Production & Supply Chain
Bench-Scale Steam Reforming of Methane for Hydrogen Production
Jul 2019
Publication
The effects of reaction parameters including reaction temperature and space velocity on hydrogen production via steam reforming of methane (SRM) were investigated using lab- and bench-scale reactors to identify critical factors for the design of large-scale processes. Based on thermodynamic and kinetic data obtained using the lab-scale reactor a series of SRM reactions were performed using a pelletized catalyst in the bench-scale reactor with a hydrogen production capacity of 10 L/min. Various temperature profiles were tested for the bench-scale reactor which was surrounded by three successive cylindrical furnaces to simulate the actual SRM conditions. The temperature at the reactor bottom was crucial for determining the methane conversion and hydrogen production rates when a sufficiently high reaction temperature was maintained (>800 ◦C) to reach thermodynamic equilibrium at the gas-hourly space velocity of 2.0 L CH4/(h·gcat). However if the temperature of one or more of the furnaces decreased below 700 ◦C the reaction was not equilibrated at the given space velocity. The effectiveness factor (0.143) of the pelletized catalyst was calculated based on the deviation of methane conversion between the lab- and bench-scale reactions at various space velocities. Finally an idling procedure was proposed so that catalytic activity was not affected by discontinuous operation.
Techno-economic Assessment of Hydrogen Production from Seawater
Nov 2022
Publication
Population growth and the expansion of industries have increased energy demand and the use of fossil fuels as an energy source resulting in release of greenhouse gases (GHG) and increased air pollution. Countries are therefore looking for alternatives to fossil fuels for energy generation. Using hydrogen as an energy carrier is one of the most promising alternatives to replace fossil fuels in electricity generation. It is therefore essential to know how hydrogen is produced. Hydrogen can be produced by splitting the water molecules in an electrolyser using the abondand water resources which are covering around ⅔ of the Earth's surface. Electrolysers however require high-quality water with conductivity in the range of 0.1–1 μS/cm. In January 2018 there were 184 offshore oil and gas rigs in the North Sea which may be excellent sites for hydrogen production from seawater. The hydrogen production process reported in this paper is based on a proton exchange membrane (PEM) electrolyser with an input flow rate of 300 L/h. A financially optimal system for producing demineralized water from seawater with conductivity in the range of 0.1–1 μS/cm as the input for electrolyser by WAVE (Water Application Value Engine) design software was studied. The costs of producing hydrogen using the optimised system was calculated to be US$3.51/kg H2. The best option for low-cost power generation using renewable resources such as photovoltaic (PV) devices wind turbines as well as electricity from the grid was assessed considering the location of the case considered. All calculations were based on assumption of existing cable from the grid to the offshore meaning that the cost of cables and distribution infrastructure were not considered. Models were created using HOMER Pro (Hybrid Optimisation of Multiple Energy Resources) software to optimise the microgrids and the distributed energy resources under the assumption of a nominal discount rate inflation rate project lifetime and CO2 tax in Norway. Eight different scenarios were examined using HOMER Pro and the main findings being as follows:<br/>The cost of producing water with quality required by the electrolyser is low compared with the cost of electricity for operation of the electrolyser and therefore has little effect on the total cost of hydrogen production (less than 1%).<br/>The optimal solution was shown to be electricity from the grid which has the lowest levelised cost of energy (LCOE) of the options considered. The hydrogen production cost using electricity from the grid was about US$ 5/kg H2.<br/>Grid based electricity resulted in the lowest hydrogen production cost even when costs for CO2 emissions in Norway that will start to apply in 2025 was considered being approximately US$7.7/kg H2.<br/>From economical point of view wind energy was found to be a more economical than solar.
A Tale of Two Phase Diagrams Interplay of Ordering and Hydrogen Uptake in Pd–Au–H
Apr 2021
Publication
Due to their ability to reversibly absorb/desorb hydrogen without hysteresis Pd–Au nanoalloys have been proposed as materials for hydrogen sensing. For sensing it is important that absorption/desorption isotherms are reproducible and stable over time. A few studies have pointed to the influence of short and long range chemical order on these isotherms but many aspects of the impact of chemical order have remained unexplored. Here we use alloy cluster expansions to describe the thermodynamics of hydrogen in Pd–Au in a wide concentration range. We investigate how different chemical orderings corresponding to annealing at different temperatures as well as different external pressures of hydrogen impact the behavior of the material with focus on its hydrogen absorption/desorption isotherms. In particular we find that a long-range ordered L12 phase is expected to form if the H2 pressure is sufficiently high. Furthermore we construct the phase diagram at temperatures from 250 K to 500 K showing that if full equilibrium is reached in the presence of hydrogen phase separation can often be expected to occur in stark contrast to the phase diagram in para-equilibrium. Our results explain the experimental observation that absorption/desorption isotherms in Pd–Au are often stable over time but also reveal pitfalls for when this may not be the case.
Towards an Understanding of Hydrogen Supply Chains: A Structured Literature Review Regarding Sustainability Evaluation
Oct 2021
Publication
Hydrogen technologies have received increased attention in research and development to foster the shift towards carbon-neutral energy systems. Depending on the specific production techniques transportation concepts and application areas hydrogen supply chains (HSCs) can be anything from part of the energy transition problem to part of the solution: Even more than battery-driven electric mobility hydrogen is a polyvalent technology and can be used in very different contexts with specific positive or negative sustainability impacts. Thus a detailed sustainability evaluation is crucial for decision making in the context of hydrogen technology and its diverse application fields. This article provides a comprehensive structured literature review in the context of HSCs along the triple bottom line dimensions of environmental economic and social sustainability analyzing a total of 288 research papers. As a result we identify research gaps mostly regarding social sustainability and the supply chain stages of hydrogen distribution and usage. We suggest further research to concentrate on these gaps thus strengthening our understanding of comprehensive sustainability evaluations for HSCs especially in social sustainability evaluation. In addition we provide an additional approach for discussion by adding literature review results from neighboring fields highlighting the joint challenges and insights regarding sustainability evaluation.
Cogeneration of Green Hydrogen in a Cascade Hydropower Plant
Apr 2021
Publication
Hydrogen is today an indispensable feedstock in various process industries but the method of its production is mostly not in line with accepted environmental guidelines. With emerging electro-energetic systems with a large share of renewable sources hydrogen is also becoming an important energy carrier which with the possibility of storing surplus energy ensures greater stability of power system operation and energy supply. Therefore the use of electricity from renewable sources is important for the production of green hydrogen using electrolysis. The first part of the article describes the possibilities for hydrogen cogeneration in one of the run-of-river hydropower plants in Slovenia. The implementation costs of the necessary equipment for hydrogen production in the case-study power plant its production costs and the profitability of hydrogen production compared to the sale of electricity are estimated. The criteria according to which the production of hydrogen is more profitable than the sale of electricity at current prices and guaranteed sales is also defined. In the second part of the article a scenario for the use of hydrogen for heating and mobility needs in the nearby local community is presented. For the regular supply of hydrogen in the range of up to 30 kg/h the necessary investment costs for the installation of the appropriate equipment in the hydropower plant are calculated along with an estimation of the payback period of the investment.
Site-Dependent Environmental Impacts of Industrial Hydrogen Production by Alkaline Water Electrolysis
Jun 2017
Publication
Industrial hydrogen production via alkaline water electrolysis (AEL) is a mature hydrogen production method. One argument in favor of AEL when supplied with renewable energy is its environmental superiority against conventional fossil-based hydrogen production. However today electricity from the national grid is widely utilized for industrial applications of AEL. Also the ban on asbestos membranes led to a change in performance patterns making a detailed assessment necessary. This study presents a comparative Life Cycle Assessment (LCA) using the GaBi software (version 6.115 thinkstep Leinfelden-Echterdingen Germany) revealing inventory data and environmental impacts for industrial hydrogen production by latest AELs (6 MW Zirfon membranes) in three different countries (Austria Germany and Spain) with corresponding grid mixes. The results confirm the dependence of most environmental effects from the operation phase and specifically the site-dependent electricity mix. Construction of system components and the replacement of cell stacks make a minor contribution. At present considering the three countries AEL can be operated in the most environmentally friendly fashion in Austria. Concerning the construction of AEL plants the materials nickel and polytetrafluoroethylene in particular used for cell manufacturing revealed significant contributions to the environmental burden.
Electronic Structure and d-Band Center Control Engineering over Ni-Doped CoP3 Nanowall Arrays for Boosting Hydrogen Production
Jun 2021
Publication
To address the challenge of highly efficient water splitting into H2 successful fabrication of novel porous three-dimensional Ni-doped CoP3 nanowall arrays on carbon cloth was realized resulting in an effective self-supported electrode for the electrocatalytic hydrogen-evolution reaction. The synthesized samples exhibit rough curly and porous structures which are beneficial for gaseous transfer and diffusion during the electrocatalytic process. As expected the obtained Ni-doped CoP3 nanowall arrays with a doping concentration of 7% exhibit the promoted electrocatalytic activity. The achieved overpotentials of 176 mV for the hydrogen-evolution reaction afford a current density of 100 mA cm−2 which indicates that electrocatalytic performance can be dramatically enhanced via Ni doping. The Ni-doped CoP3 electrocatalysts with increasing catalytic activity should have significant potential in the field of water splitting into H2. This study also opens an avenue for further enhancement of electrocatalytic performance through tuning of electronic structure and d-band center by doping.
Catalytic Hydrogen Production, Storage and Application
Jul 2021
Publication
Hydrogen is a clean fuel for transportation and energy storage. It has several attractive features including a higher energy content by weight use in fuel cells that produces only water as a by-product storage in small and large quantities by various methods and established transportation and infrastructures. A hydrogen economy consists of three steps i.e. hydrogen production storage and applications. All three steps involved in a hydrogen economy can be divided into catalytic and non-catalytic approaches. For catalytic processes the efficiency highly depends on the type and physico-chemical characteristics of the catalysts. Therefore for the improvement of these catalytic processes the development of highly efficient and stable catalysts is highly required.
Analysis of Hydrogen Production Potential from Waste Plastics by Pyrolysis and In Line Oxidative Steam Reforming
Oct 2021
Publication
A study was carried out on the valorization of different waste plastics (HDPE PP PS and PE) their mixtures and biomass/HDPE mixtures by means of pyrolysis and in line oxidative steam reforming. A thermodynamic equilibrium simulation was used for determining steam reforming data whereas previous experimental results were considered for setting the pyrolysis volatile stream composition. The adequacy of this simulation tool was validated using experimental results obtained in the pyrolysis and in line steam reforming of different plastics. The effect the most relevant process conditions i.e. temperature steam/plastic ratio and equivalence ratio have on H2 production and reaction enthalpy was evaluated. Moreover the most suitable conditions for the oxidative steam reforming of plastics of different nature and their mixtures were determined. The results obtained are evidence of the potential interest of this novel valorization route as H2 productions of up to 25 wt% were obtained operating under autothermal conditions.
A Holistic Consideration of Megawatt Electrolysis as a Key Component of Sector Coupling
May 2022
Publication
In the future hydrogen (H2) will play a significant role in the sustainable supply of energy and raw materials to various sectors. Therefore the electrolysis of water required for industrial‐ scale H2 production represents a key component in the generation of renewable electricity. Within the scope of fundamental research work on cell components for polymer electrolyte membrane (PEM) electrolyzers and application‐oriented living labs an MW electrolysis system was used to further improve industrial‐scale electrolysis technology in terms of its basic structure and systems‐ related integration. The planning of this work as well as the analytical and technical approaches taken along with the essential results of research and development are presented herein. The focus of this study is the test facility for a megawatt PEM electrolysis stack with the presentation of the design processing and assembly of the main components of the facility and stack.
Techno-economic Analysis of Hydrogen Electrolysis from Off-Grid Stand-Alone Photovoltaics Incorporating Uncertainty Analysis
Oct 2020
Publication
Solar-driven electrolysis of water to generate hydrogen is emerging as a viable strategy to decarbonize the global energy economy. However this direction is more expensive than traditional fossil fuel generation of hydrogen and effective pathways to lower this cost need to be identified. Here we report a Monte Carlo approach to explore a wide range of input assumptions to identify key cost drivers targets and localized conditions necessary for competitive stand-alone dedicated PV powered hydrogen electrolysis. We determine the levelized cost of hydrogen (LCOH) considering historical weather data for specific locations to model our PV system and optimize its size compared to the electrolyzer. This analysis and its methods show the potential for green hydrogen production using off-grid PV shows the merits of remote systems in areas of high solar resource and provides cost and performance targets for electrolyzer technologies.
Dynamic Simulation and Thermoeconomic Analysis of a Hybrid Renewable System Based on PV and Fuel Cell Coupled with Hydrogen Storage
Nov 2021
Publication
The production of “green hydrogen” is currently one of the hottest topics in the field of renewable energy systems research. Hydrogen storage is also becoming more and more attractive as a flexible solution to mitigate the power fluctuations of solar energy systems. The most promising technology for electricity-to-hydrogen conversion and vice versa is the reversible solid-oxide cell (SOC). This device is still very expensive but it exhibits excellent performance under dynamic operating conditions compared to the competing devices. This work presents the dynamic simulation of a prototypal renewable plant combining a 50 kW photovoltaic (PV) field with a 50 kW solid-oxide electrolyzer cell (SOEC) and a compressed hydrogen tank. The electricity is used to meet the energy demand of a dwelling located in the area of Campi Flegrei (Naples). The SOC efficiency is simulated by developing a mathematical model in MATLAB®. The model also calculates the cell operating temperature as a function of the input current. Once the optimal values of the operating parameters of the SOC are calculated the model is integrated in the transient system simulation tool (TRNSYS) for dynamic analysis. Furthermore this work presents a parametric analysis of the hydrogen storage system (HSS). The results of the energy and environmental analyses show that the proposed system can reach a primary energy saving by 70% and an amount of saved CO2 of 28 tons/year. Some possible future market scenarios are considered for the economic analysis. In the most realistic case the optimal configuration shows a simple pay back lower than 10 years and a profit index of 46%.
Influence of Cs Promoter on Ethanol Steam-Reforming Selectivity of Pt/m-ZrO2 Catalysts at Low Temperature
Sep 2021
Publication
The decarboxylation pathway in ethanol steam reforming ultimately favors higher selectivity to hydrogen over the decarbonylation mechanism. The addition of an optimized amount of Cs to Pt/m-ZrO2 catalysts increases the basicity and promotes the decarboxylation route converting ethanol to mainly H2 CO2 and CH4 at low temperature with virtually no decarbonylation being detected. This offers the potential to feed the product stream into a conventional methane steam reformer for the production of hydrogen with higher selectivity. DRIFTS and the temperature-programmed reaction of ethanol steam reforming as well as fixed bed catalyst testing revealed that the addition of just 2.9% Cs was able to stave off decarbonylation almost completely by attenuating the metallic function. This occurs with a decrease in ethanol conversion of just 16% relative to the undoped catalyst. In comparison with our previous work with Na this amount is—on an equivalent atomic basis—just 28% of the amount of Na that is required to achieve the same effect. Thus Cs is a much more efficient promoter than Na in facilitating decarboxylation.
Nuclear-Renewables Energy System for Hydrogen and Electricity Production
May 2011
Publication
In the future the world may have large stranded resources of low-cost wind and solar electricity. Renewable electricity production does not match demand and production is far from major cities. The coupling of nuclear energy with renewables may enable full utilization of nuclear and renewable facilities to meet local electricity demands and export pipeline hydrogen for liquid fuels fertilizer and metals production. Renewables would produce electricity at full capacity in large quantities. The base-load nuclear plants would match electricity production with demand by varying the steam used for electricity versus hydrogen production. High-temperature electrolysis (HTE) would produce hydrogen from water using (a) steam from nuclear plants and (b) electricity from nuclear plants and renewables. During times of peak electricity demand the HTE cells would operate in reverse fuel cell mode to produce power substituting for gas turbines that are used for very few hours per year and that thus have very high electricity costs. The important net hydrogen production would be shipped by pipeline to customers. Local hydrogen storage would enable full utilization of long-distance pipeline capacity with variable production. The electricity and hydrogen production were simulated with real load and wind data to understand under what conditions such systems are economic. The parametric case study uses a wind-nuclear system in North Dakota with hydrogen exported to the Chicago refinery market. North Dakota has some of the best wind conditions in the United States and thus potentially low-cost wind. The methodology allows assessments with different economic and technical assumptions - including what electrolyzer characteristics are most important for economic viability.
Catalytic Hydrogen Production from Methane: A Review on Recent Progress and Prospect
Aug 2020
Publication
Natural gas (Methane) is currently the primary source of catalytic hydrogen production accounting for three quarters of the annual global dedicated hydrogen production (about 70 M tons). Steam–methane reforming (SMR) is the currently used industrial process for hydrogen production. However the SMR process suffers with insufficient catalytic activity low long-term stability and excessive energy input mostly due to the handling of large amount of CO2 coproduced. With the demand for anticipated hydrogen production to reach 122.5 M tons in 2024 novel and upgraded catalytic processes are desired for more effective utilization of precious natural resources. In this review we summarized the major descriptors of catalyst and reaction engineering of the SMR process and compared the SMR process with its derivative technologies such as dry reforming with CO2 (DRM) partial oxidation with O2 autothermal reforming with H2O and O2. Finally we discussed the new progresses of methane conversion: direct decomposition to hydrogen and solid carbon and selective oxidation in mild conditions to hydrogen containing liquid organics (i.e. methanol formic acid and acetic acid) which serve as alternative hydrogen carriers. We hope this review will help to achieve a whole picture of catalytic hydrogen production from methane.
A Hot Syngas Purification System Integrated with Downdraft Gasification of Municipal Solid Waste
Jan 2019
Publication
Gasification of municipal solid waste (MSW) with subsequent utilization of syngas in gas engines/turbines and solid oxide fuel cells can substantially increase the power generation of waste-to-energy facilities and optimize the utilization of wastes as a sustainable energy resources. However purification of syngas to remove multiple impurities such as particulates tar HCl alkali chlorides and sulfur species is required. This study investigates the feasibility of high temperature purification of syngas from MSW gasification with the focus on catalytic tar reforming and desulfurization. Syngas produced from a downdraft fixed-bed gasifier is purified by a multi-stage system. The system comprises of a fluidized-bed catalytic tar reformer a filter for particulates and a fixed-bed reactor for dechlorination and then desulfurization with overall downward cascading of the operating temperatures throughout the system. Novel nano-structured nickel catalyst supported on alumina and regenerable Ni-Zn desulfurization sorbent loaded on honeycomb are synthesized. Complementary sampling and analysis methods are applied to quantify the impurities and determine their distribution at different stages. Experimental and thermodynamic modeling results are compared to determine the kinetic constraints in the integrated system. The hot purification system demonstrates up to 90% of tar and sulfur removal efficiency increased total syngas yield (14%) and improved cold gas efficiency (12%). The treated syngas is potentially applicable in gas engines/turbines and solid oxide fuel cells based on the dew points and concentration limits of the remaining tar compounds. Reforming of raw syngas by nickel catalyst for over 20 h on stream shows strong resistance to deactivation. Desulfurization of syngas from MSW gasification containing significantly higher proportion of carbonyl sulfide than hydrogen sulfide traces of tar and hydrogen chloride demonstrates high performance of Ni-Zn sorbents.
Graphitic Carbon Nitride Heterojunction Photocatalysts for Solar Hydrogen Production
Sep 2021
Publication
Photocatalytic hydrogen production is considered as an ideal approach to solve global energy crisis and environmental pollution. Graphitic carbon nitride (g-C3N4) has received extensive consideration due to its facile synthesis stable physicochemical properties and easy functionalization. However the pristine g-C3N4 usually shows unsatisfactory photocatalytic activity due to the limited separation efficiency of photogenerated charge carriers. Generally introducing semiconductors or co-catalysts to construct g–C3N4–based heterojunction photocatalysts is recognized as an effective method to solve this bottleneck. In this review the advantages and characteristics of various types of g–C3N4–based heterojunction are analyzed. Subsequently the recent progress of highly efficient g–C3N4–based heterojunction photocatalysts in the field of photocatalytic water splitting is emphatically introduced. Finally a vision of future perspectives and challenges of g–C3N4–based heterojunction photocatalysts in hydrogen production are presented. Predictably this timely review will provide valuable reference for the design of efficient heterojunctions towards photocatalytic water splitting and other photoredox reactions.
Advanced Catalysts for the Water Gas Shift Reaction
Apr 2022
Publication
The WGS reaction is an exothermic reaction between carbon monoxide and steam to form carbon dioxide and hydrogen. This reaction which has been used industrially for more than 100 years has recently received a great deal of attention from researchers as one of the ways to produce environmentally acceptable hydrogen from fossil fuels in large quantities. For the application of this reaction on an industrial scale the key is choosing the optimal catalysts that can ensure high CO conversion and have a long lifetime under industrial conditions. Therefore new types of catalysts are being developed that meet these requirements better than the Fe- and Cu-based catalysts commonly used in the past. The WGSR on a commercial nickel-based catalyst and a laboratory-prepared copper and cobalt-based catalyst was tested in a laboratory apparatus set up at the University of Chemistry and Technology Prague. The best performance of the laboratory-prepared catalyst was observed for the catalyst with a Cu content of 14.8 wt% and activated in a hydrogen atmosphere. The laboratory-prepared Co-based catalyst showed good WGSR activity in the temperature range of 200–450 ◦C although this was always inferior to that of the Cu-based catalyst. When subjected to the feed gas containing 0.4 mole% H2S the Co-based catalyst showed good resistance to sulphur poisoning. Therefore Co-based catalysts can be considered good sulphur-tolerant intermediate temperature WGSR catalysts.
Hubs and Clusters Approach to Unlock the Development of Carbon Capture and Storage - Case Study in Spain
Jul 2021
Publication
Xiaolong Sun,
Juan Alcalde,
Mahdi Bakhtbidar,
Javier Elío,
Víctor Vilarrasa,
Jacobo Canal,
Julio Ballesteros,
Niklas Heinemann,
Stuart Haszeldine,
Andrew Cavanagh,
David Vega-Maza,
Fernando Rubiera,
Roberto Martínez-Orio,
Gareth Johnson,
Ramon Carbonell,
Ignacio Marzan,
Anna Travé and
Enrique Gomez-Rivas
Many countries have assigned an indispensable role for carbon capture and storage (CCS) in their national climate change mitigation pathways. However CCS deployment has stalled in most countries with only limited commercial projects realised mainly in hydrocarbon-rich countries for enhanced oil recovery. If the Paris Agreement is to be met then this progress must be replicated widely including hydrocarbon-limited countries. In this study we present a novel source-to-sink assessment methodology based on a hubs and clusters approach to identify favourable regions for CCS deployment and attract renewed public and political interest in viable deployment pathways. Here we apply this methodology to Spain where fifteen emission hubs from both the power and the hard-to-abate industrial sectors are identified as potential CO2 sources. A priority storage structure and two reserves for each hub are selected based on screening and ranking processes using a multi-criteria decision-making method. The priority source-to-sink clusters are identified indicating four potential development regions with the North-Western and North-Eastern Spain recognised as priority regions due to resilience provided by different types of CO2 sources and geological structures. Up to 68.7 Mt CO2 per year comprising around 21% of Spanish emissions can be connected to clusters linked to feasible storage. CCS especially in the hard-to-abate sector and in combination with other low-carbon energies (e.g. blue hydrogen and bioenergy) remains a significant and unavoidable contributor to the Paris Agreement’s mid-century net-zero target. This study shows that the hubs and clusters approach can facilitate CCS deployment in Spain and other hydrocarbon-limited countries.
Thermodynamic Assessment of a Hybrid Methane Cracking System for Liquified Hydrogen Production and Enhanced Oil Recovery Using CO2
Oct 2022
Publication
Hydrogen fuel production from methane cracking is a cleaner process compared to steam methane reforming due to zero greenhouse gas emissions. Carbon black that is co-produced is valuable and can be marketed to other industries. As this is a high-temperature process using solar energy can further improve its sustainability. In this study an integrated solar methane cracking system is proposed and the efficient utilization of the hydrogen and carbon products is explored. The carbon by-product is used in a direct carbon fuel cell and oxy- combustion. These processes eliminate the need for carbon capture technologies as they produce pure CO2 exhaust streams. The CO2 produced from the systems is used for enhanced oil recovery to produce crude oil. The produced turquoise hydrogen is liquified to make it suitable for exportation. The process is simulated on Aspen Plus® and its energy and exergy efficiencies are evaluated by carrying out a detailed thermodynamic analysis. A reservoir simulation is used to study the amount of oil that can be produced using the captured CO2. The overall system is studied for oil production over 20 years and energy and exergy of efficiencies 42.18% and 40.18% respectively were found. Enhanced oil recovery improves the recovery rate from 24.8% to 64.3%.
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