An analytical and experimental investigation of high-pressure catalytic steam reforming of ethanol in a hydrogen selective membrane reactor

The objective of this work was to explore the benefits of high-pressure steam reforming of ethanol for the production of hydrogen needed to refuel the high-pressure tanks of fuel cell (polymer electrolyte) vehicles. This paper reports on the potential efficiency benefits and challenges of pressurized reforming and options for dealing with the challenges; it reports the results from experiments in a micro-reactor, followed by a modeling study of the reactor to project the dependence of the hydrogen yields on process parameters. The experiments were conducted in the range of approximately 7–70 atm, 600–750 °C, steam-to-carbon molar ratios of 3–12, and gas hourly space velocities of 8500–83,000 per hour. By placing a hydrogen-transporting palladium-alloy membrane within the catalyst zone, this study quantified the beneficial effect of hydrogen extraction from the reforming zone. The model was used to explore the parameter space to define the reactor and conditions that would be needed to approach the efficiency targets for distributed hydrogen production plants. The results indicate that the tested catalyst was sufficiently active, and the hydrogen yield achieved with the experimental membrane reactor was limited by the low hydrogen flux of the tested membrane. The reactor model predicts that a membrane with at least 20 times higher flux than currently evaluated would be sufficient to generate hydrogen yields to match efficiency targets of 72%.     

Numerical modeling of an automotive derivative polymer electrolyte membrane fuel cell cogeneration system with selective membranes

Cogeneration power plants based on fuel cells are a promising technology to produce electric and thermal energy with reduced costs and environmental impact. The most mature fuel cell technology for this kind of applications are polymer electrolyte membrane fuel cells, which require high-purity hydrogen.The most common and least expensive way to produce hydrogen within today's energy infrastructure is steam reforming of natural gas. Such a process produces a syngas rich in hydrogen that has to be purified to be properly used in low temperature fuel cells. However, the hydrogen production and purification processes strongly affect the performance, the cost, and the complexity of the energy system.Purification is usually performed through pressure swing adsorption, which is a semi-batch process that increases the plant complexity and incorporates a substantial efficiency penalty. A promising alternative option for hydrogen purification is the use of selective metal membranes that can be integrated in the reactors of the fuel processing plant. Such a membrane separation may improve the thermo-chemical performance of the energy system, while reducing the power plant complexity, and potentially its cost. Herein, we perform a technical analysis, through thermo-chemical models, to evaluate the integration of Pd-based H₂-selective membranes in different sections of the fuel processing plant: (i) steam reforming reactor, (ii) water gas shift reactor, (iii) at the outlet of the fuel processor as a separator device. The results show that a drastic fuel processing plant simplification is achievable by integrating the Pd-membranes in the water gas shift and reforming reactors. Moreover, the natural gas reforming membrane reactor yields significant efficiency improvements.     

Economic analysis of hydrogen production from wastewater and wood for municipal bus system

The levelized cost of hydrogen for municipal fuel cell buses has been determined using the DOE H2A model for steam methane reforming (SMR), molten carbonate fuel cell reforming (MCFC), and wood gasification using wastewater biogas and willow wood chips as energy feedstocks. 300 kg H₂/day was chosen as the design capacity. Greenhouse gas emissions were calculated for each for the three processes and compared to diesel bus emissions in order to assess environmental impact. The levelized cost per kilogram for SMR, MCFC, and gasification is $5.12, $8.59, and $10.62, respectively. SMR provided the lowest sensitivity to feedstock price, and lowest levelized cost at various scales, with competitive cost to diesel on a cost/km basis. All three technologies provide a reduction in total greenhouse gases compared to diesel bus emissions, with MCFC providing the largest reduction. These results provide preliminary evidence that small scale distributed hydrogen production for public transportation can be relatively cost-effective and have minimal environmental impact.     

Technoeconomic analysis of a methanol plant based on gasification of biomass and electrolysis of water

Methanol production process configurations based on renewable energy sources have been designed. The processes were analyzed in the thermodynamic process simulation tool DNA. The syngas used for the catalytic methanol production was produced by gasification of biomass, electrolysis of water, CO₂ from post-combustion capture and autothermal reforming of natural gas or biogas. Underground gas storage of hydrogen and oxygen was used in connection with the electrolysis to enable the electrolyser to follow the variations in the power produced by renewables. Six plant configurations, each with a different syngas production method, were compared. The plants achieve methanol exergy efficiencies of 59–72%, the best from a configuration incorporating autothermal reforming of biogas and electrolysis of water for syngas production. The different processes in the plants are highly heat integrated, and the low-temperature waste heat is used for district heat production. This results in high total energy efficiencies (∼90%) for the plants. The specific methanol costs for the six plants are in the range 11.8–25.3 €/GJ_exergy. The lowest cost is obtained by a plant using electrolysis of water, gasification of biomass and autothermal reforming of natural gas for syngas production.     

Performance analysis of a membrane‐based reformer‐combustor reactor for hydrogen generation

Hydrogen is mostly produced in conventional steam methane reforming plants. In this work, we proposed a membrane‐based reformer‐combustor reactor (MRCR) for hydrogen generation in order to improve heat recovery and overall thermal efficiency. The proposed configuration will also reduce the complexity in existing steam methane reforming (SMR) plants. The proposed MRCR comprises combustion zone, hydrogen permeate zone, and SMR zone. A computational fluid dynamics model was developed using ANSYS‐Fluent software to simulate and analyze the performance of the proposed MRCR. Results show that high hydrogen yields were observed at high reformer pressures (RPs) and low gas hourly space velocities (GHSVs). Furthermore, by increasing the steam to methane ratio and addition of excess air in the combustion side, the hydrogen yield from the MRCR decreases. This is attributed to the reduction in the effective temperature of the hydrogen membrane. High RP, low GHSV, and low steam to methane ratio that increased the hydrogen yield also decreased carbon monoxide (CO) emissions. For an increased RP from 1 to 10 bar, the CO emission decreased by about 99%. The reduction in CO emission at high RP would be attributed to the effect of water gas shift reaction in the MRCR. Results of the extensive parametric study presented in this work can be used to determine the operating conditions based on tradeoffs between hydrogen yield (mole H₂/mole CH₄), hydrogen production rate (kg of H₂/h), allowable CO emissions, and exhaust gas temperature for other applications such as gas turbine.     

Simulation of steam reforming of biogas in an industrial reformer for hydrogen production

The paper aims to investigate the steam reforming of biogas in an industrial-scale reformer for hydrogen production. A non-isothermal one dimensional reactor model has been constituted by using mass, momentum and energy balances. The model equations have been solved using MATLAB software. The developed model has been validated with the available modeling studies on industrial steam reforming of methane as well as with the those on lab-scale steam reforming of biogas. It demonstrates excellent agreement with them. Effect of change in biogas compositions on the performance of industrial steam reformer has been investigated in terms of methane conversion, yields of hydrogen and carbon monoxide, product gas compositions, reactor temperature and total pressure. For this, compositions of biogas (CH₄/CO₂ = 40/60 to 80/20), S/C ratio, reformer feed temperature and heat flux have been varied. Preferable feed conditions to the reformer are total molar feed rate of 21 kmol/h, steam to methane ratio of 4.0, temperature of 973 K and pressure of 25 bar. Under these conditions, industrial reformer fed with biogas, provides methane conversion (93.08–85.65%) and hydrogen yield (1.02–2.28), that are close to thermodynamic equilibrium condition.     

Hydrogen-rich syngas production of urea blended with biobutanol by a thermodynamic analysis

Both biobutanol and urea are the environment-friendly hydrogen carrier. This study is to compare hydrogen production between steam reforming of biobutanol and autothermal reforming of biobutanol feed using pure steam and vaporization of aqueous urea (VAU) by a thermodynamic analysis. Hydrogen-rich syngas production, carbon formation, thermal neutral temperature (TNT), and hydrogen production cost are analyzed in both steam reforming and autothermal reforming. The results show that hydrogen-rich syngas production with the use of VAU is higher than that with pure steam not only in steam reforming but also in autothermal reforming. When the VAU/butanol molar ratio is 8, and the O₂/butanol molar ratio equals 3, the reforming efficiency reaches up to 81.42%. At the same condition, the hydrogen production cost is lower than that without blending urea. Therefore, using VAU to replace pure steam in biobutanol reforming leads to benefits of increasing the hydrogen-rich syngas yield and lowering cost.     

Dry reforming of ethanol for hydrogen production: Thermodynamic investigation

Thermodynamics of ethanol reforming with carbon dioxide for hydrogen production has been studied by Gibbs free energy minimization method. The optimum conditions for hydrogen production are identified: reaction temperatures between 1200 and 1300 K and carbon dioxide-to-ethanol molar ratios of 1.2–1.3 at 0.1 MPa. Under the optimal conditions, complete conversion of ethanol, 94.75–94.86% yield of hydrogen and 96.77–97.04% yield of carbon monoxide can be achieved in the absence of carbon formation. The ethanol reforming with carbon dioxide is suitable for providing hydrogen-rich fuels for molten carbonate fuel cell and solid oxide fuel cell. The carbon-formed and carbon-free regions are found, which are useful in guiding the search for suitable catalysts for the reaction. Inert gases have a positive effect on the hydrogen and carbon monoxide yields.     

Hydrogen production by steam reforming of bio-oil/bio-ethanol mixtures in a continuous thermal-catalytic process

The feasibility of the steam reforming of bio-oil aqueous fraction and bio-ethanol mixtures has been studied in a continuous process with two in-line steps: thermal step at 300 °C (for the controlled deposition of pyrolytic lignin during the heating of the bio-oil/bio-ethanol feed) followed by steam reforming in a fluidized bed reactor on a Ni/α-Al₂O₃ catalyst. The effect of bio-ethanol content in the feed has been analyzed in both the thermal and reforming steps, and the suitable range of operating conditions (temperature and space-time) has been determined for obtaining a high and steady hydrogen yield. Higher ethanol content in the mixture feed improves the reaction indices and reduces coke deposition. Operating conditions of 700 °C and space-times higher than 0.23 g_catalyst h (g_bio-oil+EtOH)⁻¹ are suitable for attaining almost fully conversion of oxygenates (bio-oil and ethanol) and hydrogen yields above 93%, with low catalyst deactivation.     

Techno – Economic assessment of flexible decarbonized hydrogen and power co-production based on natural gas dry reforming

The need for flexible power plants could increase in the future as variable renewable energy (VRE) share will increase in the power grid. These power plants could balance the increasing strain on electricity grids by renewables. The proposed plant in this paper can adapt to these ramps in electricity demand of the power grid by maintaining a constant feed and producing also high purity hydrogen. Dry methane reforming (DMR) is incorporated into a flexible power plant model and the key performance indicators are calculated from a techno-economic perspective. The net output of the plant is 450 MW with the possibility to lower power production and produce hydrogen, maintaining a high CO₂ capture rate (72%). Two cases are compared to the base case to quantify: (i) energy and cost penalties for CO₂ capture and (ii) advantages of flexible power plant operation. The levelized cost of electricity (LCOE) for the base case is 67 Euro/MWh, the addition of a carbon capture unit increases it to 82 Euro/MWh. In the case of flexible operation, both the LCOE and levelized cost of hydrogen (LCOH) are calculated and the two depend on the cost allocation factor. The LCOE ranges from 65 to 85 Euro/MWh while the LCOH from 0.15 to 0.073 Euro/Nm³. The DMR power plant presented in Cases 1 and 2 present little advantages in today's market conditions however, the flexible plant (Case 3) can be viable option in balancing VRE.     

Natural gas usage as a heat source for integrated SMR and thermochemical hydrogen production technologies

This paper investigates various usages of natural gas (NG) as an energy source for different hydrogen production technologies. A comparison is made between the different methods of hydrogen production, based on the total amount of natural gas needed to produce a specific quantity of hydrogen, carbon dioxide emissions per mole of hydrogen produced, water requirements per mole of hydrogen produced, and a cost sensitivity analysis that takes into account the fuel cost, carbon dioxide capture cost and a carbon tax. The methods examined are the copper–chlorine (Cu–Cl) thermochemical cycle, steam methane reforming (SMR) and a modified sulfur–iodine (S–I) thermochemical cycle. Also, an integrated Cu–Cl/SMR plant is examined to show the unique advantages of modifying existing SMR plants with new hydrogen production technology. The analysis shows that the thermochemical Cu–Cl cycle out-performs the other conventional methods with respect to fuel requirements, carbon dioxide emissions and total cost of production.     

Technical assessment of cryo-compressed hydrogen storage tank systems for automotive applications

On-board and off-board performance and cost of cryo-compressed hydrogen storage are assessed and compared to the targets for automotive applications. The on-board performance of the system and high-volume manufacturing cost were determined for liquid hydrogen refueling with a single-flow nozzle and a pump that delivers liquid H₂ to the insulated cryogenic tank capable of being pressurized to 272 atm. The off-board performance and cost of delivering liquid hydrogen were determined for two scenarios in which hydrogen is produced by central steam methane reforming (SMR) or by central electrolysis. The main conclusions are that the cryo-compressed storage system has the potential of meeting the ultimate target for system gravimetric capacity, mid-term target for system volumetric capacity, and the target for hydrogen loss during dormancy under certain conditions of minimum daily driving. However, the high-volume manufacturing cost and the fuel cost for the SMR hydrogen production scenario are, respectively, 2–4 and 1.6–2.4 times the current targets, and the well-to-tank efficiency is well short of the 60% target specified for off-board regenerable materials.     

Dry reforming of methane has no future for hydrogen production: Comparison with steam reforming at high pressure in standard and membrane reactors

The methane dry-reforming and steam reforming reactions were studied as a function of pressure (1–20 atm) at 973 K in conventional packed-bed reactors and a membrane reactors. For the dry-reforming reaction in a conventional reactor the production yield of hydrogen rose and then decreased with increasing pressure as a result of the reverse water-gas shift reaction in which the hydrogen reacted with the reactant CO₂ to produce water. For the steam reforming reaction the production yield of hydrogen kept increasing with pressure because the forward water-gas shift reaction produced additional hydrogen by the reaction of CO with water. In the membrane reactors the methane conversion and the hydrogen production yields were higher for both the dry-reforming and steam reforming reactions, but for the dry reforming at high pressure half of the hydrogen was transformed into water. Thus, the dry-reforming reaction is not practical for producing hydrogen.     

Modeling study on the production of hydrogen/syngas via partial oxidation using a homogeneous charge compression ignition engine fueled with natural gas

The production of hydrogen and syngas from natural gas using a homogeneous charge compression ignition reforming engine is investigated numerically. The simulation tool used was CHEMKIN 3.7, using the GRI-3 natural gas combustion mechanism. This simulation was conducted on the changes in hydrogen and syngas concentration according to the variations of equivalence ratio, intake temperature, oxygen enrichment, engine speed, initial pressure, and fuel additives with partial oxidation combustion. The simulation results indicate that the hydrogen/syngas yields are strongly dependent on the equivalence ratio with maxima occurring at an optimal equivalence ratio varying with engine speed. The hydrogen/syngas yields increase with increasing intake temperature and oxygen contents in air. The hydrogen/syngas yields also increase with increasing initial pressure, especially at lower temperatures, yet high temperature can suppress the pressure effect. Furthermore, it was found that the hydrogen/syngas yields increase when using fuel additives, especially hydrogen peroxide. Through the parametric screening studies, optimum operating conditions for natural gas partial oxidation reforming are recommended at 3.0 equivalence ratio, 530 K intake temperature, 0.3 oxygen enrichment, 500 rpm engine speed, 1 atm initial pressure, and 7.5% hydrogen peroxide.     

Metal oxides as combustion catalysts for a stratified,dual bed partial oxidation catalyst

Bimetallic, dual bed catalysts made up of metal oxides were investigated in the millisecond catalytic partial oxidation of methane to synthesis gas. A metal oxide combustion catalyst containing manganese, chromium, or copper was coupled with a nickel reforming catalyst to carry out the partial oxidation of methane. These catalysts produce hydrogen yields that compare to a platinum/nickel dual bed catalyst at a fraction of the cost. The high space velocity of the millisecond reactor improves performance by giving high rates of heat convection from the exothermic, upstream combustion catalyst to the downstream, endothermic reforming catalyst. Additionally, over a 10 h experiment, the catalyst activity did not decrease.     

A techno-economic appraisal of hydrogen generation and the case for solid oxide electrolyser cells

There is significant interest in alternatives to fossil fuels in order to reduce carbon dioxide emissions. One option is the use of hydrogen in applications such as fuel cells. There are various routes to the production of hydrogen, one being via the electrolysis of water. Water electrolysers are already operational within industry on a small-scale, accounting for 4% of world hydrogen production. These electrolysers operate at low temperatures and require electrical power input that has been shown to be costly due to the limited efficiency of the electrolysis process. However, the use of high temperature solid oxide electrolyser cells (SOECs) has the potential to generate hydrogen with a higher electrical efficiency which may allow electrolysis to become cost competitive with steam methane reforming (SMR), depending on where the heat and electrical power to service the SOEC comes from.This paper examines the various routes to hydrogen production and, in particular electrolysis technologies. The cost of hydrogen production is examined in the context of the source of the electricity and the efficiency of the electrolysis process compared to SMR generation. It is found that to become cost competitive with SMR, the lowest cost electricity is required, sourced either from nuclear or combined cycle gas turbine plants with electrolysis efficiency as high as possible, meaning that SOEC technology is particularly attractive.     

Technical challenges for developing thermal methane cracking in small or medium scales to produce pure hydrogen - A review

Hydrogen is an important chemical commodity and plays a key role in the clean, secure and affordable energy scenarios of the future. There is a significant interest in the development of small plants for hydrogen generation besides other plants where hydrogen has been consumed as raw material and it is because of the very high cost of compression and transportation of hydrogen.Thermal methane cracking (TMC) is an alternative process for high purity hydrogen manufacturing along with the traditional commercial processes such as steam reforming, coal gasification, partial oxidation, and water electrolysis. Employing the TMC process for very high purity hydrogen production on a small or medium-scale plant with the minimum requirement of separation units is the main incentive of this review.Given the results of the review, using catalysts for TMC can decrease the working temperature to below 800 °C but it could create some significant issues, especially catalyst deactivation (a low catalyst life due to carbon deposition), so it is not yet a viable method to employ on the production plants. On the other hand, supplying the heat of reaction and reactor blockages are two basic challenges for a non-catalytic reaction way.     

Technical assessment of compressed hydrogen storage tank systems for automotive applications

The performance and cost of compressed hydrogen storage tank systems has been assessed and compared to the U.S. Department of Energy (DOE) 2010, 2015, and ultimate targets for automotive applications. The on-board performance and high-volume manufacturing cost were determined for compressed hydrogen tanks with design pressures of 350 bar (∼5000 psi) and 700 bar (∼10,000 psi) capable of storing 5.6 kg of usable hydrogen. The off-board performance and cost of delivering compressed hydrogen was determined for hydrogen produced by central steam methane reforming (SMR). The main conclusions of the assessment are that the 350-bar compressed storage system has the potential to meet the 2010 and 2015 targets for system gravimetric capacity but will not likely meet any of the system targets for volumetric capacity or cost, given our base case assumptions. The 700-bar compressed storage system has the potential to meet only the 2010 target for system gravimetric capacity and is not likely to meet any of the system targets for volumetric capacity or cost, despite the fact that its volumetric capacity is much higher than that of the 350-bar system. Both the 350-bar and 700-bar systems come close to meeting the Well-to-Tank (WTT) efficiency target, but fall short by about 5%.     

Developing an infrastructure for hydrogen vehicles: a Southern California case study

We have examined the technical feasibility and economics of developing a hydrogen vehicle refueling infrastructure for a specific area where zero emission vehicles are being considered, Southern California. Potential hydrogen demands for zero emission vehicles are estimated. We then assess in detail several near term possibilities for producing and delivering gaseous hydrogen transportation fuel including: (1) hydrogen produced from natural gas in a large, centralized steam reforming plant, and truck delivered as a liquid to refueling stations; (2) hydrogen produced in a large, centralized steam reforming plant, and delivered via small scale hydrogen gas pipeline to refueling stations; (3) by-product hydrogen from chemical industry sources; (4) hydrogen produced at the refueling station via small scale steam reforming of natural gas; and (5) hydrogen produced via small scale electrolysis at the refueling station. The capital cost of infrastructure and the delivered cost of hydrogen are estimated for each hydrogen supply option. Hydrogen is compared to other fuels for fuel cell vehicles (methanol, gasoline) in terms of vehicle cost, infrastructure cost and lifecycle cost of transportation. Finally, we discuss possible scenarios for introducing hydrogen as a fuel for fuel cell vehicles.     

Process simulation and integration of IGCC systems for H2/syngas/electricity generation with control on CO2 emissions

IGCC is a pre-combustion technology that can be effectively used to produce both hydrogen and electricity while reducing the greenhouse gas (GHG) emissions. Two process models are developed in Aspen Plus^® software and are compared techno-economically. The conventional design of IGCC process is taken as case 1, whereas, case 2 represents the conceptual design of sequential integration of reforming model with the gasification unit to enhance the syngas yield. The case 2 utilizes the steam generated in the gasification process to sustain the methane reforming process which consequently enhances both the H₂ production capacity and cold gas efficiency. It has been analyzed from results that case 2 can enhance the process performance by 4.77% and economics in terms of cost of electricity by 5.9% compared to the conventional process. However, the utilization of natural gas in the case 2 is considered as a standalone fuel so the process performance of NGCC power plants has been also incorporated to ensure the realistic analysis. The results also showed that case 2 design offers 3.9% higher process performance than the cumulative (IGCC + NGCC) processes, respectively. Moreover, the CO₂ specific emissions and LCOE for the case 2 is also lower than the case.