plant that circumvents this limitation via an added combustor after the CLC reactors. Without the added combustor the energy penalty amounts to 11.4%-points causing a high CO2 avoidance cost of $117.3/ton which is more expensive than a conventional NGCC plant with post-combustion capture ($93.8/ton) with an energy penalty of 8.1%-points. This conventional CLC plant would also require a custom gas turbine. With an added combustor fired by natural gas a standard gas turbine can be deployed and CO2 avoidance costs are reduced to $60.3/ton mainly due to a reduction in the energy penalty to only 1.4%-points. However due to the added natural gas combustion after the CLC reactor CO2 avoidance is only 52.4%. Achieving high CO2 avoidance requires firing with clean hydrogen instead increasing the CO2 avoidance cost to $96.3/ton when a hydrogen cost of $15.5/GJ is assumed. Advanced heat integration could reduce the CO2 avoidance cost to $90.3/ton by lowering the energy penalty to only 0.6%-points. An attractive alternative is therefore to construct the plant for added firing with natural gas and retrofit the added combustor for hydrogen firing when CO2 prices reach very high levels.
Low-carbon Hydrogen Via Integration of Steam Methane Reforming with Molten Carbonate Fuel Cells at Low Fuel Utilization
Feb 2021
Publication
Hydrogen production is critical to many modern chemical processes – ammonia synthesis petroleum refining direct reduction of iron and more. Conventional approaches to hydrogen manufacture include steam methane reforming and autothermal reforming which today account for the lion's share of hydrogen generation. Without CO2 capture these processes emit about 8.7 kg of CO2 for each kg of H2 produced. In this study a molten carbonate fuel cell system with CO2 capture is proposed to retrofit the flue gas stream of an existing Steam Methane Reforming plant rated at 100000 Nm3 h−1 of 99.5% pure H2. The thermodynamic analysis shows direct CO2 emissions can be reduced by more than 95% to 0.4 to 0.5 kg CO2 /kg H2 while producing 17% more hydrogen (with an increase in natural gas input of approximately 37%). Because of the additional power and hydrogen generation of the carbonate fuel cell the efficiency debit associated with CO2 capture is quite small reducing the SMR efficiency from 76.6% without capture to 75.6% with capture. In comparison the use of standard amine technology for CO2 capture reduces the efficiency below 70%. This demonstrates the synergistic nature of the carbonate fuel cells which can reform natural gas to H2 while simultaneously capturing CO2 from the SMR flue gas and producing electricity giving rise to a total system with very low emissions yet high efficiency.
Influence of Thermal Treatment on SCC and HE Susceptibility of Supermartensitic Stainless Steel 16Cr5NiMo
Apr 2020
Publication
A 16Cr5NiMo supermartensitic stainless steel was subjected to different tempering treatments and analyzed by means of permeation tests and slow strain rate tests to investigate the effect of different amounts of retained austenite on its hydrogen embrittlement susceptibility. The 16Cr5NiMo steel class is characterized by a very low carbon content. It is the new variant of 13Cr4Ni. These steels are used in many applications for example compressors for sour environments offshore piping naval propellers aircraft components and subsea applications. The typical microstructure is a soft-tempered martensite very close to a body-centered cubic with a retained austenite fraction and limited δ ferrite phase. Supermartensitic stainless steels have high mechanical properties together with good weldability and corrosion resistance. The amount of retained austenite is useful to increase low temperature toughness and stress corrosion cracking resistance. Experimental techniques allowed us to evaluate diffusion coefficients and the mechanical behaviour of metals in stress corrosion cracking (SCC) conditions.
The Role of the Flow Field Generated by Venting Process on the Pressure Time History of a Vented Deflagration
Sep 2017
Publication
Vented deflagrations are one of the most challenging phenomenon to be replicated numerically in order to predict its resulting pressure time history. As a matter of fact a number of different phenomena can contribute to modify the burning velocity of a gas mixture undergoing a deflagration especially when the flame velocity is considerably lower than the speed of sound. In these conditions acceleration generated by both the flow field induced by the expanding flame and from discontinuities as the vent opening and the venting of the combustion products affect the burning velocity and the burning behaviour of the flame. In particular the phenomena affecting the pressure time history of a deflagration after the flame front reaches the vent area such as flame acoustic interaction and local pressure peaks seem to be closely related to a change in the burning behaviour induced by the venting process. Flame acoustic interaction and local pressure peaks arise as a consequence of the change in the burning behaviour of the flame. This paper analyses the video recording of the flame front produced during the TP experimental campaign performed by UNIPI in the project HySEA to analyse qualitatively the contribution of the generated flow field in a vented deflagration in its pressure-time history.
Direct Route from Ethanol to Pure Hydrogen through Autothermal Reforming in a Membrane Reactor: Experimental Demonstration, Reactor Modelling and Design
Nov 2020
Publication
This work reports the integration of thin (~3e4 mm thick) Pd-based membranes for H2 separation in a fluidized bed catalytic reactor for ethanol auto-thermal reforming. The performance of a fluidized bed membrane reactor has been investigated from an experimental and numerical point of view. The demonstration of the technology has been carried out over 50 h under reactive conditions using 5 thin Pd-based alumina-supported membranes and a 3 wt%Pt-10 wt%Ni catalyst deposited on a mixed CeO2/SiO2 support. The results have confirmed the feasibility of the concept in particular the capacity to reach a hydrogen recovery factor up to 70% while the operation at different fluidization regimes oxygen-to-ethanol and steam-to-ethanol ratios feed pressures and reactor temperatures have been studied. The most critical part of the system is the sealing of the membranes where most of the gas leakage was detected. A fluidized bed membrane reactor model for ethanol reforming has been developed and validated with the obtained experimental results. The model has been subsequently used to design a small reactor unit for domestic use showing that 0.45 m2 membrane area is needed to produce the amount of H2 required for a 5 kWe PEM fuel-cell based micro-CHP system.
Hydrogen Production as a Clean Energy Carrier through Heterojunction Semiconductors for Environmental Remediation
Apr 2022
Publication
Today as a result of the advancement of technology and increasing environmental problems the need for clean energy has considerably increased. In this regard hydrogen which is a clean and sustainable energy carrier with high energy density is among the well-regarded and effective means to deliver and store energy and can also be used for environmental remediation purposes. Renewable hydrogen energy carriers can successfully substitute fossil fuels and decrease carbon dioxide (CO2 ) emissions and reduce the rate of global warming. Hydrogen generation from sustainable solar energy and water sources is an environmentally friendly resolution for growing global energy demands. Among various solar hydrogen production routes semiconductor-based photocatalysis seems a promising scheme that is mainly performed using two kinds of homogeneous and heterogeneous methods of which the latter is more advantageous. During semiconductor-based heterogeneous photocatalysis a solid material is stimulated by exposure to light and generates an electron–hole pair that subsequently takes part in redox reactions leading to hydrogen production. This review paper tries to thoroughly introduce and discuss various semiconductor-based photocatalysis processes for environmental remediation with a specific focus on heterojunction semiconductors with the hope that it will pave the way for new designs with higher performance to protect the environment.
Integration of Gas Switching Combustion and Membrane Reactors for Exceeding 50% Efficiency in Flexible IGCC Plants with Near-zero CO2 Emissions
Jul 2020
Publication
Thermal power plants face substantial challenges to remain competitive in energy systems with high shares of variable renewables especially inflexible integrated gasification combined cycles (IGCC). This study addresses this challenge through the integration of Gas Switching Combustion (GSC) and Membrane Assisted Water Gas Shift (MAWGS) reactors in an IGCC plant for flexible electricity and/or H2 production with inherent CO2 capture. When electricity prices are high H2 from the MAWGS reactor is used for added firing after the GSC reactors to reach the high turbine inlet temperature of the H-class gas turbine. In periods of low electricity prices the turbine operates at 10% of its rated power to satisfy the internal electricity demand while a large portion of the syngas heating value is extracted as H2 in the MAWGS reactor and sold to the market. This product flexibility allows the inflexible process units such as gasification gas treating air separation unit and CO2 compression transport and storage to operate continuously while the plant supplies variable power output. Two configurations of the GSC-MAWGS plant are presented. The base configuration achieves 47.2% electric efficiency and 56.6% equivalent hydrogen production efficiency with 94.8–95.6% CO2 capture. An advanced scheme using the GSC reduction gases for coal-water slurry preheating and pre-gasification reached an electric efficiency of 50.3% hydrogen efficiency of 62.4% and CO2 capture ratio of 98.1–99.5%. The efficiency is 8.4%-points higher than the pre-combustion CO2 capture benchmark and only 1.9%-points below the unabated IGCC benchmark.
Comprehensive Review on Fuel Cell Technology for Stationary Applications as Sustainable and Efficient Poly-Generation Energy Systems
Aug 2021
Publication
Fuel cell technologies have several applications in stationary power production such as units for primary power generation grid stabilization systems adopted to generate backup power and combined-heat-and-power configurations (CHP). The main sectors where stationary fuel cells have been employed are (a) micro-CHP (b) large stationary applications (c) UPS and IPS. The fuel cell size for stationary applications is strongly related to the power needed from the load. Since this sector ranges from simple backup systems to large facilities the stationary fuel cell market includes few kWs and less (micro-generation) to larger sizes of MWs. The design parameters for the stationary fuel cell system differ for fuel cell technology (PEM AFC PAFC MCFC and SOFC) as well as the fuel type and supply. This paper aims to present a comprehensive review of two main trends of research on fuel-cell-based poly-generation systems: tracking the market trends and performance analysis. In deeper detail the present review will list a potential breakdown of the current costs of PEM/SOFC production for building applications over a range of production scales and at representative specifications as well as broken down by component/material. Inherent to the technical performance a concise estimation of FC system durability efficiency production maintenance and capital cost will be presented.
Flammability Reduction in a Pressurised Water Electrolyser Based on a Thin Polymer Electrolyte Membrane through a Pt-alloy Catalytic Approach
Jan 2019
Publication
Various Pt-based materials (unsupported Pt PtRu PtCo) were investigated as catalysts for recombining hydrogen and oxygen back into water. The recombination performance correlated well with the surface Pt metallic state. Alloying cobalt to platinum was observed to produce an electron transfer favouring the occurrence of a large fraction of the Pt metallic state on the catalyst surface. Unsupported PtCo showed both excellent recombination performance and dynamic behaviour. In a packed bed catalytic reactor when hydrogen was fed at 4% vol. in the oxygen stream (flammability limit) 99.5% of the total H2 content was immediately converted to water in the presence of PtCo thus avoiding safety issues. The PtCo catalyst was thus integrated in the anode of the membrane-electrode assembly of a polymer electrolyte membrane electrolysis cell. This catalyst showed good capability to reduce the concentration of hydrogen in the oxygen stream under differential pressure operation (1–20 bar) in the presence of a thin (90 μm) Aquivion® membrane. The modified system showed lower hydrogen concentration in the oxygen flow than electrolysis cells based on state-of-the-art thick polymer electrolyte membranes and allowed to expand the minimum current density load down to 0.15 A cm−2 . This was mainly due to the electrochemical oxidation of permeated H2 to protons that were transported back to the cathode. The electrolysis cell equipped with a dual layer PtCo/IrRuOx oxidation catalyst achieved a high operating current density (3 A cm−2 ) as requested to decrease the system capital costs under high efficiency conditions (about 77% efficiency at 55 °C and 20 bar). Moreover the electrolysis system showed reduced probability to reach the flammability limit under both high differential pressure (20 bar) and partial load operation (5%) as needed to properly address grid-balancing service
Toward a Non-destructive Diagnostic Analysis Tool of Exercises Pipelines: Models and Experiences
Dec 2018
Publication
Strategic networks of hydrocarbon pipelines in long time service are adversely affected by the action of aggressive chemicals transported with the fluids and dissolved in the environment. Material degradation phenomena are amplified in the presence of hydrogen and water elements that increase the material brittleness and reduce the safety margins. The risk of failure during operation of these infrastructures can be reduced if not prevented by the continuous monitoring of the integrity of the pipe surfaces and by the tracking of the relevant bulk properties. A fast and potentially non-destructive diagnostic tool of material degradation which may be exploited in this context is based on the instrumented indentation tests that can be performed on metals at different scales. Preliminary validation studies of the significance of this methodology for the assessment of pipeline integrity have been carried out with the aid of interpretation models of the experiments. The main results of this ongoing activity are illustrated in this contribution.
A Preliminary Energy Analysis of a Commercial CHP Fueled with H2NG Blends Chemically Supercharged by Renewable Hydrogen and Oxygen
Dec 2016
Publication
Currently Power-to-Gas technologies are considered viable solutions to face the onset problems associated with renewable capacity firming. Indeed carbon-free hydrogen production converting renewable electricity excess and its injection into natural gas pipelines is considered a short- to medium-term solution. In this way the so-called H2NG blends can be fired within internal combustion engines and micro gas turbines operating in CHP mode offering better environmental-energy performances in machines. As regards the distributed energy generation scenario the local H2 production by means of electrolysis for methane enrichment will be more cost-effective if the oxygen is fruitfully used instead of venting it out like a by-product as usually occurs. This study focuses on the usefulness of using that oxygen to enrich the air-fuel mixture of an internal combustion engine for micro-CHP applications once it has been fuelled with H2NG blends. Thus the main aim of this paper is to provide a set of values for benchmarking in which H2NG blends ranging in 0%-15% vol. burn within an ICE in partial oxy-fuel conditions. In particular a preliminary energy analysis was carried out based on experimental data reporting the engine operating parameters gains and losses in both electrical and heat recovery efficiency. The oxygen content in the air varies up to 22% vol. A Volkswagen Blue Tender CHP commercial version (19.8 kWel. of rated electrical power output) was considered as the reference machine and its energy characterization was reported when it operated under those unconventional conditions.
Detection, Characterization and Sizing of Hydrogen Induced Cracking in Pressure Vessels Using Phased Array Ultrasonic Data Processing
Jul 2016
Publication
Pressure vessels operating in sour service conditions in refinery environments can be subject to the risk of H₂S cracking resulting from the hydrogen entering into the material. This risk which is related to the specific working conditions and to the quality of the steel used shall be properly managed in order to maintain the highest safety at a cost-effective level.<br/>Nowadays the typical management strategy is based on a risk based inspection (RBI) evaluation to define the inspection plan used in conjunction with a fitness for service (FFS) approach in defining if the vessel although presenting dangerous defects such as cracks can still be considered “fit for purpose” for a given time window based on specific fracture mechanics analysis.<br/>These vessels are periodically subject to non-destructive evaluation typically ultrasonic testing. Phased Array (PA) ultrasonic is the latest technology more and more used for this type of application.<br/>This paper presents the design and development of an optimized Phased Array ultrasonic inspection technique for the detection and sizing of hydrogen induced cracking (HIC) type flaws used as reference for comparison. Materials used containing natural operational defects were inspected in “as-service” conditions.<br/>Samples have then been inspected by means of a “full matrix capture” (FMC) acquisition process followed by “total focusing method” (TFM) data post processing. FCM-TFM data have been further post-processed and then used to create a 3D geometrical reconstruction of the volume inspected. Results obtained show the significant improvement that FMC/TFM has over traditional PA inspection techniques both in terms of sensitivity and resolution for this specific type of defect. Moreover since the FMC allows for the complete time domain signal to be captured from every element of a linear array probe the full set of data is available for post-processing.<br/>Finally the possibility to reconstruct the geometry of the component from the scans including the defects present in its volume represents the ideal solution for a reliable data transferring process to the engineering function for the subsequent FFS analysis.
Water Electrolysis for the Production of Hydrogen to Be Employed in the Ironmaking and Steelmaking Industry
Nov 2021
Publication
The way to decarbonization will be characterized by the huge production of hydrogen through sustainable routes. Thus the basic production way is water electrolysis sustained by renewable energy sources allowing for obtaining “green hydrogen”. The present paper reviews the main available technologies for the water electrolysis finalized to the hydrogen production. We describe the fundamental of water electrolysis and the problems related to purification and/or desalinization of water before electrolysis. As a matter of fact we describe the energy efficiency issues with particular attention to the potential application in the steel industry. The fundamental aspects related to the choice of high-temperature or low-temperature technologies are analyzed.
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