Production & Supply Chain
Renewable Power-to-Gas: A Technological and Economic Review
Aug 2015
Publication
The Power-to-Gas (PtG) process chain could play a significant role in the future energy system. Renewable electric energy can be transformed into storable methane via electrolysis and subsequent methanation. This article compares the available electrolysis and methanation technologies with respect to the stringent requirements of the PtG chain such as low CAPEX high efficiency and high flexibility. Three water electrolysis technologies are considered: alkaline electrolysis PEM electrolysis and solid oxide electrolysis. Alkaline electrolysis is currently the cheapest technology; however in the future PEM electrolysis could be better suited for the PtG process chain. Solid oxide electrolysis could also be an option in future especially if heat sources are available. Several different reactor concepts can be used for the methanation reaction. For catalytic methanation typically fixed-bed reactors are used; however novel reactor concepts such as three-phase methanation and micro reactors are currently under development. Another approach is the biochemical conversion. The bioprocess takes place in aqueous solutions and close to ambient temperatures. Finally the whole process chain is discussed. Critical aspects of the PtG process are the availability of CO2 sources the dynamic behaviour of the individual process steps and especially the economics as well as the efficiency.
Techno-Economic Assessment of Green Hydrogen Production by an Off-Grid Photovoltaic Energy System
Jan 2023
Publication
Green hydrogen production is essential to meeting the conference of the parties’ (COP) decarbonization goals; however this method of producing hydrogen is not as cost-effective as hydrogen production from fossil fuels. This study analyses an off-grid photovoltaic energy system designed to feed a proton-exchange membrane water electrolyzer for hydrogen production to evaluate the optimal electrolyzer size. The system has been analyzed in Baghdad the capital of Iraq using experimental meteorological data. The 12 kWp photovoltaic array is positioned at the optimal annual tilt angle for the selected site. The temperature effect on photovoltaic modules is taken into consideration. Several electrolyzers with capacities in the range of 2–14 kW were investigated to assess the efficiency and effectiveness of the system. The simulation process was conducted using MATLAB and considering the project life span from 2021 to 2035. The results indicate that various potentially cost-competitive alternatives exist for systems with market combinations resembling renewable hydrogen wholesale. It has been found that the annual energy generated by the analyzed photovoltaic system is 18892 kWh at 4313 operating hours and the obtained hydrogen production cost ranges from USD 5.39/kg to USD 3.23/kg. The optimal electrolyzer capacity matches a 12 kWp PV system equal to 8 kW producing 37.5 kg/year/kWp of hydrogen for USD 3.23/kg.
Thermodynamic Assessment of a Solar-Driven Integrated Membrane Reactor for Ethanol Steam Reforming
Nov 2020
Publication
To efficiently convert and utilize intermittent solar energy a novel solar-driven ethanol steam reforming (ESR) system integrated with a membrane reactor is proposed. It has the potential to convert low-grade solar thermal energy into high energy level chemical energy. Driven by chemical potential hydrogen permeation membranes (HPM) can separate the generated hydrogen and shift the ESR equilibrium forward to increase conversion and thermodynamic efficiency. The thermodynamic and environmental performances are analyzed via numerical simulation under a reaction temperature range of 100–400 ◦C with permeate pressures of 0.01–0.75 bar. The highest theoretical conversion rate is 98.3% at 100 ◦C and 0.01 bar while the highest first-law efficiency solar-to-fuel efficiency and exergy efficiency are 82.3% 45.3% and 70.4% at 215 ◦C and 0.20 bar. The standard coal saving rate (SCSR) and carbon dioxide reduction rate (CDRR) are maximums of 101 g·m−2 ·h −1 and 247 g·m−2 ·h −1 at 200 ◦C and 0.20 bar with a hydrogen generation rate of 22.4 mol·m−2 ·h −1 . This study illustrates the feasibility of solar-driven ESR integrated with a membrane reactor and distinguishes a novel approach for distributed hydrogen generation and solar energy utilization and upgradation.
Electric Load Influence on Performances of a Composite Plant for Hydrogen Production from RES and its Conversion in Electricity
Nov 2019
Publication
The analysis here presented investigates the influence of electrical load on the operational performances of a plant for hydrogen production from solar energy and its conversion in electricity via a fuel cell. The plant is an actual one currently under construction in Reggio Calabria (Italy) at the site of the Mediterranean university campus; it is composed of a Renewable Energy Source (RES) section (photovoltaic panels) a hydrogen production section and a fuel cell power section feeding the electrical energy demand of the load. Two different load configurations have been analysed and simulations have been carried out through HomerTM simulation code. Results allow interesting conclusions regarding the plant operation to be drawn. The study could have a remarkable role in supporting further research activities aimed at the assessment of the optimal configuration of this type of pioneering plants designed for feeding electrical loads possibly in a self-sufficient way.
Ammonia as a Carrier for Hydrogen Production by using Lanthanum Based Perovskites
Sep 2021
Publication
LaNiO3 and LaCoO3 perovskites synthesized by self-combustion were characterised and studied in the ammonia decomposition reaction for obtaining hydrogen. Both the fuel to metal nitrates molar ratio and calcination temperature were found to be crucial to synthesize perovskites by self-combustion. Moreover generating non-precursor species during synthesis and small metal size were two factors which significantly influenced catalytic activity. Hence with a citric acid to metal nitrates molar ratio equal to one a LaNiO3 perovskite was obtained with suitable physicochemical properties (specific surface area lower impurities and basicity). In addition a lower calcination temperature (650 ◦C) resulted in small and well-dispersed Ni0 crystallite size after reduction which in turn promoted the catalytic transformation of ammonia into hydrogen. For cobalt perovskites calcination temperature below 900 ◦C did not have a significant influence on the size of the metallic cobalt crystallite size. The nickel and cobalt perovskite-derived catalysts calcined at 650 ◦C and 750 ◦C respectively yielded excellent H2 production from ammonia decomposition. In particular at 450 ◦C almost 100% of the ammonia was converted over the LaNiO3 under study. Furthermore these materials displayed admirable performance and stability after one day of reaction.
Cotton Stalk Activated Carbon-supported Co–Ce–B Nanoparticles as Efficient Catalysts for Hydrogen Generation Through Hydrolysis of Sodium Borohydride
Nov 2019
Publication
Porous cotton stalk activated carbons (CSAC) were prepared by phosphoric acid activation of cotton stalks in a fluidized bed. The CSAC-supported Co–B and Co–Ce–B catalysts were prepared by the impregnation-chemical reduction method. The samples were characterized by the nitrogen adsorption XRD FTIR and TEM measurements. The effects of the sodium borohydride (NaBH4) and sodium hydroxide (NaOH) concentrations reaction temperature and recyclability on the rate of NaBH4 hydrolysis over the CSAC-supported Co–Ce–B catalysts were systematically investigated. The results showed that the agglomeration of the Co–Ce–B nanoclusters on the CSAC support surface was significantly reduced with the introduction of cerium. The CSAC-supported Co–Ce–B catalyst exhibited superior catalytic activity and the average hydrogen generation rate was 16.42 L min−1 g−1 Co at 25°C which is higher than the most reported cobalt-based catalysts. The catalytic hydrolysis of NaBH4 was zero order with respect to the NaBH4 concentration and the hydrogen generation rate decreased with the increase in the NaOH concentration. The activation energy of the hydrogen generation reaction on the prepared catalyst was estimated to be 48.22 kJ mol−1. A kinetic rate equation was also proposed.
Renewable Hydrogen Production from Butanol Steam Reforming over Nickel Catalysts Promoted by Lanthanides
Oct 2021
Publication
Hydrogen is mainly produced by steam reforming of natural gas a non-renewable resource. Alternative and renewable routes for hydrogen production play an important role in reducing dependence on oil and minimizing the emission of greenhouse gases. In this work butanol a model compound of bio-oil was employed for hydrogen production by steam reforming. The reaction was evaluated for 30 h in a tubular quartz reactor at 500 ◦C atmospheric pressure GHSV of 500000 h−1 and an aqueous solution feed of 10% v/v butanol. For this reaction catalysts with 20 wt.% NiO were prepared by wet impregnation using three supports: γ-alumina and alumina modified with 10 wt.% of cerium and lanthanum oxides. Both promoters increased the reduction degree of the catalysts and decreased catalyst acidity which is closely related to coke formation and deactivation. Ni/La2O3– Al2O3 presented a higher nickel dispersion (14.6%) which combined with other properties led to a higher stability higher mean hydrogen yield (71%) and lower coke formation per mass (56%). On the other hand the nonpromoted catalyst suffered a significant deactivation associated with coke formation favored by its highest acidity (3.1 µmol m−2 ).
The Use of Strontium Ferrite in Chemical Looping Systems
May 2020
Publication
This work reports a detailed chemical looping investigation of strontium ferrite (SrFeO3−δ) a material with the perovskite structure type able to donate oxygen and stay in a nonstoichiometric form over a broad range of oxygen partial pressures starting at temperatures as low as 250°C (reduction in CO measured in TGA). SrFeO3−δ is an economically attractive simple but remarkably stable material that can withstand repeated phase transitions during redox cycling. Mechanical mixing and calcination of iron oxide and strontium carbonate was evaluated as an effective way to obtain pure SrFeO3−δ. In–situ XRD was performed to analyse structure transformations during reduction and reoxidation. Our work reports that much deeper reduction from SrFeO3−δ to SrO and Fe is reversible and results in oxygen release at a chemical potential suitable for hydrogen production. Thermogravimetric experiments with different gas compositions were applied to characterize the material and evaluate its available oxygen capacity. In both TGA and in-situ XRD experiments the material was reduced below δ=0.5 followed by reoxidation either with CO2 or air to study phase segregation and reversibility of crystal structure transitions. As revealed by in-situ XRD even deeply reduced material regenerates at 900°C to SrFeO3−δ with a cubic structure. To investigate the catalytic behaviour of SrFeO3−δ in methane combustion experiments were performed in a fluidized bed rig. These showed SrFeO3−δ donates O2 into the gas phase but also assists with CH4 combustion by supplying lattice oxygen. To test the material for combustion and hydrogen production long cycling experiments in a fluidized bed rig were also performed. SrFeO3−δ showed stability over 30 redox cycles both in experiments with a 2-step oxidation performed in CO2 followed by air as well as a single step oxidation in CO2 alone. Finally the influence of CO/CO2 mixtures on material performance was tested; a fast and deep reduction in elevated pCO2 makes the material susceptible to carbonation but the process can be reversed by increasing the temperature or lowering pCO2.
Outlook of Fermentative Hydrogen Production Techniques: An Overview of Dark, Photo and Integrated Dark-photo Fermentative Approach to Biomass
Jan 2019
Publication
Biomass can be a sustainable choice for bioenergy production worldwide. Biohydrogen production using fermentative conversion of biomass has gained great interest during the last decade. Besides being an efficient transportation fuel biohydrogen can also be also be a low-carbon source of heat and electricity. Microbes assisted conversion (bioconversion) can be take place either in presence or absence of light. This is called photofermentation or dark-fermentation respectively. This review provides an overview of approaches of fermentative hydrogen production. This includes: dark photo and integrated fermentative modes of hydrogen production; the molecular basis behind its production and diverse range of its applicability industrially. Mechanistic understanding of the metabolic pathways involved in biomass-based fermentative hydrogen production are also reviewed.
Power-to-Gas: Electrolysis and Methanation Status Review
Jun 2019
Publication
This review gives a worldwide overview on Power-to-Gas projects producing hydrogen or renewable substitute natural gas focusing projects in central Europe. It deepens and completes the content of previous reviews by including hitherto unreviewed projects and by combining project names with details such as plant location. It is based on data from 153 completed recent and planned projects since 1988 which were evaluated with regards to plant allocation installed power development plant size shares and amounts of hydrogen or substitute natural gas producing examinations and product utilization phases. Cost development for electrolysis and carbon dioxide methanation was analyzed and a projection until 2030 is given with an outlook to 2050.<br/>The results show substantial cost reductions for electrolysis as well as for methanation during the recent years and a further price decline to less than 500 euro per kilowatt electric power input for both technologies until 2050 is estimated if cost projection follows the current trend. Most of the projects examined are located in Germany Denmark the United States of America and Canada. Following an exponential global trend to increase installed power today's Power-to-Gas applications are operated at about 39 megawatt. Hydrogen and substitute natural gas were investigated on equal terms concerning the number of projects.
The Global Status of CCS 2020: Vital to Achieve Net Zero
Dec 2020
Publication
The Global Status of CCS Report 2020 demonstrates the vital role of carbon capture and storage technologies (CCS) in reducing emissions to net-zero by 2050 as well as documenting the current status and important milestones for the technology over the past 12 months.<br/>The report provides detailed information on and analyses of the global CCS facility pipeline international policy perspectives CO2 storage and the CCS legal and regulatory environment.<br/>In addition four regional updates provide further detail about CCS progress across the Americas Europe Asia Pacific and the Gulf Cooperation Council States and a Technology section provides updates on key innovations and applications of CCS.
Prediction of Gaseous Products from Refuse Derived Fuel Pyrolysis Using Chemical Modelling Software - Ansys Chemkin-Pro
Nov 2019
Publication
There can be observed global interest in waste pyrolysis technology due to low costs and availability of raw materials. At the same time there is a literature gap in forecasting environmental effects of thermal waste treatment installations. In the article was modelled the chemical composition of pyrolysis gas with main focus on the problem in terms of environmental hazards. Not only RDF fuel was analysed but also selected waste fractions included in its composition. This approach provided comprehensive knowledge about the chemical composition of gaseous pyrolysis products which is important from the point of view of the heterogeneity of RDF fuel. The main goal of this article was to focus on the utilitarian aspect of the obtained calculation results. Final results can be the basis for estimating ecological effects both for existing and newly designed installations.
Pyrolysis process was modelled using Ansys Chemkin-Pro software. The investigation of the process were carried out for five different temperatures (700 750 800 850 and 900 °C). As an output the mole fraction of H2 H2O CH4 C2H2C2H4 C3H6 C3H8 CO CO2 HCl and H2S were presented. Additionally the reaction pathways for selected material were presented.
Based on obtained results it was established that the residence time did not influenced on the concentration of products contrary to temperature. The chemical composition of pyrolytic gas is closely related to wastes origin. The application of Chemkin-Pro allowed the calculation of formation for each products at different temperatures and formulation of hypotheses on the reaction pathways involved during pyrolysis process. Further based on the obtained results confirmed the possibilities of using pyrolysis gas from RDF as a substitute for natural gas in energy consumption sectors. Optimization of the process can be conducted with low financial outlays and reliable results by using calculation tools. Moreover it can be predicted negative impact of obtained products on the future installation.
Pyrolysis process was modelled using Ansys Chemkin-Pro software. The investigation of the process were carried out for five different temperatures (700 750 800 850 and 900 °C). As an output the mole fraction of H2 H2O CH4 C2H2C2H4 C3H6 C3H8 CO CO2 HCl and H2S were presented. Additionally the reaction pathways for selected material were presented.
Based on obtained results it was established that the residence time did not influenced on the concentration of products contrary to temperature. The chemical composition of pyrolytic gas is closely related to wastes origin. The application of Chemkin-Pro allowed the calculation of formation for each products at different temperatures and formulation of hypotheses on the reaction pathways involved during pyrolysis process. Further based on the obtained results confirmed the possibilities of using pyrolysis gas from RDF as a substitute for natural gas in energy consumption sectors. Optimization of the process can be conducted with low financial outlays and reliable results by using calculation tools. Moreover it can be predicted negative impact of obtained products on the future installation.
Interfacial Confinement of Ni-V2O3 in Molten Salts for Enhanced Electrocatalytic Hydrogen Evolution
Apr 2020
Publication
Implementation of non-precious electrocatalysts is key-enabling for water electrolysis to relieve challenges in energy and environmental sustainability. Self-supporting Ni-V2O3.electrodes consisting of nanostrip-like V2O3.perpendicularly anchored on Ni meshes are herein constructed via the electrochemical reduction of soluble NaVO3 in molten salts for enhanced electrocatalytic hydrogen evolution. Such a special configuration in morphology and composition creates a well confined interface between Ni and V2O3. Experimental and Density-Functional-Theory results confirm that the synergy between Ni and V2O3.accelerates the dissociation of H2O for forming hydrogen intermediates and enhances the combination of H* for generating H2.
Thermodynamic Assessment of the Novel Concept of the Energy Storage System Using Compressed Carbon Dioxide, Methanation and Hydrogen Generator
Jul 2021
Publication
The main aim of this paper is to characterize the concept of a novel energy storage system based on compressed CO2 storage installation that uses an infrastructure of depleted coal mines to provide required volume of tanks and additionally hydrogen generators and a methanation installation to generate synthetic natural gas that can be used within the system or taken out of it e.g. to a gas grid. A detailed mathematical model of the proposed solution was built using own codes and Aspen Plus software. Thermodynamic evaluation aiming at determining parameters composition and streams in all the most important nodes of the system for the nominal point and when changing a defined decision variable δ (in the range from 0.1 to 0.9) was made. The evaluation was made based on the storage efficiency volume of the tanks and flows of energy within the system. The storage efficiency in the nominal point reached 45.08% but was changing in the range from 35.06% (for δ = 0.1) to 63.93% (for δ = 0.9). For the nominal value of δ equal to 0.5 volume of the low-pressure tank (LPT) was equal to 132869 m3 while of the high pressure tank (HPT) to 1219 m3 . When changing δ these volumes were changing from 101900 m3 to 190878 m3 (for LPT) and from 935 to 1751 m3 (for HPT) respectively. Detailed results are presented in the paper and indicate high storage potential of the proposed solution in regions with underground mine infrastructure.
Self-sustainable Protonic Ceramic Electrochemical cells Using a Triple Conducting Electrode for Hydrogen and Power Production
Apr 2020
Publication
The protonic ceramic electrochemical cell (PCEC) is an emerging and attractive technology that converts energy between power and hydrogen using solid oxide proton conductors at intermediate temperatures. To achieve efficient electrochemical hydrogen and power production with stable operation highly robust and durable electrodes are urgently desired to facilitate water oxidation and oxygen reduction reactions which are the critical steps for both electrolysis and fuel cell operation especially at reduced temperatures. In this study a triple conducting oxide of PrNi0.5Co0.5O3-δ perovskite is developed as an oxygen electrode presenting superior electrochemical performance at 400~600 °C. More importantly the self-sustainable and reversible operation is successfully demonstrated by converting the generated hydrogen in electrolysis mode to electricity without any hydrogen addition. The excellent electrocatalytic activity is attributed to the considerable proton conduction as confirmed by hydrogen permeation experiment remarkable hydration behavior and computations.
Hydrogen Production by Steam Reforming of Ethanol on Rh-Pt Catalysts: Influence of CeO2, ZrO2, and La2O3 as Supports
Nov 2015
Publication
CeO2- ZrO2- and La2O3-supported Rh-Pt catalysts were tested to assess their ability to catalyze the steam reforming of ethanol (SRE) for H2 production. SRE activity tests were performed using EtOH:H2O:N2 (molar ratio 1:3:51) at a gaseous space velocity of 70600 h−1 between 400 and 700 °C at atmospheric pressure. The SRE stability of the catalysts was tested at 700 °C for 27 h time on stream under the same conditions. RhPt/CeO2 which showed the best performance in the stability test also produced the highest H2 yield above 600 °C followed by RhPt/La2O3 and RhPt/ZrO2. The fresh and aged catalysts were characterized by TEM XPS and TGA. The higher H2 selectivity of RhPt/CeO2 was ascribed to the formation of small (~5 nm) and stable particles probably consistent of Rh-Pt alloys with a Pt surface enrichment. Both metals were oxidized and acted as an almost constant active phase during the stability test owing to strong metal-support interactions as well as the superior oxygen mobility of the support. The TGA results confirmed the absence of carbonaceous residues in all the aged catalysts.
Pyrolysis-gasification of Wastes Plastics for Syngas Production Using Metal Modified Zeolite Catalysts Under Different Ratio of Nitrogen/Oxygen
Jun 2020
Publication
The aim of this study was the syngas production by the gasification of plastic waste (polyethylene polypropylene and terephthalate polyethylene). Ca Ce La Mg and Mn were used to promote the Ni/ZSM-5 catalyst in order to enhance the production of higher syngas yield. The modified catalysts can enhanced the reaction rate of the pyrolysis process and resulting in high syngas in the product yields. Especially cerium lanthanum promoted catalysts can enhance the yield of syngas. The effect of the reaction temperature and nitrogen/oxygen ratio of the carrier gas was also investigated. The maximum syngas production was obtained with lanthanum catalyst (112.2 mmol/g (95%N2 and 5%O2) and 130.7 mmol/g (90%N2 and 10%O2) at 850 °C. Less carbon depositions was found at 850 °C or even by the using of catalyst and more oxygen in the carrier gas. The oxygen content of the pyrolysis-gasification atmosphere had a key role to the syngas yield and affects significantly the carbon-monoxide/carbon-dioxide ratio. Catalysts can also accelerate the methanization reactions and isomerize the main carbon frame. Increasing in both temperature and oxygen in the atmosphere led to higher n-paraffin/n-olefin ratio and more multi-ring aromatic hydrocarbons in pyrolysis oils. The concentration of hydrocarbons containing oxygen and branched compounds was also significantly affected by catalysts.
Storable Energy Production from Wind over Water
Apr 2020
Publication
The current status of a project is described which aims to demonstrate the technical and economic feasibility of converting the vast wind energy available over the globe’s oceans and lakes into storable energy. To this end autonomous high-performance sailing ships are equipped with hydrokinetic turbines whose output is stored either in electric batteries or is fed into electrolysers to produce hydrogen which then is compressed and stored in tanks. In the present paper the previous analytical studies which showed the potential of this “energy ship concept” are summarized and progress on its hardware demonstration is reported involving the conversion of a model sailboat to autonomous operation. The paper concludes with a discussion of the potential of this concept to achieve the IPCC-mandated requirement of reducing the global CO2 emissions by about 45% by 2030 reaching net zero by 2050.
Graphene Oxide @ Nickel Phosphate Nanocomposites for Photocatalytic Hydrogen Production
Mar 2021
Publication
The graphene oxide @nickel phosphate (GO:NPO) nanocomposites (NCs) are prepared by using a one-pot in-situ solar energy assisted method by varying GO:NPO ratio i.e. 0.00 0.25 0.50 0.75 1.00 1.25 1.50 and 2.00 without adding any surfactant or a structure-directing reagent. As produced GO:NPO nanosheets exhibited an improved photocatalytic activity due to the spatial seperation of charge carriers through interface where photoinduced electrons transferred from NiPO4 to the GO sheets without charge-recombination. Out of the series the system 1.00 GO:NPO NC show the optimum hydrogen production activity (15.37 μmol H2 h−1) towards water splitting under the visible light irradiation. The electronic environment of the nanocomposite GO-NiO6/NiO4-PO4 elucidated in the light of advance experimental analyses and theoretical DFT spin density calculations. Structural advanmcement of composites are well correlated with their hydrogen production activity.
Direct Conversion of CO2 to Dimethyl Ether in a Fixed Bed Membrane Reactor: Influence of Membrane Properties and Process Conditions
Jun 2021
Publication
The direct hydrogenation of CO2 to dimethyl ether (DME) is a promising technology for CO2 valorisation. In this work a 1D phenomenological reactor model is developed to evaluate and optimize the performance of a membrane reactor for this conversion otherwise limited by thermodynamic equilibrium and temperature gradients. The co-current circulation of a sweep gas stream through the permeation zone promotes both water and heat removal from the reaction zone thus increasing overall DME yield (from 44% to 64%). The membrane properties in terms of water permeability (i.e. 4·10−7 mol·Pa−1m−2s−1) and selectivity (i.e. 50 towards H2 30 towards CO2 and CO 10 towards methanol) for optimal reactor performance have been determined considering for the first time non-ideal separation and non-isothermal operation. Thus this work sheds light into suitable membrane materials for this applications. Then the non-isothermal performance of the membrane reactor was analysed as a function of the process parameters (i.e. the sweep gas to feed flow ratio the gradient of total pressure across the membrane the inlet temperature to the reaction and permeation zone and the feed composition). Owing to its ability to remove 96% of the water produced in this reaction the proposed membrane reactor outperforms a conventional packed bed for the same application (i.e. with 36% and 46% improvement in CO2 conversion and DME yield respectively). The results of this work demonstrate the potential of the membrane reactor to make the CO2 conversion to DME a feasible process.
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