Steam Reforming Research Articles

Assessment of the polygeneration approach in wastewater treatment plants for enhanced energy efficiency and green hydrogen/ammonia production

Wastewater treatment plants (WWTPs) offer opportunities to optimize resource utilization and enhance energy efficiency. This study provides a comprehensive analysis of using the polygeneration approach in WWTPs to reduce grid energy dependence, optimize energy distribution, and utilize surplus energy for hydrogen (H2) and ammonia (NH3) production. Several models were employed, including photovoltaic (PV) cells, parabolic trough collectors (PTCs), steam methane reforming, and polymer electrolyte membranes, to assess the feasibility of this approach. Three scenarios were evaluated and compared: Scenario 1 (Baseline) represents the current situation, Scenario 2 maximizes the Net Present Value (NPV), and Scenario 3 minimizes NH3 production costs. Real data from As-Samra WWTP in Jordan was used to accurately assess the feasibility of each scenario. The results show that Scenario 2 offers the highest profitability and efficiency, with a NPV of 87.48 million USD and an annual NH3 production of 15,417 tons, reducing both grid dependency and biogas fuel consumption. Both Scenarios 2 and 3 demonstrate the ability to meet thermal demands efficiently while generating significant revenue from NH3 production. Scenario 3, in particular, achieves competitive H2 and NH3 production costs. Environmentally, Scenario 2 significantly reduces annual greenhouse gas emissions by 12.66 kilotons of CO2eq, with near-zero carbon intensity for thermal energy due to solar reliance. In conclusion, the polygeneration approach offers a promising pathway for WWTPs to achieve greater sustainability, economic gains, and reduced environmental impact, providing valuable insights for decision-makers.

Catalytic enhancement of water gas shift reaction with Cu/ZnO/ZSM-5: Overcoming challenges of CO2 and H2 rich feeds

Water gas shift (WGS) reaction commonly converts CO to CO2 using H2O and produces H2 and CO2 in a catalytic fixed bed reactor. This study aims to develop a Cu/ZnO/ZSM-5 catalyst loaded in water gas shift reactor for converting typical synthesis gas produced from dry reforming of methane (DRM) at medium temperature shift (MTS, 200–350 oC) conditions and for preventing reverse reaction due to high feed concentrations of CO2 and H2. The Cu/ZnO/ZSM-5 catalyst was prepared by impregnation method with lower Cu metal loading of 5, 10, and 15 wt%, respectively, compared to commercial catalysts. The synthesized catalyst was characterized using XRF, XRD, SEM, H2-TPR, NH3-TPD, and TGA. The catalyst activity and stability for the WGS reaction were tested in the fixed bed reactor at atmospheric pressure and temperature of 325 °C. The experimental results show that CO conversion increases with increasing Cu loading. The 15 wt% Cu/ZnO/ZSM-5 catalyst showed the best results with a CO conversion of 35% and a yield of H2 of 36% and showed good stability for 32 h. Based on the TGA, the 15 wt% Cu/ZnO/ZSM-5 catalyst forms a 0.04 g carbon/g catalyst, which is much lower when compared to commercial catalyst (0.105 g carbon/g catalyst). The relative activity of the synthesized catalyst indicates 2.4 times better when compared to commercial catalysts. High concentrations of H2 and CO2 in the feed may initiate side reactions, including reverse WGS, methanation, and carbon formation, which will decrease H2 yield.

Thermodynamic analysis of a novel compressed carbon dioxide energy storage coupled dry methane reforming system with integrated carbon capture

Chemical absorption CO2 capture, compressed carbon dioxide energy storage (CCES) and dry reforming of methane (DRM) can be used for continuous carbon capture, storage and utilization. However, CO2 capture is often accompanied by significant energy consumption. Considering the waste high-grade thermal energy at the exit of solar methane reforming, the article proposes a coupled system in which the thermal energy at the exit of the DRM system is used in CCES to improve the system's work capacity, and the remaining heat and the compression heat of the CCES are used for CO2 capture. The study established mathematical models of the three subsystems, performed thermodynamic analyses, and completed experiments on dry reforming of methane. The results show that the coupled system can increase the electro-electric conversion efficiency by 150.49 % reaching 220.33 % and the energy efficiency by 7.25 % reaching 77.09 %. The coupled system can save up to 43.33 % of CO2 capture heat. The DRM subsystem can utilize the higher temperature CO2 in the tail end of the CCES system, and its methane conversion efficiency and solar-fuel efficiency can be increased by 3.54 % and 3.20 % respectively to reach 58.22 % and 61.02 %. And the economic analysis found that the coupled system has better economics.

Design and Optimization of a Chemical Looping Hydrogen Production System Using Steam Reforming for Petrochemical Plants

Design and Optimization of a Chemical Looping Hydrogen Production System Using Steam Reforming for Petrochemical Plants

Thermodynamic evaluation of a Ca-Cu looping post-combustion CO2 capture system integrated with thermochemical recuperation based on steam methane reforming

The calcium looping integrated with the chemical looping combustion (CaL-CLC) process is an efficient and cost-effective CO2 capture technology that avoids the energy-intensive air separation unit in the calcium looping (CaL) process. However, in these CaL-CLC and CaL system integration schemes, the carbonation heat is utilized for steam generation, resulting a significant temperature difference and considerable irreversible loss. To prevent temperature mismatch, this paper proposes a novel Ca-Cu looping post-combustion CO2 capture method with thermochemical recuperation based on steam methane reforming. Additionally, a novel system integrated with turbine exhaust heat recovery is introduced to effectively reduce carbon emissions from flue gas. Results show that the proposed system has superior performance compared to the reference system based on the Ca-Cu looping method. The specific primary energy consumption for CO2 avoidance decreased from 2.40 MJLHV/kg CO2 in the reference system to 2.02 MJLHV/kg CO2. Exergy analysis indicates that a total of 3.0 % reduction in exergy destruction can be achieved in chemical reaction processes and heat recovery processes, contributing to the superior performance of the proposed system. Furthermore, the effects of key operating parameters indicate that cascaded turbine exhaust recovery is essential for improving the thermodynamic efficiency of the proposed system. Overall, recovering the mid-temperature carbonation heat via thermochemical regeneration and integrating with exhaust heat recovery contribute to reducing SPECCA, thus providing a promising low-energy-consumption alternative for CO2 capture.

Kinetic Characterization of Pt/Al2O3 Catalyst for Hydrogen Production via Methanol Aqueous-Phase Reforming

Compared to steam reforming, methanol aqueous-phase reforming (APR) converts methanol to hydrogen and carbon dioxide at lower temperatures, but also displays lower conversion rates. Herein, methanol APR is studied over the active Pt/Al2O3 catalyst under different operating conditions. Studies were conducted at different temperatures, pressures, methanol mass fractions, and residence times. APR performance was evaluated in terms of methanol conversion, hydrogen production rate, hydrogen selectivity, and by-product formation. The results revealed that an increase in operating pressure and methanol mass fraction had an adverse effect on the APR performance. Conversely, it was found that hydrogen selectivity was unaffected by the operating pressure and residence time for the methanol feed mass fraction of 5%. For the methanol feed mass fraction of 55%, hydrogen selectivity was improved by operating pressure and residence time. The alumina support phase change to boehmite as well as sintering and leaching of the catalytic particles were observed during catalyst stability experiments. Additionally, a comparison between methanol steam reforming (MSR) and APR was also performed.

Comparative Hydrogen Production Routes via Steam Methane Reforming and Chemical Looping Reforming of Natural Gas as Feedstock

Hydrogen production is essential in the transition to sustainable energy. This study examines two hydrogen production routes, steam methane reforming (SMR) and chemical looping reforming (CLR), both using raw natural gas as feedstock. SMR, the most commonly used industrial process, involves reacting methane with steam to produce hydrogen, carbon monoxide, and carbon dioxide. In contrast, CLR uses a metal oxide as an oxygen carrier to facilitate hydrogen production without generating additional carbon dioxide. Simulations conducted using Aspen HYSYS analyzed each method’s performance and energy consumption. The results show that SMR achieved 99.98% hydrogen purity, whereas CLR produced 99.97% purity. An energy analysis revealed that CLR requires 31% less energy than SMR, likely due to the absence of low- and high-temperature water–gas shift units. Overall, the findings suggest that CLR offers substantial advantages over SMR, including lower energy consumption and the production of cleaner hydrogen, free from carbon dioxide generated during the water–gas shift process.

Modeling and Numerical Investigations of Flowing N-Decane Partial Catalytic Steam Reforming at Supercritical Pressure

Steam reforming is an effective method for improving heat sinks of hypersonic aircraft at high flight Mach numbers. However, unlike the industrial process of producing hydrogen with a high water content, the catalytic steam reforming mechanism for the regeneration cooling process of hydrocarbon fuels with a water content below 30% is still unclear. Catalytic steam reforming (CSR) and catalytic thermal cracking (CTC) reactions occur at low temperatures, with the main products being hydrogen and carbon oxides. Thermal cracking (TC) reactions occur at high temperatures, with the main products being alkanes and alkenes. The above reaction exists simultaneously in the regeneration cooling channel, which is referred to as partial catalytic steam reforming (PCSR). Based on the experimental measurement results, an improved neural network correction method was used to establish a four-step global reaction model for the PCSR of n-decane under low water conditions. The reliability of the four-step model was verified by combining the model with a numerical simulation program and comparing it with the experimental results obtained by electric heating hydrocarbon fuels with a pressure of 3 MPa and a water content of 5/10/15%. The experimental and predicted results using the developed kinetic model are consistent with an error of less than 5% in the decane conversion rate. The average absolute error between the fuel outlet temperature and total heat sink is less than 10%. Using the PCSR model to predict the heat transfer characteristics of mixed fuels with different water contents, the convective heat transfer coefficient is basically the same, and the Nu number is affected by the thermal conductivity coefficient, showing different patterns with changes in the water content.

Favorable formation of needle-shaped NiAl2O4 phase over macroporous Ni/CexZr1-xO2–Al2O3 catalysts in one-pot preparation and coke-resistant catalytic performance in dry reforming of methane

In this study, we report the formation of needle-shaped NiAl2O4 via favorable interactions between Ni and Al species over macroporous Ni/CexZr1-xO2–Al2O3 catalysts for dry reforming of methane (DRM) and its remarkable improvement in the catalytic performance. The macroporous catalysts prepared by a one-pot (OP) method promote a favorable interaction between Ni and Al species that results in the formation of unique needle-shaped NiAl2O4 due to easy access to each other compared with that by incipient wetness impregnation. The NiAl2O4 phase in the calcined catalysts transforms into highly dispersed Ni and defective Al2O3 via the Ni exsolution in the reduction step. The presence of oxygen vacancies near Ni0 species facilitates the CO2 activation and enhances the catalyst stability over DRM. The optimized distribution of active sites with abundant defects over macroporous Ni/CexZr1-xO2-Al2O3 catalysts (OP) result in high conversions of CH4 and CO2 and a low coking rate in DRM.

Physical and chemical characteristics and activity of nickel-modified cobalt-iron-containing catalysts in the reaction of dry reforming of methane

In the process of dry reforming of methane (DRM), the activity of low-percentage catalysts based on cobalt and iron oxides and their modification with nickel oxide was studied. It has been established that the addition of nickel oxide into the Fe2O3/γ-Al2O3 catalyst increases the degree of methane conversion from 14 to 89%, and also increases the yield of target reaction products H2 to 43.0 vol.%, CO to 46.1 vol.% at 850 °C. On a Co3О4-NiО/γ-Al2O3 catalyst at 850 °C, methane conversion reaches to 88.1%, the yield of H2 and CO is 44.8%. TPR-H2 analyzes showed that the introduction of nickel oxide into Fe2O3/γ-Al2O3 composition, in contrast to the Co3O4/γ-Al2O3 catalyst, the temperature peaks of Fe2O3-NiО/γ-Al2O3, reduction shift towards lower temperatures and weaken the interaction of metals with the support - γ-Al2O3 and thereby the amount of active reduced particles of iron and nickel oxides increases, which ensures good catalytic activity of Fe2O3-NiО/γ-Al2O3. According to the XRD results, spinel-like form - NiFe2O4, NiAl2O4 and CoAl2O4, also phase as Fe2O3 were obtained on the Fe2O3-NiО/γ-Al2O3 catalyst. This indicates that the developed catalysts form new phases that are active at high temperatures to produce synthesis gas in reduction-oxidation processes during the DRM reaction.

Dry Reforming of Methane (DRM) over Hydrotalcite-Based Ni-Ga/(Mg, Al)Ox Catalysts: Tailoring Ga Content for Improved Stability

Dry reforming of methane (DRM) is a promising way to convert methane and carbon dioxide into syngas, which can be further utilized to synthesize value-added chemicals. One of the main challenges for the DRM process is finding catalysts that are highly active and stable. This study explores the potential use of Ni-based catalysts modified by Ga. Different Ni-Ga/(Mg, Al)Ox catalysts, with various Ga/Ni molar ratios (0, 0.1, 0.3, 0.5, and 1), were synthesized by the co-precipitation method. The catalysts were tested for the DRM reaction to evaluate their activity and stability. The Ni/(Mg, Al)Ox and its Ga-modified Ni-Ga/(Mg, Al)Ox were characterized by N2 adsorption–desorption, Fourier Transform Infrared Spectroscopy (FTIR), H2-temperature-programmed reduction (TPR), X-ray diffraction (XRD), thermogravimetric analysis (TGA) and Raman techniques. The test of catalytic activity, at 700 °C, 1 atm, GHSV of 42,000 mL/h/g, and a CH4: CO2 ratio of 1, revealed that Ga incorporation effectively enhanced the catalyst stability. Particularly, the Ni-Ga/(Mg, Al)Ox catalyst with Ga/Ni ratio of 0.3 exhibited the best catalytic performance, with CH4 and CO2 conversions of 66% and 74%, respectively, and an H2/CO ratio of 0.92. Furthermore, the CH4 and CO2 conversions increased from 34% and 46%, respectively, when testing at 600 °C, to 94% and 96% when the catalytic activity was operated at 850 °C. The best catalyst’s 20 h stream performance demonstrated its great stability. DFT analysis revealed an alteration in the electronic properties of nickel upon Ga incorporation, the d-band center of the Ga modified catalyst (Ga/Ni ratio of 0.3) shifted closer to the Fermi level, and a charge transfer from Ga to Ni atoms was observed. This research provides valuable insights into the development of Ga-modified catalysts and emphasizes their potential for efficient conversion of greenhouse gases into syngas.

Hydrogen production from the steam reforming of biogas over Ni-based catalyst: The role of promoters and supports

Biogas steam reforming (BSR) is a sustainable and low-carbon strategy for H2 production. Herein, the conventional Ni/Al2O3 catalyst was modified by distinct promoters (Co, Cu, Fe) and supports (ZrO2, MgO, CeO2) for H2 production from BSR. The effects of modification methods on the catalytic performance were evaluated based on the activity tests and characterizations of catalysts. The introduction of the mono-metal promoter or the mono-metal oxide support was beneficial for the BSR to different degrees. Ni-Co/Al2O3 exhibited higher CH4 conversion ratio (xCH4), and Ni-Fe/Al2O3 showed the least carbon deposition among the catalysts modified by the mono-metal promoter. Both Ni/ZrO2-Al2O3 and Ni/MgO-Al2O3 modified with mono-metal oxide support showed high xCH4 approaching 90 %, with the former leading to less carbon deposition. The coupled modification by metal promoter and metal oxide support did not show a satisfactory performance. The modification by bi-metal oxide support, ZrO2 and MgO, showed the most promising catalytic conversion of CH4 and H2 production among all these modified catalysts, and the maximum values of xCH4 and H2 yield (YH2) reached 90.71 % and 86.06 %, respectively. Ni/MgO-ZrO2-Al2O3 also exhibited excellent stability with a total carbon deposition of 0.042 g·gcata−1 in the 10 h stability test.

Hydrogen-Rich Syngas Production in a Ce0.9Zr0.05Y0.05O2−δ/Ag and Molten Carbonates Membrane Reactor

This study proposes a new dense membrane for selectively separating CO2 and O2 at high temperatures and simultaneously producing syngas. The membrane consists of a cermet-type material infiltrated with a ternary carbonate phase. Initially, the co-doped ceria of composition Ce0.9Zr0.05Y0.05O2−δ (CZY) was synthesized by using the conventional solid-state reaction method. Then, the ceramic was mixed with commercial silver powders using a ball milling process and subsequently uniaxially pressed and sintered to form the disk-shaped cermet. The dense membrane was finally formed via the infiltration of molten salts into the porous cermet supports. At high temperatures (700–850 °C), the membranes exhibit CO2/N2 and O2/N2 permselectivity and a high permeation flux under different CO2 concentrations in the feed and sweeping gas flow rates. The observed permeation properties make its use viable for CO2 valorization via the oxy-CO2 reforming of methane, wherein both CO2 and O2 permeated gases were effectively utilized to produce hydrogen-rich syngas (H2 + CO) through a catalytic membrane reactor arrangement at different temperatures ranging from 700 to 850 °C. The effect of the ceramic filler in the cermet is discussed, and continuous permeation testing, up to 115 h, demonstrated the membrane’s superior chemical and thermal stability by confirming the absence of any chemical interaction between the material and the carbonates as well as the absence of significant sintering concerns with the pure silver.

Insights into Photothermocatalytic Dry Reforming of Methane on Ru/La‐Al2O3 using Carbonate Species and Reactive Oxygen Species to Enhance the Fuel Production Rates and Completely Prevent Coking

AbstractPhotothermocatalytic dry reforming of methane (DRM) offers a promising strategy for converting solar energy into fuel. However, the high light intensity required for high fuel production rates and thermodynamically more favorable coking side reactions limit this strategy. Herein, a nanocomposite of La‐doped Al2O3 supporting Ru nanoparticles (NPs) (Ru/La‐Al2O3) is synthesized. At relatively low light intensity (80.2 kW m−2), Ru/La‐Al2O3 obtains high production rates of CO and H2 per gram of Ru (rRu, CO and rRu, H2, 8410.19 and 7181.94 mmol gRu−1 min−1) with light‐to‐fuel efficiency (η, 26.6%), and completely prohibits coking. In striking contrast, the reference catalyst without La doping (Ru/Al2O3) exhibits lower rRu, CO, rRu, H2, η and produces large amounts of coke. The improved photothermocatalytic performance stems from the fact that reactive oxygen species and carbonate species are involved in the oxidation of carbon species (rate‐determining steps of DRM) through two different reaction pathways, which significantly increases catalytic activity and prevents the carbon species from polymerizing into coke. Additionally, light not only enhances the DRM on Ru NPs and the oxidation reaction between carbonate species and carbon species but also promotes the dissociation of CH4 and desorption of H2, which improves the catalytic activity and product selectivity of Ru/La‐Al2O3.

Atomic structure of different surface terminations of polycrystalline ZnPd

The intermetallic compound ZnPd has been found to have desirable characteristics as a catalyst for the steam reforming of methanol. The understanding of the surface structure of ZnPd is important to optimize its catalytic behavior. However, due to the lack of bulk single-crystal samples and the complexity of characterizing surface properties in the available polycrystalline samples using common experimental techniques, all previous surface science studies of this compound have been performed on surface alloy samples formed through thin-film deposition. In this study, we present findings on the chemical and atomic structure of the surfaces of bulk polycrystalline ZnPd studied by a variety of complementary experimental techniques, including scanning tunneling microscopy (STM), x-ray photoelectron spectroscopy (XPS), low energy electron microscopy (LEEM), photoemission electron microscopy (PEEM), and microspot low-energy electron diffraction (μ-LEED). These experimental techniques, combined with density functional theory (DFT)-based thermodynamic calculations of surface free energy and detachment kinetics at the step edges, confirm that surfaces terminated by atomic layers composed of both Zn and Pd atoms are more stable than those terminated by only Zn or Pd layers. DFT calculations also demonstrate that the primary contribution to the tunneling current arises from Pd atoms, in agreement with the STM results. The formation of intermetallics at surfaces may contribute to the superior catalyst properties of ZnPd over Zn or Pd elemental counterparts. Published by the American Physical Society 2024

Co-M (M = Ru, Pd, Pt) Bimetallic Catalysts on the CeO2 Nanofiber Prepared Using the Electrospinning Method for Dry Reforming of Methane

Co-M (M = Ru, Pd, Pt) Bimetallic Catalysts on the CeO₂ Nanofiber Prepared Using the Electrospinning Method for Dry Reforming of Methane

An innovative solar reactor with Gaussian-pattern geometry for syngas production from dry reforming of methane

Solar reactors are promising energy storage technologies that convert solar energy into the heating value of passing fluids. This study is focused on a foam-based solar reactor, one of the most common types of solar reactors, supposed to produce syngas from the dry reforming of methane (DRM). The novelty of the present study is that it proposes a new Gaussian-pattern reactor geometry inspired by the Gaussian distribution of the incident solar flux. Local thermal non-equilibrium (LTNE) model and the finite volume method (FVM) numerical approach are employed to assess the performance of the proposed solar reactor design. A comparison between the present design and the benchmark design (the design with cylindrical geometry) shows that the new design leads to better temperature distribution and improves energy storage efficiency by about 3.3%.

Maximized Ir atom utilization via downsizing active sites to single-atom scale for highly stable dry reforming of methane

Maximized Ir atom utilization via downsizing active sites to single-atom scale for highly stable dry reforming of methane

Perovskite-Based Catalysts for Syngas Upgrading by Intensified Steam Reforming of Biomass Tar

Perovskite-Based Catalysts for Syngas Upgrading by Intensified Steam Reforming of Biomass Tar

Optimizing process parameters and materials for the conversion of plastic waste into hydrogen

Abstract This study has investigated hydrogen production from waste plastics using pyrolysis, steam methane reforming, and water-gas-shift reactions modelled via Aspen Plus. After evaluating multiple alternatives, polypropylene (PP) was selected as the feedstock. The research has been focused on how reformer temperature, steam-to-fuel ratio (S/F), reformer pressure, and pyrolysis temperature impact syngas composition, heating values, syngas (H2/CO) ratios, and yields of hydrogen (H2), methane (CH4), and carbon dioxide (CO2). Key findings have indicated that raising reformer temperatures to around 1000°C maximizes hydrogen production in syngas, reaching peak levels of 2360 Nm3/Ton and 2525 Nm3/Ton for reformer temperature and steam-to-fuel ratio (S/F) ratios, respectively, via processes like steam methane reforming and the water-gas-shift reaction. Moreover, other parameters like steam-to-fuel (S/F) ratio and reformer pressure have produced the highest amount of hydrogen at 0.25 and 1 atm, respectively. Optimizing reformer temperature and steam-to-fuel ratio (S/F) have been selected as key in hydrogen production, with peak lower heating values (LHV) of 1.15 MJ/kg for temperature and 1.035 MJ/kg for S/F ratios, highlighting the importance of balancing these parameters for efficiency. Additionally, syngas' hydrogen (H2) composition increased with pyrolysis temperature, peaking at 8.5% at 700°C. Finally, this research has provided valuable insights into optimizing process parameters for sustainable hydrogen production. Moreover, the simulation process has provided cost-effective adjustments and informed decision-making for sustainable and scalable technologies, benefiting researchers, investors, engineers, and policymakers involved in innovative hydrogen generation.