Production & Supply Chain

With global warming and the depletion of fossil resources our fossil fuel-dependent society is expected to shift to one that instead uses hydrogen (H2) as a clean and renewable energy. To realize this the photocatalytic water-splitting reaction which produces H2 from water and solar energy through photocatalysis has attracted much attention. However for practical use the functionality of water-splitting photocatalysts must be further improved to efficiently absorb visible (Vis) light which accounts for the majority of sunlight. Considering the mechanism of water-splitting photocatalysis researchers in the various fields must be employed in this type of study to achieve this. However for researchers in fields other than catalytic chemistry ceramic (semiconductor) materials chemistry and electrochemistry to participate in this field new reviews that summarize previous reports on water-splitting photocatalysis seem to be needed. Therefore in this review we summarize recent studies on the development and functionalization of Vis-light-driven water-splitting photocatalysts. Through this summary we aim to share current technology and future challenges with readers in the various fields and help expedite the practical application of Vis-light-driven water-splitting photocatalysts.

According to European Directive 2014/94/EU hydrogen providers have the responsibility to prove that their hydrogen is of suitable quality for fuel cell vehicles. Contaminants may originate from hydrogen production transportation refuelling station or maintenance operation. This study investigated the probability of presence of the 13 gaseous contaminants (ISO 14687-2) in hydrogen on 3 production processes: steam methane reforming (SMR) process with pressure swing adsorption (PSA) chlor-alkali membrane electrolysis process and water proton exchange membrane electrolysis process with temperature swing adsorption. The rationale behind the probability of contaminant presence according to process knowledge and existing barriers is highlighted. No contaminant was identified as possible or frequent for the three production processes except oxygen (frequent for chlor-alkali membrane process) carbon monoxide (frequent) and nitrogen (possible) for SMR with PSA. Based on it a hydrogen quality assurance plan following ISO 19880-8 can be devised to support hydrogen providers in monitoring the relevant contaminants.

The widespread penetration of hydrogen in mainstream energy systems requires hydrogen production processes to be economically competent and environmentally efficient. Hydrogen if produced efficiently can play a pivotal role in decarbonizing the global energy systems. Therefore this study develops a framework which evaluates hydrogen production processes and quantifies deficiencies for improvement. The framework integrates slack-based data envelopment analysis (DEA) with fuzzy analytical hierarchy process (FAHP) and fuzzy technique for order of preference by similarity to ideal solution (FTOPSIS). The proposed framework is applied to prioritize the most efficient and sustainable hydrogen production in Pakistan. Eleven hydrogen production alternatives were analyzed under five criteria including capital cost feedstock cost O&M cost hydrogen production and CO2 emission. FAHP obtained the initial weights of criteria while FTOPSIS determined the ultimate weights of criteria for each alternative. Finally slack-based DEA computed the efficiency of alternatives. Among the 11 three alternatives (wind electrolysis PV electrolysis and biomass gasification) were found to be fully efficient and therefore can be considered as sustainable options for hydrogen production in Pakistan. The rest of the eight alternatives achieved poor efficiency scores and thus are not recommended.

This paper presents the optimal design and operation of integrated wind-hydrogen-electricity networks using the general mixed integer linear programming energy network model STeMES (Samsatli and Samsatli 2015). The network comprises: wind turbines; electrolysers fuel cells compressors and expanders; pressurised vessels and underground storage for hydrogen storage; hydrogen pipelines and electricity overhead/underground transmission lines; and fuelling stations and distribution pipelines.<br/>The spatial distribution and temporal variability of energy demands and wind availability were considered in detail in the model. The suitable sites for wind turbines were identified using GIS by applying a total of 10 technical and environmental constraints (buffer distances from urban areas rivers roads airports woodland and so on) and used to determine the maximum number of new wind turbines that can be installed in each zone.<br/>The objective is the minimisation of the total cost of the network subject to satisfying all of the demands of the domestic transport sector in Great Britain. The model simultaneously determines the optimal number size and location of each technology whether to transmit the energy as electricity or hydrogen the structure of the transmission network the hourly operation of each technology and so on. The cost of distribution was estimated from the number of fuelling stations and length of the distribution pipelines which were determined from the demand density at the 1 km level.<br/>Results indicate that all of Britain's domestic transport demand can be met by on-shore wind through appropriately designed and operated hydrogen-electricity networks. Within the set of technologies considered the optimal solution is: to build a hydrogen pipeline network in the south of England and Wales; to supply the Midlands and Greater London with hydrogen from the pipeline network alone; to use Humbly Grove underground storage for seasonal storage and pressurised vessels at different locations for hourly balancing as well as seasonal storage; for Northern Wales Northern England and Scotland to be self-sufficient generating and storing all of the hydrogen locally. These results may change with the inclusion of more technologies such as electricity storage and electric vehicles.

The need for energy storage to balance intermittent and inflexible electricity supply with demand is driving interest in conversion of renewable electricity via electrolysis into a storable gas. But high capital cost and uncertainty regarding future cost and performance improvements are barriers to investment in water electrolysis. Expert elicitations can support decision-making when data are sparse and their future development uncertain. Therefore this study presents expert views on future capital cost lifetime and efficiency for three electrolysis technologies: alkaline (AEC) proton exchange membrane (PEMEC) and solid oxide electrolysis cell (SOEC). Experts estimate that increased R&D funding can reduce capital costs by 0–24% while production scale-up alone has an impact of 17–30%. System lifetimes may converge at around 60000–90000 h and efficiency improvements will be negligible. In addition to innovations on the cell-level experts highlight improved production methods to automate manufacturing and produce higher quality components. Research into SOECs with lower electrode polarisation resistance or zero-gap AECs could undermine the projected dominance of PEMEC systems. This study thereby reduces barriers to investment in water electrolysis and shows how expert elicitations can help guide near-term investment policy and research efforts to support the development of electrolysis for low-carbon energy systems.

Hydrogen is a promising carbon-neutral energy carrier for a future decarbonized energy sector. This work presents process simulation studies of the gas switching reforming (GSR) process for hydrogen production with integrated CO₂ capture (GSR-H₂ process) at a minimal energy penalty. Like the conventional steam methane reforming (SMR) process GSR combusts the off-gas fuel from the pressure swing adsorption unit to supply heat to the endothermic reforming reactions. However GSR completes this combustion using the chemical looping combustion mechanism to achieve fuel combustion with CO₂ separation. For this reason the GSR-H₂ plant incurred an energy penalty of only 3.8 %-points relative to the conventional SMR process with 96% CO₂ capture. Further studies showed that the efficiency penalty is reduced to 0.3 %-points by including additional thermal mass in the reactor to maintain a higher reforming temperature thereby facilitating a lower steam to carbon ratio. GSR reactors are standalone bubbling fluidized beds that will be relatively easy to scale up and operate under pressurized conditions and the rest of the process layout uses commercially available technologies. The ability to produce clean hydrogen with no energy penalty combined with this inherent scalability makes the GSR-H2 plant a promising candidate for further research.

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.

Biomimetic sulfur-deficient indium sulfide (In_2.77S₄) was synthesized by a template-assisted hydrothermal method using leaves of Mimosa pudica as a template for the first time. The effect of this template in modifying the morphology of the semiconductor particles was determined by physicochemical characterization revealing an increase in surface area decrease in microsphere size and pore size and an increase in pore volume density in samples synthesized with the template. X-ray photoelectron spectroscopy (XPS) analysis showed the presence of organic sulfur (Ssingle bondO/Ssingle bondC/Ssingle bondH) and sulfur oxide species (single bondSO₂ SO₃²− SO₄²−) at the surface of the indium sulfide in samples synthesized with the template. Biomimetic indium sulfide also showed significant amounts of Fe introduced as a contaminant present on the Mimosa pudica leaves. The presence of these sulfur and iron species favors the photocatalytic activity for hydrogen production by their acting as a sacrificial reagent and promoting water oxidation on the surface of the templated particles respectively. The photocatalytic hydrogen production rates over optimally-prepared biomimetic indium sulfide and indium sulfide synthesized without the organic template were 73 and 22 μmol g⁻¹ respectively indicating an improvement by a factor of three in the templated sample.

The proof of concept for the production of pure pressurized hydrogen from hydrocarbons in combination with the sequestration of a pure stream of carbon dioxide with the reformer steam iron cycle is presented. The iron oxide based oxygen carrier (95% Fe₂O₃ 5% Al₂O₃) is reduced with syngas and oxidized with steam at 1023 K. The carbon dioxide separation is achieved via partial reduction of the oxygen carrier from Fe₂O₃ to Fe₃O₄ yielding thermodynamically to a product gas only containing CO₂ and H₂O. By the subsequent condensation of steam pure CO₂ is sequestrated. After each steam oxidation phase an air oxidation was applied to restore the oxygen carrier to hematite level. Product gas pressures of up to 30.1 bar and hydrogen purities exceeding 99% were achieved via steam oxidations. The main impurities in the product gas are carbon monoxide and carbon dioxide which originate from solid carbon depositions or from stored carbonaceous molecules inside the pores of the contact mass. The oxygen carrier samples were characterized using elemental analysis BET surface area measurement XRD powder diffraction SEM and light microscopy. The maximum pressure of 95 bar was demonstrated for hydrogen production in the steam oxidation phase after the full oxygen carrier reduction significantly reducing the energy demand for compressors in mobility applications.

Hydrogen can be produced from the decomposition of methane (also called pyrolysis). Many studies assume that this process emits few greenhouse gas (GHG) because the reaction from methane to hydrogen yields only solid carbon and no CO₂. This paper assesses the life-cycle GHG emissions and the levelized costs for hydrogen provision from methane decomposition in three configurations (plasma molten metal and thermal gas). The results of these configurations are then compared to electrolysis and steam methane reforming (SMR) with and without CO₂capture and storage (CCS). Under the global natural gas supply chain conditions hydrogen from methane decomposition still causes significant GHG emissions between 43 and 97 g CO₂-eq./MJ. The bandwidth is predominately determined by the energy source providing the process heat i.e. the lowest emissions are caused by the plasma system using renewable electricity. This configuration shows lower GHG emissions compared to the “classical” SMR (99 g CO₂-eq./MJ) but similar emissions to the SMR with CCS (46 g CO2-eq./MJ). However only electrolysis powered with renewable electricity leads to very low GHG emissions (3 g CO₂-eq./MJ). Overall the natural gas supply is a decisive factor in determining GHG emissions. A natural gas supply with below-global average GHG emissions can lead to lower GHG emissions of all methane decomposition configurations compared to SMR. Methane decomposition systems (1.6 to 2.2 €/kg H2) produce hydrogen at costs substantially higher compared to SMR (1.0 to 1.2 €/kg) but lower than electrolyser (2.5 to 3.0 €/kg). SMR with CCS has the lowest CO₂abatement costs (24 €/t CO₂-eq. other > 141 €/t CO₂-eq.). Finally fuels derived from different hydrogen supply options are assessed. Substantially lower GHG emissions compared to the fossil reference (natural gas and diesel/gasoline) are only possible if hydrogen from electrolysis powered by renewable energy is used (>90% less). The other hydrogen pathways cause only slightly lower or even higher GHG emissions.