Techno-economic analysis (TEA) for CO2 reforming of methane in a membrane reactor for simultaneous CO2 utilization and ultra-pure H2 production

Techno-economic analysis (TEA) for CO₂ reforming of methane in a membrane reactor (MR) was conducted by using process simulation and economic analysis. Parametric studies for key operating conditions like a H₂ permeance, a H₂O sweep gas flow rate, operating temperature, and a CO₂/CH₄ ratio were carried out for a conventional packed-bed reactor (PBR) and a MR using Aspen HYSYS^®, a commercial process simulator program and some critical design guidelines for a MR in terms of a H₂O sweep gas flow rate and a CO₂/CH₄ ratio were obtained. Further economic analysis based on process simulation results showed about 42% reduction in a unit H₂ production cost in a MR (6.48 $ kgH₂^?1) than a PBR (11.18 $ kgH₂^?1) mostly due to the elimination of a pressure swing adsorption (PSA) system in a MR. In addition, sensitivity analysis (SA) revealed that reactant price and labor were the most influential economic factors to determine a unit H₂ production cost for both a PBR and a MR. Lastly, profitability analysis (PA) from cumulative cash flow diagram (CCFD) in Korea provided positive net present value (NPV) of $443,760～$240,980, discounted payback period (DPBP) of 3.03–3.18 y, and present value ratio (PVR) of 7.51–4.97 for discount rates from 2 to 10% showing economic feasibility of the use of a MR as simultaneous CO₂ utilization and ultra-pure H₂ production.     

Techno-economic and environmental assessment of methanol steam reforming for H2 production at various scales

According to global trend of transition to a hydrogen society, needs for alternative hydrogen (H₂) production methods have been on the rise. Among them, methanol steam reforming (MSR) in a membrane reactor (MR) has received a great attention due to its improved H₂ yield and compact design. In this study, 3 types of economic analysis – itemized cost estimation, sensitivity analysis, and uncertainty analysis – and integrative carbon footprint analysis (iCFA) were carried out to investigate economic and environmental feasibility. Unit H₂ production costs of MSR in a packed-bed reactor (PBR) and an MR for various H₂ production capacities of 30, 100, 300, and 700 m³ h⁻¹ and CO₂ emission rates for both a PBR and an MR in H₂ production capacity of 30 m³ h⁻¹ were estimated. Through itemized cost estimation, unit H₂ production costs of a PBR and an MR were obtained and scenario analysis was carried out to find a minimum H₂ production cost. Sensitivity analysis was employed to identify key economic factors. In addition, comprehensive uncertainty analysis reflecting unpredictable fluctuation of key economic factors of reactant, labor, and natural gas obtained from sensitivity analysis was also performed for a PBR and an MR by varying them both simultaneously and individually. Through iCFA, lowered CO₂ emission rates were obtained showing environmental benefit of MSR in an MR.     

Vehicle refueling with liquid hydrogen thermal compression

We have modeled an approach for dispensing pressurized hydrogen to 350 and/or 700 bar vehicle vessels. Instead of relying on compressors, this concept stores liquid hydrogen in cryogenic pressure vessels where pressurization occurs through heat transfer, reducing the station energy footprint from 12 kW h/kgH₂ of energy from the US grid mix to 1.5–2 kW h/kgH₂ of heating. This thermal compression station presents capital cost and reliability advantages by avoiding the expense and maintenance of high-pressure hydrogen compressors, at the detriment of some evaporative losses. The total installed capital cost for a 475 kg/day thermal compression hydrogen refueling station is estimated at about $611,500, an almost 60% cost reduction over today's refueling station cost. The cost for 700 bar dispensing is $5.23/kg H₂ for a conventional station vs. $5.45/kg H₂ for a thermal compression station. If there is a demand for 350 bar H₂ in addition to 700 bar dispensing, the cost of dispensing from a thermal compression station drops to $4.81/kg H₂, which is similar to the cost of a conventional station that dispenses 350 bar H₂ only. Thermal compression also offers capacity flexibility (wide range of pressure, temperature, and station demand) that makes it appealing for early market applications.     

ZnO nanofiber skeleton induced robust zeolitic imidazolate framework membranes for gas separation

Rationally designing compact metal-organic framework (MOF) membrane is highly desired but challenging. Herein, we proposed a ZnO nanofiber skeleton induced zeolitic imidazolate framework (ZIF) membrane inspired by the reinforced concrete structure. In this process, the ZnO nanofiber skeleton was employed as active anchor sites to assist the heteroepitaxial growth of continuous membranes, like the reinforcing steel in structure. The formed ZIFs particles were tightly embedded in the skeleton like the concrete. With this approach, highly compact Co-based ZIF-9 membrane and Zn-based ZIF-8 membrane were successfully achieved and exhibit effective H₂ separation performance. For ZIF-9 membrane, the H₂ permeance and the ideal selectivity of H₂/CO₂ are 2.19 × 10⁻⁷ mol m⁻² s⁻¹ Pa⁻¹ and 15.3, respectively. For ZIF-8 membrane, the H₂ permeance and the ideal selectivity of H₂/CH₄ are 2.26 × 10⁻⁶ mol m⁻² s⁻¹ Pa⁻¹ and 9.7, respectively. More importantly, benefiting from the novel structure, the membrane showed a highly robust architecture under different pressures, good durability against rubbing, and separation stability of 100 h. This strategy provides a new approach toward other compact and robust MOF membrane.     

Bioethanol steam reforming over monoliths washcoated with RhPt/CeO2–SiO2: The use of residual biomass to stably produce syngas

Ethanol steam reforming of synthetic bioethanol (i.e., anhydrous ethanol plus water), as well as bioethanol obtained from glucose standards and sugarcane press-mud was evaluated on monoliths washcoated with RhPt/CeO₂–SiO₂. Tests with synthetic bioethanol indicated that the lower pressure drop favors higher ethanol conversion in the monoliths with respect to the powder samples. Also, two monoliths in series with 0.08 g_cat/cm³ improved H₂ yield compared to just one monolith with 0.16 g_cat/cm³. Similarly, a decrease in the amount of carrier gas contributes to diffusion limitations in the monoliths, reducing the H₂/CO ratio. Monoliths stability was also evaluated with “real” bioethanol samples (from glucose standards and sugarcane press-mud-SPM). In all cases, a syngas with >60% of H₂ was produced. For SPM-bioethanol, 3.1 ± 0.2 mol H₂/mol EtOH were obtained without evidence of deactivation for 120 h, at a cost of 6.9 $/kgH₂, becoming a promising way to develop a technology for sustainable energy production.     

Sustainable hydrogen production: Technological advancements and economic analysis

Hydrogen (H₂) is pivotal to phasing out fossil fuel-based energy systems. It can be produced from different sources and using different technologies. Very few studies comprehensively discuss all available state-of-the-art technologies for H₂ production, the challenges facing each process, and their economic feasibility and sustainability. The current study thus addresses these gaps to effectively direct future research towards improving H₂ production techniques. Many conventional methods contribute to large greenhouse gas footprints, with high production costs and low efficiency. Steam methane reforming and coal gasification dominate the supply side of H₂, due to their low production costs (<$3.50/kg). Water-splitting offers one of the most environmentally benign production methods when integrated with renewable energy sources. However, it is considerably expensive and ridden with the flaw of production of harmful by-products that affect efficiency. Fossil fuel processing technologies remain one of the most efficient forms of H₂ production sources, with yields exceeding 80% and reaching up to 100%, with the lowest cost despite their high reliance on expensive catalysts. Whereas solar-driven power systems cost slightly less than $10 kg^?1, coal gasification and steam reforming cost below $3.05 kg^?1. Future research thus needs to be directed towards cost reduction of renewable energy-based H₂ production systems, as well as in their decarbonization and designing more robust H₂ storage systems that are compatible with long-distance distribution networks with adequate fuelling stations.     

Cost analysis of wind-electrolyzer-fuel cell system for energy demand in Pınarbaşı-Kayseri

In this study, the hydrogen production potential and costs by using wind/electrolysis system in P?narba??-Kayseri were considered. In order to evaluate costs and quantities of produced hydrogen, for three different hub heights (50 m, 80 m and 100 m) and two different electrolyzer cases, such as one electrolyzer with rated power of 120 kW (Case-I) and three electrolyzers with rated power of 40 kW (Case-II) were investigated. Levelised cost of electricity method was used in order to determine the cost analysis of wind energy and hydrogen production. The results of calculations brought out that the electricity costs of the wind turbines and hydrogen production costs of the electrolyzers are decreased with the increase of turbine hub height. The maximum hydrogen production quantity was obtained 14192 kgH₂/year and minimum hydrogen cost was obtained 8.5 $/kgH₂ at 100 m hub height in the Case-II.     

Development of a H2-permeable Pd60Cu40-based composite membrane using a reverse build-up method

A new reverse build-up method is developed to fabricate an economical H₂-permeable composite membrane. Sputtering and electroplating are used for the formation of a membrane comprised of a 3.7-μm-thick Pd₆₀Cu₄₀ (wt.%) alloy layer and a 13-μm-thick porous Ni support layer, respectively. The H₂-permeation measurements are performed under the flow of a gaseous mixture of H₂ and He at 300–320 °C and 50–100 kPa of H₂ partial pressure. The H₂/He selectivity values exceed 300. The activation energy at 300–320 °C is 10.9 kJ mol⁻¹. The H₂ permeability of the membrane is 1.25 × 10⁻⁸ mol m⁻¹ s⁻¹ Pa^−0.5 at 320 °C after 448 h. The estimated Pd cost of the proposed membrane is approximately 1/8 of the cost for a pure Pd₆₀Cu₄₀ membrane. This study demonstrates that the proposed method allows the facile production of low-cost, Pd-based membranes for H₂ separation.     

Improved hydrogen production of the downstream bioreactor by coupling single chamber microbial fuel cells between series-connected photosynthetic biohydrogen reactors

To obtain additional hydrogen recovery from the downstream photosynthetic biohydrogen reactor (PBR), a system (PBR1–MFCs–PBR2) that combined PBRs with three single chamber microbial fuel cells (MFCs) was proposed in this study. The results revealed that the PBR2 in PBR1–MFCs–PBR2 showed a hydrogen production rate of 0.44 ± 0.22 mmol L h⁻¹, which was 15 and 4 times higher than those obtained by direct connecting the two PBRs (PBR1–PBR2) and pH regulated system (PBR1–pH regulation–PBR2), respectively. In addition, the PBR1–MFCs–PBR2 exhibited the highest glucose utilization (η_g) of 97.6 ± 2.1 %, while lower η_g values of 75.6 ± 2.2% and 70.1 ± 1.2% was obtained for PBR1–PBR2 and PBR1–pH regulation–PBR2, respectively. These improvements were due to the removal of inhibitory byproduct and H⁺ from the PBR1 effluent by the MFCs.     

In2S3/AgIO3 photoanode coupled I−/I3− cyclic redox system for solar-electrocatalytic recovery of H2 and S from toxic H2S

The abundant availability of toxic H₂S in many industrial and natural resources and its low thermodynamic decomposition makes it a viable economic source for the production of environmentally clean fuel (H₂). Here, a highly efficient In₂S₃/AgIO₃ photoanode and Pt/C–based waterproofed carbon fibre cathode were prepared for the recovery of H₂ and S from toxic H₂S in a cyclic redox system of I⁻/I₃⁻. The H₂S was oxidized to S by I₃⁻ in the photoanode compartment and H⁺ was efficiently reduced to H₂ in the photocathode region. A maximum H₂ and S production rate of ∼0.26 mmol h⁻¹ cm⁻² and ∼0.23 mmol h⁻¹ cm⁻² were achieved, respectively and the photocurrent density of ∼0.9 mA cm⁻² was attained during the entire operation. The In₂S₃/AgIO₃ photoanode exhibited high energy conversion efficiency and polysulfides were not detected after the reaction, suggesting that the toxic H₂S was completely converted into H₂ and S. The proposed system with I⁻/I₃⁻ redox provides an energy-sustaining method for simultaneous treatment of toxic H₂S and clean fuel production.     

Ozonation aided mesophilic biohydrogen production from palm oil mill effluent

Ozone pretreatment of palm oil mill effluent (POME) was employed to improve sustrate biodegradability prior to biological H₂ production. The H₂ production was conducted at varing pHs from 4.0 to 6.0 to examine the impact of pH on the H₂ mesophilic production (37 °C). The optimal pH for H₂ production was 6.0 for both raw and ozonated POME. The POME concentrations were greatly influenced the yields and rates of H₂ production. At the optimal pH, the maximum H₂ production yield of 182 ± 7.2 mL.g⁻¹ COD (7.96 mmoL.g⁻¹ COD) was achieved at the ozonated POME concentration of 30,000 mg COD.L⁻¹. The maximum H₂ production rate (R_max) of 43.1 ± 2.5 mL.h⁻¹ was obtained at the ozonated POME concentration of 25,000 mg COD.L⁻¹. The highest total COD removal was 44% at of 15,000 mg COD.L⁻¹ ozonated POME. Acetic and butyric acids were dominant products during H₂ fermentation and tended to increase with the increased POME concentrations. Ozonation as a pretreatment process showed significant enhancement of the POME biodegradability , and subsequently improved the H₂ production H₂.     

Parametric study of membrane reactors for hydrogen production via high-temperature water gas shift reaction

This study presents numerical studies of hydrogen production performance via water gas shift reaction in membrane reactor. The pre-exponential factor in describing the hydrogen permeation flux is used as the main parameter to account for the membrane permeance variation. The operating pressure, temperature and H₂O/CO molar ratio are chosen in the 1–20 atm, 400–600 °C and 1–3 ranges, respectively. Based on the numerical simulation results three distinct CO conversion regimes exist based on the pre-exponential factor value. For low pre-exponential factors corresponding to low membrane permeance, the CO conversion approaches to that obtained from a conventional reactor without hydrogen removal. For high pre-exponential factor, high CO conversion and H₂ recovery with constant values can be obtained. For intermediate pre-exponential factor range both CO conversion and H₂ recovery vary linearly with the pre-exponential factor. In the high membrane permeation case CO conversion and H₂ recovery approach limiting values as the operating pressure increases. Increasing the H₂O/CO molar ratio results in an increase in CO conversion but decrease in H₂ recovery due to hydrogen permeation driving force reduction. As the feed rate increases in the reaction side both the CO conversion and hydrogen recovery decrease because of decreased reactant residence time. The sweep gas flow rate has a significant effect on hydrogen recovery. Low sweep gas flow rate results in low CO conversion H₂ recovery while limiting CO conversion and hydrogen recovery can be reached for the high membrane permeance and high sweep gas flow rate cases.     

A technoeconomic analysis of centralised and distributed processes of ammonia dissociation to hydrogen for fuel cell vehicle applications

Ammonia (NH₃) has been proposed as a hydrogen (H₂) carrier for energy services in the carbon-constrained future. This paper presents a technoeconomic feasibility study of using NH₃ as H₂ carrier for fuel cell vehicles (FCVs) applications. Two cases with different scales of anticipated operations: (1) centralised installation (1000 tonnes day⁻¹) and (2) distributed refuelling station (500 kg day⁻¹), were considered. Aspen HYSYS v8.6 was utilised to simulate the processes. The H₂ production cost, internal rate of return, payback period and net present value were examined and compared. The results indicate the centralised H₂ production is both technically and economically feasible while distributed H₂ production, falling foul of economy of scale, is not economically viable. The overall H₂ production cost of the centralised H₂ production can reach as low as USD 5.50 kg⁻¹ H₂ accounting for capital expenditure, operating expenses, and decommissioning costs. The sensitivity analysis shown that the overall H₂ production cost is highly sensitive to NH₃ price and moderately affected by utility price and various corporate tax rates considered.     

Pd-thickness reduction in electroless pore-plated membranes by using doped-ceria as interlayer

This work presents the use of doped CeO₂ particles with palladium as intermediate barrier for the preparation of fully dense Pd films by Electroless Pore-Plating. The use of doped ceria particles instead of non-doped ones clearly helps to reduce the final palladium thickness required to prepare a fully dense membrane over porous stainless steel supports from 15 to 9 μm (average values by gravimetric analyses), thus saving around 40% of total palladium required in the process. Pure hydrogen permeation tests reveal a consequent increase in the H₂ flux in the range 15–30%, depending on the operation mode. Thus, a H₂ permeance of 6.26·10⁻⁴ mol m⁻² s⁻¹ Pa^−0.5 at 400 °C and ΔP = 1 bar is reached, maintaining a really high H₂/N₂ ideal separation factor (≥10,000) and an activation energy within the typical range for these type of membranes, E_a = 13.1 kJ mol⁻¹. Permeation of binary H₂/N₂ gas mixtures and the effect of feeding the mixture from the inner or the outer side of the membrane have been also studied. A significant concentration-polarization effect was observed, being higher when the gas is fed from the inner to the outer side of the membrane. This effect becomes more relevant for the membrane prepared with doped CeO₂, instead of raw CeO₂, due to its lower Pd thickness and higher relative influence of the surface processes. However, it should be emphasized that higher H₂ permeance values were obtained for the entire set of experiments when using the Pd-membranes containing doped ceria. Finally, long-term permeation tests for more than 850 h with pure gases at T = 400 °C and ΔP = 1 bar were also carried out, demonstrating a suitable mechanical stability of membranes at these operating conditions.     

Comparative kinetic modeling of growth and molecular hydrogen overproduction by engineered strains of Thermotoga maritima

Thermotoga maritima is an anaerobic hyperthermophilic bacterium known for its high amounts of hydrogen (H₂) production. In the current study, the kinetic modeling was applied on the engineered strains of T. maritima that surpassed the natural H₂ production limit. The study generated a kinetic model explaining H₂ overproduction and predicted a continuous fermentation system. A Leudking-Piret equation-based model predicted that H₂ production by Tma200 (0.217 mol-H₂ g⁻¹-biomass) and Tma100 (0.147 mol-H₂ g⁻¹-biomass) were higher than wild type (0.096 mol-H₂ g⁻¹ -biomass) with reduced rates of maltose utilization. Sensitivity analysis confirmed satisfactory fitting of the experimental data. The slow growth rates of Tma200 (0.550 h⁻¹) and Tma100 (0.495 h⁻¹) are compared with the wild type (0.663 h⁻¹). A higher maintenance energy along with growth and non-growth H₂ coefficients corroborate the higher H₂ productivity of the engineered strains. The modeled data established a continuous fermentation system for the sustainable H₂ production.     

Cost‐competitive methane steam reforming in a membrane reactor for H2 production: Technical and economic evaluation with a window of a H2 selectivity

Techno‐economic viability studies of employing a membrane reactor (MR) equipped with H₂ separation membranes for methane steam reforming (MSR) were carried out for H₂ production in Korea using HYSYS®, a well‐known chemical process simulator, including economic analysis based on itemized cost estimation and sensitivity analysis (SA). With the reaction kinetics for MSR reported by Xu and Froment, the effect of a wide range of H₂ selectivity (10‐10,000) on the performance in an MR was investigated in this study. Because of the equilibrium shift owing to the Le Chatelier's principle, great performance of enhancement of methane conversion ( ) and H₂ yield and reaction temperature reduction was observed in an MR compared with a packed‐bed reactor (PBR). A window of a H₂ selectivity from 100 to 300 is proposed as a new criterion for better MR performance of MSR depending on potential applications from in‐depth analysis of and H₂ yield enhancements, a H₂ purity, and temperature reduction. In addition, economic analysis to evaluate the feasibility of an MR technology for MSR was carried out focusing on a levelized cost of H₂ based on itemized cost estimation of capital and operating costs as well as SA. Techno‐economic assessment showed 36.7% cost reduction in an MR compared with a PBR and revealed that this MR technology can be possibly opted for a cost‐competitive H₂ production process for MSR.     

Optimization of dilute acid and enzymatic hydrolysis for dark fermentative hydrogen production from the empty fruit bunch of oil palm

Pretreatment of the empty fruit brunch (EFB) from oil palm was investigated for H₂ fermentation. The EFB was hydrolyzed at various temperatures, H₂SO₄ concentrations, and reaction times. Subsequently, the acid-hydrolysate underwent enzymatic saccharification under various temperature, pH, and enzymatic loading conditions. Response surface methodology derived the optimum sugar concentration (SC), hydrogen production rate (HPR), and hydrogen yield (HY) as 28.30 g L⁻¹, 2601.24 mL H₂ L⁻¹d⁻¹, and 275.75 mL H₂ g⁻¹ total sugar (TS), respectively, at 120 °C, 60 min of reaction, and 6 vol% H₂SO₄, with the combined severity factor of 1.75. Enzymatic hydrolysis enhanced the SC, HY, and HPR to 34.52 g L⁻¹, 283.91 mL H₂ g⁻¹ TS, and 3266.86 mL H₂ L⁻¹d⁻¹, respectively, at 45 °C, pH 5.0, and 1.17 mg enzyme mL⁻¹. Dilute acid hydrolysis would be a viable pretreatment for biohydrogen production from EFB. Subsequent enzymatic hydrolysis can be performed if enhanced HPR is required.     

Techno-economic assessment of pellets produced from steam pretreated biomass feedstock

Minimum production cost and optimum plant size are determined for pellet plants for three types of biomass feedstock – forest residue, agricultural residue, and energy crops. The life cycle cost from harvesting to the delivery of the pellets to the co-firing facility is evaluated. The cost varies from 95 to 105 $ t⁻¹ for regular pellets and 146–156 $ t⁻¹ for steam pretreated pellets. The difference in the cost of producing regular and steam pretreated pellets per unit energy is in the range of 2–3 $ GJ⁻¹. The economic optimum plant size (i.e., the size at which pellet production cost is minimum) is found to be 190 kt for regular pellet production and 250 kt for steam pretreated pellet. Sensitivity and uncertainty analyses were carried out to identify sensitivity parameters and effects of model error.     

Optimization of biohydrogen production of palm oil mill effluent by ozone pretreatment

The biohydrogen (H₂) production in batch experiments under varying concentrations of raw and ozonated palm oil mill effluent (POME) of 5000–30,000 mg COD.L⁻¹, at initial pH 6, under mesophilic (37 °C), thermophilic (55 °C) and extreme-thermophilic (70 °C) conditions. Effects of ozone pretreatment, substrate concentration and fermentation temperature on H₂ production using mesophilic seed sludge was undertaken. The results demonstrated that H₂ can be produced from both raw and ozonated POME, and the amounts of H₂ production were directly increased as the POME concentrations were increased. H₂ was successfully produced under the mesophilic fermentation of ozonated POME, with maximum H₂ yield, and specific H₂ production rate of 182 mL.g⁻¹ COD_removed (30,000 mg COD.L⁻¹) and 6.2 mL.h⁻¹.g⁻¹ TVS (25,000 mg COD.L⁻¹), respectively. Thus, indicating that the ozone pretreatment could elevate on the biodegradability of major constituents of the POME, which significantly enhanced yields and rates of the H₂ production. H₂ production was not achieved under the thermophilic and extreme-thermophilic fermentation. In both fermentation temperatures with ozonated POME, the maximum H₂ yield was 62 mL.g⁻¹ COD_removed (30,000 mg COD.L⁻¹) and 63 mL.g⁻¹ COD_removed (30,000 mg COD.L⁻¹), respectively. The highest efficiency of total and soluble COD removal was obtained at 44 and 37%, respectively following the mesophilic fermentation, of 24 and 25%, respectively under the thermophilic fermentation, of 32 and 20%, respectively under the extreme-thermophilic fermentation. The production of volatile fatty acids increased with an increased fermentation time and temperature in both raw and ozonated POME under all three fermentation temperatures. The accumulation of volatile fatty acids in the reactor content were mostly acetic and butyric acids. H₂ fermentation under the mesophilic condition of 37 °C was the better selection than that of the thermophilic and extreme-thermophilic fermentation.     

A CFD study on H2-permeable membrane reactor for methane CO2 reforming: Effect of catalyst bed volume

A 2D axisymmetric model is developed for a H₂-permeable membrane reactor for methane CO₂ reforming. The effect of catalyst bed volume on CH₄ conversion and H₂ permeation rate is investigated. The simulation results indicate that catalyst bed volume with a shell radius of 9 mm is optimal for a tubular Vycor glass membrane with a diameter of 10 mm and H₂ permeance of 2x10⁻⁶ mol/m²/Pa/s. The concentration polarization at the retentate side and the accumulation of H₂ at permeate side make it hard to extract the H₂ production at the zone far from the membrane surface. Though increasing pressure at the retentate side enhances H₂ permeation, CH₄ conversion is even decreased due to unfavorable thermodynamics. And increasing sweep gas flow rate at permeate side benefits to both CH₄ conversion and H₂ permeation. This work highlights the importance of determining the optimal catalyst bed volume to match the membrane in the design of membrane reactors.