Production & Supply Chain
Investigation of an Intensified Thermo-Chemical Experimental Set-Up for Hydrogen Production from Biomass: Gasification Process Performance—Part I
Jun 2021
Publication
Biomass gasification for energy purposes has several advantages such as the mitigation of global warming and national energy independency. In the present work the data from an innovative and intensified steam/oxygen biomass gasification process integrating a gas filtration step directly inside the reactor are presented. The produced gas at the outlet of the 1 MWth gasification pilot plant was analysed in terms of its main gaseous products (hydrogen carbon monoxide carbon dioxide and methane) and contaminants. Experimental test sets were carried out at 0.25–0.28 Equivalence Ratio (ER) 0.4–0.5 Steam/Biomass (S/B) and 780–850 °C gasification temperature. Almond shells were selected as biomass feedstock and supplied to the reactor at approximately 120 and 150 kgdry/h. Based on the collected data the in-vessel filtration system showed a dust removal efficiency higher than 99%-wt. A gas yield of 1.2 Nm3dry/kgdaf and a producer gas with a dry composition of 27–33%v H2 23–29%v CO 31–36%v CO2 9–11%v CH4 and light hydrocarbons lower than 1%v were also observed. Correspondingly a Low Heating Value (LHV) of 10.3–10.9 MJ/Nm3dry and a cold gas efficiency (CGE) up to 75% were estimated. Overall the collected data allowed for the assessment of the preliminary performances of the intensified gasification process and provided the data to validate a simulative model developed through Aspen Plus software.
Water Photo-Oxidation Reaction on Clean and Doped Two-Dimensional Graphitic C2N
Apr 2020
Publication
In the search for new efficient photo-catalysts for hydrogen production through water splitting the main attention has been paid to tuning the band gap width and its position with respect to vacuum level. However actual electro-catalytic activity for the water oxidation reaction on a catalyst surface is no less important than those quantities. In this work we evaluate from first principles the thermodynamics of the reaction on relatively new candidates for water splitting: two-dimensional C2N and that doped with phosphorus. We find that the 4-step reaction usually expected for water splitting will not proceed on these systems resulting in oxygen atoms left strongly adsorbed to the surface. Another option a 3-step reaction is also found to be unfavorable. We also test an effect of higher oxygen coverage on the reaction thermodynamics as suggested elsewhere. We find that indeed the doubled O-coverage makes the 4-step reaction feasible for the doped C2N. However an unacceptably high anode potential is required to make this reaction proceed. We thus conclude that the materials under consideration may not be efficient electro-catalysts for water splitting.
Electric Field Effects on Photoelectrochemical Water Splitting: Perspectives and Outlook
Feb 2022
Publication
The grand challenges in renewable energy lie in our ability to comprehend efficient energy conversion systems together with dealing with the problem of intermittency via scalable energy storage systems. Relatively little progress has been made on this at grid scale and two overriding challenges still need to be addressed: (i) limiting damage to the environment and (ii) the question of environmentally friendly energy conversion. The present review focuses on a novel route for producing hydrogen the ultimate clean fuel from the Sun and renewable energy source. Hydrogen can be produced by light-driven photoelectrochemical (PEC) water splitting but it is very inefficient; rather we focus here on how electric fields can be applied to metal oxide/water systems in tailoring the interplay with their intrinsic electric fields and in how this can alter and boost PEC activity drawing both on experiment and non-equilibrium molecular simulation.
Thermodynamic Analysis of the Effect of Green Hydrogen Addition to a Fuel Mixture on the Steam Methane Reforming Process
Oct 2021
Publication
Steam methane (CH4–H2O) reforming in the presence of a catalyst usually nickel is the most common technology for generating synthesis gas as a feedstock in chemical synthesis and a source of pure H2 and CO. What is essential from the perspective of further gas use is the parameter describing a ratio of equilibrium concentration of hydrogen to carbon monoxide (/ = 2/). The parameter is determined by operating temperature and the initial ratio of steam concentration to methane = 2 0 /4 0 . In this paper the author presents a thermodynamic analysis of the effect of green hydrogen addition to a fuel mixture on the steam methane reforming process of gaseous phase (CH4/H2)–H2O. The thermodynamic analysis of conversion of hydrogen-enriched methane (CH4/H2)–H2O has been performed using parametric equation formalism allowing for determining the equilibrium composition of the process in progress. A thermodynamic condition of carbon precipitation in methane reforming (CH4/H2) with the gaseous phase of H2O has been interpreted. The ranges of substrate concentrations creating carbon deposition for temperature T = 1000 K have been determined based on the technologies used. The results obtained can serve as a model basis for describing the properties of steam reforming of methane and hydrogen mixture (CH4/H2)– H2O.
Integration of a Dark Fermentation Effluent in a Microalgal-based Biorefinery for the Production of High-added Value Omega-3 Fatty Acids
Mar 2019
Publication
Dark fermentation is an anaerobic digestion process of biowaste used to produce hydrogen- for generation of energy- that however releases high amounts of polluting volatile fatty acids such as acetic acid in the environment. In order for this biohydrogen production process to become more competitive the volatile fatty acids stream can be utilized through conversion to high added-value metabolites such as omega-3 fatty acids. The docosahexaenoic acid is one of the two most known omega-3 fatty acids and has been found to be necessary for a healthy brain and proper cardiovascular function. The main source is currently fish which obtain the fatty acid from the primary producers microalgae through the food chain. Crypthecodinium cohnii a heterotrophic marine microalga is known for accumulating high amounts of docosahexaenoic acid while offering the advantage of assimilating various carbon sources such as glucose ethanol glycerol and acetic acid. The purpose of this work was to examine the ability of a C. cohnii strain to grow on different volatile fatty acids as well as on a pre-treated dark fermentation effluent and accumulate omega-3. The strain was found to grow well on relatively high concentrations of acetic butyric or propionic acid as main carbon source in a fed-batch pH-auxostat. Most importantly C. cohnii totally depleted the organic acid content of an ultra-filtrated dark fermentation effluent after 60 h of fed-batch cultivation therefore offering a bioprocess not only able to mitigate environmental pollutants but also to provide a solution for a sustainable energy production process. The accumulated docosahexaenoic acid content was as high as 29.8% (w/w) of total fatty acids.
Economic Conditions for Developing Hydrogen Production Based on Coal Gasification with Carbon Capture and Storage in Poland
Sep 2020
Publication
This study documents the results of economic assessment concerning four variants of coal gasification to hydrogen in a shell reactor. That assessment has been made using discounting methods (NPV: net present value IRR: internal rate of return) as well as indicators based on a free cash flow to firm (FCFF) approach. Additionally sensitivity analysis has been carried out along with scenario analysis in current market conditions concerning prices of hard coal lignite hydrogen and CO2 allowances as well as capital expenditures and costs related to carbon capture and storage (CCS) systems. Based on NPV results a negative economic assessment has been obtained for all the analyzed variants varying within the range of EUR −903 to −142 million although the variants based on hard coal achieved a positive IRR (5.1–5.7%) but lower than the assumed discount rates. In Polish conditions the gasification of lignite seems to be unprofitable in the assumed scale of total investment outlays and the current price of coal feedstock. The sensitivity analyses indicate that at least a 20% increase of hydrogen price would be required or a similar reduction of capital expenditures (CAPEX) and costs of operation for the best variant to make NPV positive. Analyses have also indicated that on the economic basis only the prices of CO2 allowances exceeding EUR 40/Mg (EUR 52/Mg for lignite) would generate savings due to the availability of CCS systems.
Comparison Between Hydrogen Production by Alkaline Water Electrolysis and Hydrogen Production by PEM Electrolysis
Sep 2021
Publication
Hydrogen is an ideal clean energy source that can be used as an energy storage medium for renewable energy sources. The water electrolysis hydrogen production technology which is one of the mainstream hydrogen production methods can be used to produce high-purity hydrogen and other energy sources can be converted into hydrogen storage by electrolysis. Hydrogen production by alkaline water electrolysis and hydrogen production by PEM electrolysis are all water electrolysis hydrogen production technologies that have been industrially applied. From the application point of view the paper compares the working principle of the two kinds of electrolyzers the process flow of hydrogen production equipment advantages and disadvantages. This article provides a reference for relevant researchers.
Towards the Hydrogen Economy—A Review of the Parameters That Influence the Efficiency of Alkaline Water Electrolyzers
May 2021
Publication
Environmental issues make the quest for better and cleaner energy sources a priority. Worldwide researchers and companies are continuously working on this matter taking one of two approaches: either finding new energy sources or improving the efficiency of existing ones. Hydrogen is a well-known energy carrier due to its high energy content but a somewhat elusive one for being a gas with low molecular weight. This review examines the current electrolysis processes for obtaining hydrogen with an emphasis on alkaline water electrolysis. This process is far from being new but research shows that there is still plenty of room for improvement. The efficiency of an electrolyzer mainly relates to the overpotential and resistances in the cell. This work shows that the path to better electrolyzer efficiency is through the optimization of the cell components and operating conditions. Following a brief introduction to the thermodynamics and kinetics of water electrolysis the most recent developments on several parameters (e.g. electrocatalysts electrolyte composition separator interelectrode distance) are highlighted.
Hydrogen Production: State of Technology
May 2020
Publication
Presently hydrogen is for ~50% produced by steam reforming of natural gas – a process leading to significant emissions of greenhouse gas (GHG). About 30% is produced from oil/naphtha reforming and from refinery/chemical industry off-gases. The remaining capacity is covered for 18% from coal gasification 3.9% from water electrolysis and 0.1% from other sources. In the foreseen future hydrogen economy green hydrogen production methods will need to supply hydrogen to be used directly as fuel or to generate synthetic fuels to produce ammonia and other fertilizers (viz. urea) to upgrade heavy oils (like oil sands) and to produce other chemicals. There are several ways to produce H2 each with limitations and potential such as steam reforming electrolysis thermal and thermo-chemical water splitting dark and photonic fermentation; gasification and catalytic decomposition of methanol. The paper reviews the fundamentals and potential of these alternative process routes. Both thermo-chemical water splitting and fermentation are marked as having a long term but high "green" potential.
Hydrogen Production by Fluidized Bed Reactors: A Quantitative Perspective Using the Supervised Machine Learning Approach
Jul 2021
Publication
The current hydrogen generation technologies especially biomass gasification using fluidized bed reactors (FBRs) were rigorously reviewed. There are involute operational parameters in a fluidized bed gasifier that determine the anticipated outcomes for hydrogen production purposes. However limited reviews are present that link these parametric conditions with the corresponding performances based on experimental data collection. Using the constructed artificial neural networks (ANNs) as the supervised machine learning algorithm for data training the operational parameters from 52 literature reports were utilized to perform both the qualitative and quantitative assessments of the performance such as the hydrogen yield (HY) hydrogen content (HC) and carbon conversion efficiency (CCE). Seven types of operational parameters including the steam-to-biomass ratio (SBR) equivalent ratio (ER) temperature particle size of the feedstock residence time lower heating value (LHV) and carbon content (CC) were closely investigated. Six binary parameters have been identified to be statistically significant to the performance parameters (hydrogen yield (HY)) hydrogen content (HC) and carbon conversion efficiency (CCE) by analysis of variance (ANOVA). The optimal operational conditions derived from the machine leaning were recommended according to the needs of the outcomes. This review may provide helpful insights for researchers to comprehensively consider the operational conditions in order to achieve high hydrogen production using fluidized bed reactors during biomass gasification.
Global Status of CCS 2021: CCS Accelerating to Net Zero
Oct 2021
Publication
Carbon capture and storage (CCS) continues to make significant progress around the world against a backdrop of greater climate action from countries and private companies. The Global Status of CCS 2021 demonstrates the critical role of CCS as nations and industry accelerate to net-zero.<br/>The report provides detailed analyses of the global project pipeline international policy finance and emerging trends. In addition four regional overviews highlight the rapid development of CCS across North America Asia Pacific Europe and nearby regions and the Gulf Cooperation Council states.
Performance Study on Methanol Steam Reforming Rib Micro-Reactor with Waste Heat Recovery
Mar 2020
Publication
Automobile exhaust heat recovery is considered to be an effective means to enhance fuel utilization. The catalytic production of hydrogen by methanol steam reforming is an attractive option for onboard mobile applications due to its many advantages. However the reformers of conventional packed bed type suffer from axial temperature gradients and cold spots resulting from severe limitations of mass and heat transfer. These disadvantages limit reformers to a low efficiency of catalyst utilization. A novel rib microreactor was designed for the hydrogen production from methanol steam reforming heated by automobile exhaust and the effect of inlet exhaust and methanol steam on reactor performance was numerically analyzed in detail with computational fluid dynamics. The results showed that the best operating parameters were the counter flow water-to-alcohol (W/A) of 1.3 exhaust inlet velocity of 1.1 m/s and exhaust inlet temperature of 773 K when the inlet velocity and inlet temperature of the reactant were 0.1 m/s and 493 K respectively. At this condition a methanol conversion of 99.4% and thermal efficiency of 28% were achieved together with a hydrogen content of 69.6%.
Faraday’s Efficiency Modeling of a Proton Exchange Membrane Electrolyzer Based on Experimental Data
Sep 2020
Publication
In electrolyzers Faraday’s efficiency is a relevant parameter to assess the amount of hydrogen generated according to the input energy and energy efficiency. Faraday’s efficiency expresses the faradaic losses due to the gas crossover current. The thickness of the membrane and operating conditions (i.e. temperature gas pressure) may affect the Faraday’s efficiency. The developed models in the literature are mainly focused on alkaline electrolyzers and based on the current and temperature change. However the modeling of the effect of gas pressure on Faraday’s efficiency remains a major concern. In proton exchange membrane (PEM) electrolyzers the thickness of the used membranes is very thin enabling decreasing ohmic losses and the membrane to operate at high pressure because of its high mechanical resistance. Nowadays high-pressure hydrogen production is mandatory to make its storage easier and to avoid the use of an external compressor. However when increasing the hydrogen pressure the hydrogen crossover currents rise particularly at low current densities. Therefore faradaic losses due to the hydrogen crossover increase. In this article experiments are performed on a commercial PEM electrolyzer to investigate Faraday’s efficiency based on the current and hydrogen pressure change. The obtained results have allowed modeling the effects of Faraday’s efficiency by a simple empirical model valid for the studied PEM electrolyzer stack. The comparison between the experiments and the model shows very good accuracy in replicating Faraday’s efficiency.
Life Cycle Performance of Hydrogen Production via Agro-Industrial Residue Gasification—A Small Scale Power Plant Study
Mar 2018
Publication
This study evaluates the environmental profile of a real biomass-based hydrogen production small-scale (1 MWth) system composed of catalytic candle indirectly heated steam gasifier coupled with zinc oxide (ZnO) guard bed water gas shift (WGS) and pressure swing absorber (PSA) reactors. Environmental performance from cradle-to-gate was investigated by life cycle assessment (LCA) methodology. Biomass production shows high influence over all impact categories. In the syngas production process the main impacts observed are global warming potential (GWP) and acidification potential (AP). Flue gas emission from gasifier burner has the largest proportion of total GWP. The residual off gas use in internal combustion engine (ICE) leads to important environmental savings for all categories. Hydrogen renewability score is computed as 90% due to over 100% decline in non-renewable energy demand. Sensitivity analysis shows that increase in hydrogen production efficiency does not necessarily result in decrease in environmental impacts. In addition economic allocation of environmental charges increases all impact categories especially AP and photochemical oxidation (POFP).
Modulating Electronic Structure of Metal-organic Frameworks by Introducing Atomically Dispersed Ru for Efficient Hydrogen Evolution
Mar 2021
Publication
Developing high-performance electrocatalysts toward hydrogen evolution reaction is important for clean and sustainable hydrogen energy yet still challenging. Herein we report a single-atom strategy to construct excellent metal-organic frameworks (MOFs) hydrogen evolution reaction electrocatalyst (NiRu0.13-BDC) by introducing atomically dispersed Ru. Significantly the obtained NiRu0.13-BDC exhibits outstanding hydrogen evolution activity in all pH especially with a low overpotential of 36 mV at a current density of 10 mA cm−2 in 1 M phosphate buffered saline solution which is comparable to commercial Pt/C. X-ray absorption fine structures and the density functional theory calculations reveal that introducing Ru single-atom can modulate electronic structure of metal center in the MOF leading to the optimization of binding strength for H2O and H* and the enhancement of HER performance. This work establishes single-atom strategy as an efficient approach to modulate electronic structure of MOFs for catalyst design.
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.
Economic Analysis of Improved Alkaline Water Electrolysis
Feb 2017
Publication
Alkaline water electrolysis (AWE) is a mature hydrogen production technology and there exists a range of economic assessments for available technologies. For advanced AWEs which may be based on novel polymer-based membrane concepts it is of prime importance that development comes along with new configurations and technical and economic key process parameters for AWE that might be of interest for further economic assessments. This paper presents an advanced AWE technology referring to three different sites in Europe (Germany Austria and Spain). The focus is on financial metrics the projection of key performance parameters of advanced AWEs and further financial and tax parameters. For financial analysis from an investor’s (business) perspective a comprehensive assessment of a technology not only comprises cost analysis but also further financial analysis quantifying attractiveness and supply/market flexibility. Therefore based on cash flow (CF) analysis a comprehensible set of metrics may comprise levelised cost of energy or respectively levelized cost of hydrogen (LCH) for cost assessment net present value (NPV) for attractiveness analysis and variable cost (VC) for analysis of market flexibility. The German AWE site turns out to perform best in all three financial metrics (LCH NPV and VC). Though there are slight differences in investment cost and operation and maintenance cost projections for the three sites the major cost impact is due to the electricity cost. Although investment cost is slightly lower and labor cost is significantly lower in Spain the difference can not outweigh the higher electricity cost compared to Germany. Given the assumption that the electrolysis operators are customers directly and actively participating in power markets and based on the regulatory framework in the three countries in this special case electricity cost in Germany is lowest. However as electricity cost is profoundly influenced by political decisions as well as the implementation of economic instruments for transforming electricity systems toward sustainability it is hardly possible to further improve electricity price forecasts.
Discussion on the Feasibility of the Integration of Wind Power and Coal Chemical Industries for Hydrogen Production
Oct 2021
Publication
To improve the utilization rate of the energy industry and reduce high energy consumption and pollution caused by coal chemical industries in north western China a planning scheme of a wind‐coal coupling energy system was developed. This scheme involved the analysis method evaluation criteria planning method and optimization operation check for the integration of a comprehensive evaluation framework. A system was established to plan the total cycle revenue to maximize the net present value of the goal programming model and overcome challenges associated with the development of new forms of energy. Subsequently the proposed scheme is demonstrated using a 500‐MW wind farm. The annual capacity of a coal‐to‐methanol system is 50000. Results show that the reliability of the wind farm capacity and the investment subject are the main factors affecting the feasibility of the wind‐coal coupled system. Wind power hydrogen production generates O2 and H2 which are used for methanol preparation and electricity production in coal chemical systems respectively. Considering electricity price constraints and environmental benefits a methanol production plant can construct its own wind farm matching its output to facilitate a more economical wind‐coal coupled system. Owing to the high investment cost of wind power plants an incentive mechanism for saving energy and reducing emissions should be provided for the wind‐ coal coupled system to ensure economic feasibility and promote clean energy transformation.
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.
Techno-economic calculations of small-scale hydrogen supply systems for zero emission transport in Norway
Jun 2019
Publication
In Norway where nearly 100% of the power is hydroelectric it is natural to consider water electrolysis as the main production method of hydrogen for zero-emission transport. In a start-up market with low demand for hydrogen one may find that small-scale WE-based hydrogen production is more cost-efficient than large-scale production because of the potential to reach a high number of operating hours at rated capacity and high overall system utilization rate. Two case studies addressing the levelized costs of hydrogen in local supply systems have been evaluated in the present work: (1) Hydrogen production at a small-scale hydroelectric power plant (with and without on-site refuelling) and (2) Small hydrogen refuelling station for trucks (with and without on-site hydrogen production). The techno-economic calculations of the two case studies show that the levelized hydrogen refuelling cost at the small-scale hydroelectric power plant (with a local station) will be 141 NOK/kg while a fleet of 5 fuel cell trucks will be able to refuel hydrogen at a cost of 58 NOK/kg at a station with on-site production or 71 NOK/kg at a station based on delivered hydrogen. The study shows that there is a relatively good business case for local water electrolysis and supply of hydrogen to captive fleets of trucks in Norway particularly if the size of the fleet is sufficiently large to justify the installation of a relatively large water electrolyzer system (economies of scale). The ideal concept would be a large fleet of heavy-duty vehicles (with a high total hydrogen demand) and a refuelling station with nearly 100% utilization of the installed hydrogen production capacity.
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