Assessment of hydrogen supply solutions for hydrogen fueling station: A Shanghai case study

Shanghai is one of the fastest growing regions of hydrogen energy in China. This paper researched feasible hydrogen sources in both internal and external Shanghai. This study comes up 9 hydrogen production methods and 6 transportation routes, ultimately forms 12 hydrogen supply solutions according to local conditions. The total cost in each solution is estimated including processes of hydrogen production, treatments, storage and transportation based on different transport distance. The results indicate that hydrogen supply cost is above 50 CNY/kgH₂ for external hydrogen sources after long-distance transportation to Shanghai, such as hydrogen production from coal in Inner Mongolia and from renewables in Hebei. The total cost of on-site hydrogen production from natural gas can be controlled under 40 CNY/kgH₂. When the price of wind power reduces to 0.5 CNY/kWh, hydrogen production from offshore wind power cooperating with hydrogen pipeline network has the greatest development potential for Shanghai hydrogen supply.     

Exergy analysis of hydrogen production via steam methane reforming

The performance of hydrogen production via steam methane reforming (SMR) is evaluated using exergy analysis, with emphasis on exergy flows, destruction, waste, and efficiencies. A steam methane reformer model was developed using a chemical equilibrium model with detailed heat integration. A base-case system was evaluated using operating parameters from published literature. Reformer operating parameters were varied to illustrate their influence on system performance. The calculated thermal and exergy efficiencies of the base-case system are lower than those reported in literature. The majority of the exergy destruction occurs due to the high irreversibility of chemical reactions and heat transfer. A significant amount of exergy is wasted in the exhaust stream. The variation of reformer operating parameters illustrated an inverse relationship between hydrogen yield and the amount of methane required by the system. The results of this investigation demonstrate the utility of exergy analysis and provide guidance for where research and development in hydrogen production via SMR should be focused.     

Research and development of on-site small skid-mounted natural gas to hydrogen generator in China

Using skid-mounted natural gas to hydrogen generator in hydrogen refueling station can significantly reduce the cost of hydrogen. In 2021, China successfully built the first 250 Nm³/h on-site skid-mounted natural gas to hydrogen generator, which was successfully debug-ed in Foshan, providing hydrogen products with purity ≥99.999% for FCVs. This paper summarized the technological process and development, analyzed the risk and the safety design of skid-mounted natural gas to hydrogen generator. Several key factors affecting compactness are analyzed, including process and technical route, reforming reformer and catalyst, heat exchange network, heat exchanger and steam generation system, PSA unit and overall integrated design, etc. In addition, innovative strategies to optimize the compactness of the device are given from the aspects of process flow, reforming reformer and steam generation system.The suggestions are put forward for the development and application of on-site skid-mounted natural gas to hydrogen generator.     

A multi-scale dynamic two-dimensional heterogeneous model for catalytic steam methane reforming reactors

A multi-scale, dynamic, two-dimensional, heterogeneous model for catalytic steam methane reforming (SMR) is developed. The model, derived from first principles, accounts for diffusional limitations for both mass and energy within large industrial-scale catalyst particles. The diffusional limitations have been incorporated, not by the conventional method of computing the effectiveness factor, but by accounting for the transfer of species as a function of the concentration and temperature gradients existing between the gas phase and catalyst surface along the reactor length. The model has been validated with available industrial steady-state data from literature. The model was then used to study the dynamic behaviour of key variables and the effects of feed disturbances on catalyst core and tube wall temperatures.     

Assessment of CO2 capture options from various points in steam methane reforming for hydrogen production

Steam methane reforming (SMR) is currently the main hydrogen production process in industry, but it has high emissions of CO₂, at almost 7 kg CO₂/kg H₂ on average, and is responsible for about 3% of global industrial sector CO₂ emissions. Here, the results are reported of an investigation of the effect of steam-to-carbon ratio (S/C) on CO₂ capture criteria from various locations in the process, i.e. synthesis gas stream (location 1), pressure swing adsorber (PSA) tail gas (location 2), and furnace flue gases (location 3). The CO₂ capture criteria considered in this study are CO₂ partial pressure, CO₂ concentration, and CO₂ mass ratio compared to the final exhaust stream, which is furnace flue gases. The CO₂ capture number (N_cc) is proposed as measure of capture favourability, defined as the product of the three above capture criteria. A weighting of unity is used for each criterion. The best S/C ratio, in terms of providing better capture option, is determined. CO₂ removal from synthesis gas after the shift unit is found to be the best location for CO₂ capture due to its high partial pressure of CO₂. However, furnace flue gases, containing almost 50% of the CO₂ in produced in the process, are of great significance environmentally. Consequently, the effects of oxygen enrichment of the furnace feed are investigated, and it is found that this measure improves the CO₂ capture conditions for lower S/C ratios. Consequently, for an S/C ratio of 2.5, CO₂ capture from a flue gas stream is competitive with two other locations provided higher weighting factors are considered for the full presence of CO₂ in the flue gases stream. Considering carbon removal from flue gases, the ratio of hydrogen production rate and N_cc increases with rising reformer temperature.     

Economic analysis of hydrogen production from steam reforming process: A literature review

The interest in steam reforming process as an efficient method for hydrogen production has been greatly increasing, due to its efficiency during hydrogen production and low environmental problems compared to other techniques. The main objective of this review was to present a comprehensive study of environmental, economic aspects of hydrogen production from steam reforming of raw materials such as biomass, bio-gas, ethanol, and natural gas. From literature review, it was found that among methods for hydrogen production, steam reforming of natural gas has lower installed capital due to the precence of high amounts of unconverted hydrocarbons in the produced gas (so-called tar) during other methods such as steam reforming of bio-gas.     

Millisecond methane steam reforming for hydrogen production: A computational fluid dynamics study

The potential of methane steam reforming to produce hydrogen in thermally integrated micro-chemical systems at short contact times was theoretically explored. Methane steam reforming coupled with methane catalytic combustion in microchannel reactors for hydrogen production was studied numerically. A two-dimensional computational fluid dynamics model with detailed chemistry and transport was developed. To provide guidelines for optimal design, reactor behavior was studied, and the effect of design parameters such as catalyst loading, channel height, and flow arrangement was evaluated. To understand how steam reforming can happen at millisecond contact times, the relevant process time scales were analyzed, and a heat and mass transfer analysis was performed. The importance of energy management was also discussed in order to obtain a better understanding of the mechanism responsible for efficient heat exchange between highly exothermic and endothermic reactions. The results demonstrated the feasibility of the design of millisecond reforming systems, but only under certain conditions. To achieve this goal, process intensification through miniaturization and the improvement in catalyst performance is very important, but not sufficient; very careful design and implementation of the system is also necessary to enable high thermal integration. The channel height plays an important role in determining the efficiency of heat exchange. A proper balance of the flow rates of the combustible and reforming streams is an important design criterion. Reactor performance is significantly affected by flow arrangement, and co-current operation is recommended to achieve a good energy balance within the system. The catalyst loading must be carefully designed to avoid insufficient reactant conversion or hot spots. Finally, operating windows were identified, and engineering maps for designing devices with desired power were constructed.     

Optimal design of a sleeve-type steam methane reforming reactor for hydrogen production from natural gas

The three-dimensional computational fluid dynamics (CFD) model was used in a sleeve-type steam methane reforming (SMR) reactor for H₂ production of 2.5 Nm³/h from natural gas. The feed and combustion gases acted as a counter-current heat exchange owing to a narrow sleeve equipped between the combustor and catalyst-bed. The CFD results were validated against the experimental data of the SMR reactor with a sleeve gap size of 3 mm. The effect of the sleeve gap size and the flame shape on process performances such as H₂ production rate, thermal efficiency, and uniformity of catalyst-bed temperature was investigated using the CFD model. The sleeve gap size influenced the gas velocity inside the sleeve gap and the convective heat transfer. The SMR reactor with a sleeve gap size of 7 mm showed the highest H₂ production rate and thermal efficiency when comparing six sleeve gap sizes ranging from 2 to 10 mm. A new flame shape for the SMR reactor with the sleeve gap size of 7 mm was proposed to improve the process performances.     

Development and CFD analysis for determining the optimal operating conditions of 250 kg/day hydrogen generation for an on-site hydrogen refueling station (HRS) using steam methane reforming

The objective of this study to develop and undertake a comprehensive CFD analysis of an effective state-of-the-art 250 kg/day hydrogen generation unit for an on-site hydrogen refueling station (HRS), an essential part of the infrastructure required for fuel cell vehicles and various aspects of hydrogen mobility. This design consists of twelve reforming tubes and one newly designed metal fiber burner to ensure superior emission standards and performance. Experimental and computational modeling steps are conducted to investigate the effects of various operating conditions, the excess air ratio (EAR) at the burner, the gas hourly space velocity (GHSV), the process gas inlet temperature, and the operating pressure on the hydrogen production rate and thermal efficiency. The results indicate that the performance of the steam methane reforming reactor increased significantly by improving the combustion characteristics and preventing local peak temperatures along the reforming tube. It is shown that EAR should be chosen appropriately to maximize the hydrogen production rate and lifetime operation of the reformer tube. It is found that high inlet process gas temperatures and low operating pressure are beneficial, but these parameters have to be chosen carefully to ensure proper efficiency. Also, a high GHSV shortens the residence time and provides unfavorable heat transfer in the bed, leading to decreased conversion efficiency. Thus, a moderate GHSV should be used. It is shown that heat transfer is an essential factor for obtaining increased hydrogen production. This study addresses the pressing need for the HRS to adopt such a compact system, whose processes can ensure greater hydrogen production rates as well as better durability, reliability, and convenience.     

Exergoenvironmental analysis of a steam methane reforming process for hydrogen production

Steam methane reforming (SMR) is one of the most promising processes for hydrogen production. Several studies have demonstrated its advantages from the economic viewpoint. Nowadays process development is based on technical and economical aspects; however, in the near future, the environmental impact will play a significant role in the design of such processes. In this paper, an SMR process is studied from the viewpoint of overall environmental impact, using an exergoenvironmental analysis. This analysis presents the combination of exergy analysis and life cycle assessment. Components where chemical reactions occur are the most important plant components from the exergoenvironmental point of view, because, in general, there is a high environmental impact associated with these components. This is mainly caused by the exergy destruction within the components, and this in turn is mainly due to the chemical reactions. The obtained results show that the largest potential for reducing the overall environmental impact is associated with the combustion reactor, the steam reformer, the hydrogen separation unit and the major heat exchangers. The environmental impact in these components can mainly be reduced by improving their exergetic efficiency. A sensitivity analysis for some important exergoenvironmental variables is also presented in the paper.     

Thermodynamic analysis of hydrogen production via sorption-enhanced steam methane reforming in a new class of variable volume batch-membrane reactor

Combined reaction–separation processes are a widely explored method to produce hydrogen from endothermic steam reforming of hydrocarbon feedstock at a reduced reaction temperature and with fewer unit operation steps, both of which are key requirements for energy efficient, distributed hydrogen production. This work introduces a new class of variable volume batch reactors for production of hydrogen from catalytic steam reforming of methane that operates in a cycle similar to that of an internal combustion engine. It incorporates a CO₂ adsorbent and a selectively permeable hydrogen membrane for in situ removal of the two major products of the reversible steam methane reforming reaction. Thermodynamic analysis is employed to define an envelope of ideal reactor performance and to explore the tradeoff between thermal efficiency and hydrogen yield density with respect to critical operating parameters, including sorbent mass, steam to methane ratio and fraction of product gas recycled. Particular attention is paid to contrasting the variable volume batch-membrane reactor approach to a conventional fixed bed reaction–separation approach. The results indicates that the proposed reactor is a viable option for low temperature distributed production of hydrogen from methane, the primary component of natural gas feedstock, motivating a detailed study of reaction/adsorption kinetics and heat/mass transfer effects.     

Evaluation of the economic impact of hydrogen production by methane decomposition with steam reforming of methane process

There has been considerable interest in the development of more efficient processes to generate hydrogen. Currently, steam methane reforming (SMR) is the most widely applied route for producing hydrogen from natural gas. Researchers worldwide have been working to invent more efficient routes to produce hydrogen. One of the routes is thermocatalytic decomposition of methane (TCDM) - a process that decomposes methane thermally to produce hydrogen from natural gas. TCDM has not yet been commercialized. However, the aim of this work was to conduct an economic and environmental analysis to determine whether the TCDM process is competitive with the more popular SMR process. The results indicate that the TCDM process has a lower carbon footprint. Further research on TCDM catalysts could make this process economically competitive with steam methane reforming.     

CFD simulation with detailed chemistry of steam reforming of methane for hydrogen production in an integrated micro-reactor

micro-reactor has drawn more and more attention in recent years due to the process intensification on basic transport phenomena in micro-channels, which would often lead to the improved reactor performance. Steam reforming of methane (SRM) in micro-reactor has great potential to realize a low-cost, compact process for hydrogen production via an evident shortening of reaction time from seconds to milliseconds. This work focuses on the detailed modeling and simulation of a micro-reactor design for SRM reaction with the integration of a micro-channel for Rh-catalyzed endothermic reaction, a micro-channel for Pt-catalyzed exothermic reaction and a wall in between with Rh or Pt-catalyst coated layer. The elementary reaction kinetics for SRM process is adopted in the CFD model, while the combustion channel is described by global reaction kinetics. The model predictions were quantitatively validated by the experimental data in the literature. For the extremely fast reactions in both channels, the simulations indicated the significance of the heat conduction ability of the reactor wall as well as the interplay between the exothermic and endothermic reactions (e.g., the flow rate ratio of fuel gas to reforming gas). The characteristic width of 0.5 mm is considered to be a suitable channel size to balance the trade-off between the heat transfer behavior in micro-channels and the easy fabrication of micro-channels.     

Preparation of Ni-based egg-shell-type catalyst on cylinder-shaped alumina pellets and its application for hydrogen production via steam methane reforming

Nickel-based ‘egg-shell-type’ catalysts were prepared using cylinder-shaped alumina pellets as supports. In the egg-shell-type catalysts, nickel was selectively located in the outer region of the alumina pellets. Ethylene glycol or 1-octanol were used as hydrophobic solvents to retard internal penetration of the alumina pellets by the nickel nitrate solution. Without hydrophobic solvent, a ‘homo-type’ catalyst with even nickel distribution inside the alumina pellets was achieved. Cross-sectional images and SEM-EDS analysis of the cylinder-shaped alumina pellets showed that nickel concentration in the egg-shell-type catalyst was higher in the outer region and decreased towards the inner region of the alumina pellets. The egg-shell-type nickel distribution was maintained after subsequent magnesium impregnation and calcination processes. X-ray diffraction patterns and temperature programmed reduction profiles showed that the only difference between homo-type and egg-shell type catalysts, when their nickel loading was the same, was the nickel distribution inside pellets; and this was shown to cause significant difference in their catalytic activity in the steam methane reforming (SMR) reaction. For the homo-type catalyst, nickel loading of 3.5 wt% was insufficient for the SMR reaction, as metallic nickel particles were evenly distributed through the entire alumina pellet. However, nickel loading of 3.5 wt% was sufficient for the egg-shell-type catalyst, because active sites with metallic nickel particles were concentrated in the outer region of the pellets. These experimental results confirmed that the egg-shell-type nickel distribution is a favorable design for an SMR reaction catalyst.     

A framework for assessing economics of blue hydrogen production from steam methane reforming using carbon capture storage & utilisation

Hydrogen (H₂) generation using Steam Methane Reforming (SMR) is at present the most economical and preferred pathway for commercial H₂ generation. This process, however, emits a considerable amount of CO₂, ultimately negating the benefit of using H₂ as a clean industrial feedstock and energy carrier. That has prompted growing interest in enabling CO₂ capture from SMR for either storage or utilisation and producing zero-emission “blue H₂”. In this paper, we propose a spatial techno-economic framework for assessing blue hydrogen production SMR hubs with carbon capture, utilisation and storage (CCUS), using Australia as a case study. Australia offers a unique opportunity for developing such ‘blue H₂’ hubs given its extensive natural gas resources, availability of known carbon storage reservoirs and an ambitious government target to produce clean/zero-emission H₂ at the cost of <A$2 kg^?1 by 2030. Our results highlight that the H₂ production costs are unsurprisingly dominated by natural gas, with the additional capital requirement of carbon capture and storage (CCS) also playing a critical role. These outcomes are especially pertinent for eastern Australian states, as they are experiencing high natural gas costs and would generally require extensive CO₂ transport and storage infrastructure to tap potential storage reservoirs, ultimately resulting in a higher cost of producing H₂ (>A$2.7 kg_H2^?1). On the other hand, Western Australia offers lower gas pricing and relatively lesser storage costs, which would lead to more economically favourable hydrogen production (<A$2.2 kg_H2^?1). We further explore the possibility of utilising the emissions captured at blue SMR hubs by converting them into formic acid through CO₂ electroreduction, yielding revenue that will decrease the cost of blue H₂ and reduce the reliance on CO₂ storage. Our analysis reveals that formic acid production utilising a 10 MW CO₂ electrolyser can potentially reduce H₂ production costs by between 4 and 9%. Further cost reduction is possible by scaling the CO₂ electrolyser capacity to convert a larger portion of the emissions captured, albeit at the cost of higher capital investment, electricity consumption and saturating the market for formic acid. Thus, carbon utilisation for a range of products with high market demand represents a more promising approach to replacing the need for costly carbon storage. Overall, our modelling framework can be adapted for global application, particularly for regions interested in generating blue H₂ and extended to include other CO₂ utilisation opportunities and evaluate other hydrogen production technologies.     

Synthesis and characterization of supportless Ni-Pd-CNT nanocatalyst for hydrogen production via steam reforming of methane

Supportless Ni-Pd-0.1CNT foamy nanocatalyst with specific surface area of 611.3 m²/g was produced by electroless deposition of nickel, palladium and multiwall carbon nanotube (MWCNT) on interim polyurethane substrate. Application of temperature programmed reduction (TPR) and temperature programmed oxidation (TPO) data into Kissinger (Redhead) kinetic model showed lessening of their activation energies due to Pd and CNT addition. Presence of foamy Ni/SiC caused 8% higher steam reforming of methane; while Ni-Pd-0.1CNT presence resulted in 22% higher methane conversion. The catalytic behavior of the samples was described by morphological and compositional studies which were carried out by transmission electron microscope (TEM), field emission scanning electron microscope (FESEM) equipped with energy dispersive spectroscopy (EDS) and atomic absorption spectrometer (AAS) pondered with Brunauer–Emmett–Teller (BET), TPR, TPO and X-ray diffraction (XRD).     

Hydrogen production from methane and natural gas steam reforming in conventional and microreactor reaction systems

Ni-based (over MgO and Al₂O₃) and noble metal-based (Pd and Pt over Al₂O₃) catalysts were prepared by wet impregnation method and thereafter impregnated in microreactors. The catalytic activity was measured at several temperatures, atmospheric pressure and different steam to carbon, S/C, ratios. These conditions were the same for conventional, fixed bed reactor system, and microreactors. Weight hourly space velocity, WHSV, was maintained equal in order to compare the activity results from both reaction systems. For microreactor systems, similar activities of Ni-based catalyst were measured in the steam methane reforming (SMR) activity tests, but not in the case of natural gas steam reforming tests. When noble metal-based catalysts were used in the conventional reaction system no significant activity was measured but all catalysts showed some activity when they were tested in the microreactor systems. The analysis by SEM and TEM revealed a carbon-free surface for Ni-based catalyst as well as carbon filaments growth in case of noble metal-based catalysts.     

Numerical and experimental study on hydrogen production via dimethyl ether steam reforming

This work presents the characteristics of catalytic dimethyl ether (DME)/steam reforming based on a Cu–Zn/γ-Al₂O₃ catalyst for hydrogen production. A kinetic model for a reformer that operates at low temperature (200 °C–500 °C) is simulated using COMSOL 5.2 software. Experimental verification is performed to examine the critical parameters for the reforming process. During the experiment, superior Cu–Zn/γ-Al₂O₃catalysts are manufactured using the sol-gel method, and ceramic honeycombs coated with this catalyst (1.77 g on each honeycomb, five honeycombs in the reactor) are utilized as catalyst bed in the reformer to enhance performance. The steam, DME mass ratio is stabilized at 3:1 using a mass flow controller (MFC) and a generator. The hydrogen production rate can be significantly affected depending on the reactant's mass flow rate and temperature. And the maximum hydrogen yield can reach 90% at 400 °C. Maximum 8% error for the hydrogen yield is achieved between modeling and experimental results. These experiments can be further explored for directly feeding hydrogen to proton exchange membrane fuel cell (PEMFC) under the load variations.