A strategy of mid-temperature natural gas based chemical looping reforming for hydrogen production

Steam methane reforming (SMR) needs the reaction heat at a temperature above 800 °C provided by the combustion of natural gas and suffers from adverse environmental impact and the hydrogen separated from other chemicals needs extra energy penalty. In order to avoid the expensive cost and high power consumption caused by capturing CO₂ after combustion in SMR, natural gas Chemical Looping Reforming (CLR) is proposed, where the chemical looping combustion of metal oxides replaced the direct combustion of NG to convert natural gas to hydrogen and carbon dioxide. Although CO₂ can be separated with less energy penalty when combustion, CLR still require higher temperature heat for the hydrogen production and cause the poor sintering of oxygen carriers (OC). Here, we report a high-rate hydrogen production and low-energy penalty of strategy by natural gas chemical-looping process with both metallic oxide reduction and metal oxidation coupled with steam. Fe₃O₄ is employed as an oxygen carrier. Different from the common chemical looping reforming, the double side reactions of both the reduction and oxidization enable to provide the hydrogen in the range of 500–600 °C under the atmospheric pressure. Furthermore, the CO₂ is absorbed and captured with reduction reaction simultaneously.Through the thermodynamic analysis and irreversibility analysis of hydrogen production by natural gas via chemical looping reforming at atmospheric pressure, we provide a possibility of hydrogen production from methane at moderate temperature. The reported results in this paper should be viewed as optimistic due to several idealized assumptions: Considering that the chemical looping reaction is carried out at the equilibrium temperature of 500 °C, and complete CO₂ capture can be achieved. It is assumed that the unreacted methane and hydrogen are completely separated by physical adsorption. This paper may have the potential of saving the natural gas consumption required to produce 1 m³ H₂ and reducing the cost of hydrogen production.     

Production of hydrogen through the carbonation–calcination reaction applied to CH4/CO2 mixtures

The production of hydrogen combined with carbon capture represents a possible option for reducing CO₂ emissions in atmosphere and anthropogenic greenhouse effect. Nowadays the worldwide hydrogen production is based mainly on natural gas reforming, but the attention of the scientific community is focused also on other gas mixtures with significant methane content. In particular mixtures constituted mainly by methane and carbon dioxide are extensively used in energy conversion applications, as they include land-fill gas, digester gas and natural gas. The present paper addresses the development of an innovative system for hydrogen production and CO₂ capture starting from these mixtures. The plant is based on steam methane reforming, coupled with the carbonation and calcination reactions for CO₂ absorption and desorption, respectively. A thermodynamic approach is proposed to investigate the plant performance in relation to the CH₄ content in the feeding gas. The results suggest that, in order to optimize the hydrogen purity and the efficiency, two different methodologies can be adopted involving both the system layout and operating parameters. In particular such methodologies are suitable for a methane content, respectively, higher and lower than 65%.     

Novel quasi-autothermal hydrogen production process in a fixed-bed using a chemical looping approach: A numerical study

This paper presents a novel quasi-autothermal hydrogen production process. The proposed layout couples a Chemical Looping Combustion (CLC) section and a Steam Methane Reforming (SMR) one. In CLC section, four packed-beds are operated using Ni as oxygen carrier and CH₄ as fuel to continuously produce a hot gaseous mixture of H₂O and CO₂. In SMR section, two fixed-beds filled with Ni-based catalyst convert CH₄ and H₂O into a H₂-rich syngas. Four heat exchangers were employed to recover residual heat content of all the exhaust gas currents. By means of a previously developed 1D numerical model, a dynamic simulation study was carried out to evaluate feasibility of the proposed system in terms of methane conversion (100% circa), hydrogen yield (about 0.65 mol_H2/mol_CH4) and selectivity (about 70%), and syngas ratio (about 2.3 mol_H2/mol_CO). Energetic and environmental analyses of the system performed with respect to conventional steam methane reforming, highlights an energy saving of about 98% and avoided CO₂ emission of about 99%.     

Performance comparison among different multifunctional reactors operated under energy self-sufficiency for sustainable hydrogen production from ethanol

Four ethanol-derived hydrogen production processes including conventional ethanol steam reforming (ESR), sorption enhanced steam reforming (SESR), chemical looping reforming (CLR) and sorption enhanced chemical looping reforming (SECLR) were simulated on the basis of energy self-sufficiency, i.e. process energy requirement supplied by burning some of the produced hydrogen. The process performances in terms of hydrogen productivity, hydrogen purity, ethanol conversion, CO₂ capture ability and thermal efficiency were compared at their maximized net hydrogen. The simulation results showed that the sorption enhanced processes yield better performances than the conventional ESR and CLR because their in situ CO₂ sorption increases hydrogen production and provides heat from the sorption reaction. SECLR is the most promising process as it offers the highest net hydrogen with high-purity hydrogen at low energy requirement. Only 12.5% of the produced hydrogen was diverted into combustion to fulfill the process's energy requirement. The thermal efficiency of SECLR was evaluated at 86% at its optimal condition.     

A comparison of electricity and hydrogen production systems with CO2 capture and storage. Part A: Review and selection of promising conversion and capture technologies

We performed a consistent comparison of state-of-the-art and advanced electricity and hydrogen production technologies with CO₂ capture using coal and natural gas, inspired by the large number of studies, of which the results can in fact not be compared due to specific assumptions made. After literature review, a standardisation and selection exercise has been performed to get figures on conversion efficiency, energy production costs and CO₂ avoidance costs of different technologies, the main parameters for comparison. On the short term, electricity can be produced with 85–90% CO₂ capture by means of NGCC and PC with chemical absorption and IGCC with physical absorption at 4.7–6.9 €ct/kWh, assuming a coal and natural gas price of 1.7 and 4.7 €/GJ. CO₂ avoidance costs are between 15 and 50 €/t CO₂ for IGCC and NGCC, respectively. On the longer term, both improvements in existing conversion and capture technologies are foreseen as well as new power cycles integrating advanced turbines, fuel cells and novel (high-temperature) separation technologies. Electricity production costs might be reduced to 4.5–5.3 €ct/kWh with advanced technologies. However, no clear ranking can be made due to large uncertainties pertaining to investment and O&M costs. Hydrogen production is more attractive for low-cost CO₂ capture than electricity production. Costs of large-scale hydrogen production by means of steam methane reforming and coal gasification with CO₂ capture from the shifted syngas are estimated at 9.5 and 7 €/GJ, respectively. Advanced autothermal reforming and coal gasification deploying ion transport membranes might further reduce production costs to 8.1 and 6.4 €/GJ. Membrane reformers enable small-scale hydrogen production at nearly 17 €/GJ with relatively low-cost CO₂ capture.     

Integrated fossil fuel and solar thermal systems for hydrogen production and CO2 mitigation

In most current fossil-based hydrogen production methods, the thermal energy required by the endothermic processes of hydrogen production cycles is supplied by the combustion of a portion of the same fossil fuel feedstock. This increases the fossil fuel consumption and greenhouse gas emissions. This paper analyzes the thermodynamics of several typical fossil fuel-based hydrogen production methods such as steam methane reforming, coal gasification, methane dissociation, and off-gas reforming, to quantify the potential savings of fossil fuels and CO₂ emissions associated with the thermal energy requirement. Then matching the heat quality and quantity by solar thermal energy for different processes is examined. It is concluded that steam generation and superheating by solar energy for the supply of gaseous reactants to the hydrogen production cycles is particularly attractive due to the engineering maturity and simplicity. It is also concluded that steam-methane reforming may have fewer engineering challenges because of its single-phase reaction, if the endothermic reaction enthalpy of syngas production step (CO and H₂) of coal gasification and steam methane reforming is provided by solar thermal energy. Various solar thermal energy based reactors are discussed for different types of production cycles as well.     

Gas Switching Reforming for syngas production with iron-based oxygen carrier-the performance under pressurized conditions

A four-stage Gas Switching Reforming for syngas production with integrated CO₂ capture using an iron-based oxygen carrier was investigated in this study. The oxygen carrier was first reduced using dry methane, where high methane conversion rate was achieved producing CO₂ and steam. Following the reduction stage is a transition to syngas production in an intermediate stage that begins with partial oxidation of methane while methane cracking dominates the rest of the stage. This results in substantial carbon deposition that gasifies in a subsequent reforming stage by cofeeding steam and methane, contributing to more syngas yield. Some of the deposited carbon that could not gasify during the reforming stage slip to the oxidation stage and get combusted by oxygen in the air feed to release CO₂, thereby reducing the CO₂ capture efficiency of the process. It is in this oxidation stage that heat is being generated for the whole cycle given the high exothermicity nature of this reaction. Methane conversion was found to drop substantially in the reforming stage as the pressure increases driven by the negative effect of pressure on both carbon gasification by steam and on the steam methane reforming. The intermediate stage (after reduction) was found less sensitive to the pressure in terms of methane conversion, but the mechanism of carbon deposition tends to change from methane cracking in the POX stage to Boudouard reaction in the reforming stage. However, methane cracking shows a tendency to reduce substantially at higher pressures. This is could be a promising result indicating that high-pressure operation would remove the need for the reforming stage with steam as no carbon would have been deposited in the POX stage.     

Absorption behaviors study on doped Li4SiO4 under a humidified atmosphere with low CO2 concentration

Potassium carbonate was used as a doping agent to improve the absorption properties of Li₄SiO₄ for CO₂ capture during critical sorption-enhanced steam methane reforming (SESMR) under moderate temperature and low CO₂ concentration with moisture.     

CO2 reforming of methane combined with steam reforming or partial oxidation of methane to syngas over NdCoO3 perovskite-type mixed metal-oxide catalyst

CO₂ reforming with simultaneous steam reforming or partial oxidation of methane to syngas over NdCoO₃ perovskite-type mixed metal oxide catalyst (prereduced by H₂) at different process conditions has been investigated. In the simultaneous CO₂ and steam reforming, the conversion of methane and H₂O and also the H₂/CO product ratio are strongly influenced by the CO₂/H₂O feed-ratio. In the simultaneous CO₂ reforming and partial oxidation of methane, the conversion of methane and CO₂, H₂ selectivity and the net heat of reaction are strongly influenced by the process parameters (viz. temperature, space velocity and relative concentration of O₂ in the feed). In both cases, no carbon deposition on the catalyst was observed. The reduced NdCoO₃ perovskite-type mixed-oxide catalyst (Co dispersed on Nd₂O₃) is a highly promising catalyst for carbon-free CO₂ reforming combined with steam reforming or partial oxidation of methane to syngas.     

Pure hydrogen production via autothermal reforming of ethanol in a fluidized bed membrane reactor: A simulation study

In this paper the production of ultra-pure hydrogen via autothermal reforming of ethanol in a fluidized bed membrane reactor has been studied. The heat needed for the steam reforming of ethanol is obtained by burning part of the hydrogen recovered via the hydrogen perm-selective membrane thereby integrating CO₂ capture. Simulation results based on a phenomenological model show that it is possible to obtain overall autothermal reforming of ethanol while 100% of hydrogen can in principle be recovered at relatively high temperatures and at high reaction pressures. At the same operating conditions, ethanol is completely converted, while the methane produced by the reaction is completely reformed to CO, CO₂ and H₂.     

Hydrogen generation with CO2 utilization: A solvay cluster study

The fuel cell economy is yet to start research programs in hydrogen generation with CO₂ utilization for hydrocarbon reforming processes used in fuel processor applications. A simple thermodynamic study using solvay clusters was done to investigate the feasibility of using the carbon species produced in the steam methane reforming process to produce value added chemicals. The results of this study are highly encouraging to start process development of closed systems of hydrogen generation with CO₂ conversion to acetic acid/acrylic acid making easier the commercialization of fuel cells and hydrogen energy. Such studies can be specifically carried out for different fuel processor systems.     

In-situ CO2 capture in a pilot-scale fluidized-bed membrane reformer for ultra-pure hydrogen production

A novel pilot fluidized-bed membrane reformer (FBMR) with permselective palladium membranes was operated with a limestone sorbent to remove CO₂in-situ, thereby shifting the thermodynamic equilibrium to enhance pure hydrogen production. The reactor was fed with methane to fluidize a mixture of calcium oxide (CaO)/limestone (CaCO₃) and a Ni-alumina catalyst. Experimental tests investigated the influence of limestone loading, total membrane area and natural gas feed rates. Hydrogen-permeate to feed methane molar ratios in excess of 1.9 were measured. This value could increase further if additional membrane area were installed or by purifying the reformer off-gas given its high hydrogen content, especially during the carbonation stages. A maximum of 0.19 mol of CO₂ were adsorbed per mole of CaO during carbonation. For the conditions studied, the maximum carbon capture efficiency was 87%. The reformer operated for up to 30 min without releasing CO₂ and for up to 240 min with some degree of CO₂ capture. It was demonstrated that CO₂ adsorption can significantly improve the productivity of the reforming process. In-situ CO₂ capture enhanced the production of hydrogen whose purity exceeded 99.99%.     

Kinetic study and modeling of the high temperature CO2 capture by Na2ZrO3 solid absorbent

Hydrogen production through sorption enhanced reforming (SER) use a solid CO₂ absorbent to increase hydrogen purity (98%) and to perform reforming and WGS reactions in one single step, thus producing high methane conversions and important energy savings. Na₂ZrO₃ is as an alternate synthetic CO₂ solid absorbent for SER applications. The present research is aimed to establish CO₂ sorption kinetics parameters; reaction order, rate constant, apparent, intrinsic and diffusional activation energies. Na₂ZrO₃ sorption kinetics was studied through TGA as a function of CO₂ concentration and temperature. A global reaction rate of first order in CO₂ and a strong dependence in temperature was found. The approximate solution to the shrinking core model was used to fit the data. Modeling results indicated the surface reaction as the main resistance to the reaction rate, controlling reaction kinetics with only a minor contribution of the product layer diffusion resistance toward the end of the reaction.     

Techno-economic analysis of e-waste based chemical looping reformer as hydrogen generator with co-generation of metals,electricity and syngas

Chemical looping reforming (CLR) is an efficient technology to convert hydrocarbon fuels into CO₂ and H₂ using metal oxide based oxygen carriers. The novelty of the present study is to utilize electronic waste such as printed circuit board (PCB) to generate high quality syngas and metallic components for the CLR process. A portion of the syngas generated during e-waste pyrolysis is used with coal and polypropylene for effective combustion. A techno-economic analysis is performed for the production of hydrogen and electricity in the CLR method. The levelized costs for electricity (LCOE), hydrogen (LCOH), syngas (LCOS), and metal (LCOM) production using e-wastes are estimated as 92.28 $/MWh, 3.67 $/kg, 0.0034 $/kWh, and 24.32 $/ton, respectively. The LCOH is found to be the least of 2.90 $/kg under the co-feed conditions of PCB syngas-PP. The integration of the e-waste based CLR with a steam turbine system achieved a net efficiency of 50%.     

Exploring the opportunities for carbon capture in modular,small-scale steam methane reforming: An energetic perspective

Small-scale steam methane reforming units produce more than 12% of all the CO₂-equivalent emissions from hydrogen production and, unlike large-scale units, are usually not integrated with other processes. In this article, the authors examine the hitherto under-explored potential to utilise the excess heat available in the small-scale steam methane reforming process for partial carbon dioxide capture. Reforming temperature has been identified as a critical operating parameter to affect the amount of excess heat available in the steam methane reforming process. Calculations suggest that reforming the natural gas at 850 °C, rather than 750 °C, increases the amount of excess heat available by about 28.4% (at 180 °C) while, sacrificing about 1.62% and 1.09% in the thermal and exergetic efficiency of the process, respectively. Preliminary calculations suggest that this heat could potentially be utilised for partial carbon capture from reformer flue gas, via structured adsorbents, in a compact capture unit. The reforming temperature can be adjusted in order to regulate the amount of excess heat, and thus the carbon capture rate.     

Optimization of H2 production with CO2 capture by steam reforming of methane integrated with a chemical-looping combustion system

Methane steam reforming (SR) integrated with a chemical-looping combustion (CLC) system is a new process for producing hydrogen from natural gas, allowing carbon dioxide capture with a low energy penalty. In this study, mass and enthalpy balances of an SR-CLC system were carried out to determine the autothermal operating conditions for optimal H₂ production. The evaluation was conducted using iron-based oxygen carriers. Two configurations were analysed, firstly with the reformer tubes inside the fuel reactor and, secondly, with the reformer tubes inside the air reactor. This paper analyses the effect of two parameters affecting the SR process, namely the conversion of methane in the reformer (XCH₄$X_{{\text{CH}}_4}$) and the efficiency of the hydrogen separation of a pressure swing adsorption (PSA) unit (η_PSA), as well as two parameters affecting the CLC system, namely the Fe₂O₃ content in the oxygen carrier and its conversion variation (ΔX_OC), on the H₂ yields. Moreover, it also analyses the reduction of Fe₂O₃ to Fe₃O₄ or to FeAl₂O₄. The results shown that a H₂ yield value of 2.45 mol H₂ per mol of CH₄ can be obtained with the reformer tubes located inside the air reactor and with Fe₂O₃ being reduced to Fe₃O₄. This corresponds to a CH₄ to H₂ conversion of 74.2%, which is similar to state-of-the-art H₂ production technologies, but with inherent CO₂ capture in the SR-CLC process.     

An oxy-fuel mass-recirculating process for H2 production with CO2 capture by autothermal catalytic oxyforming of methane

A new oxy-fuel H₂ generation process with CO₂ avoidance is provided. The process utilizes mass recirculation of CO and H₂O to the oxyforming reactor. A comparison between non-recirculating and mass-recirculating oxyforming reactor operation is given. Main benefits of mass recirculation are emphasized. The oxyforming reactor is integrated with the H₂ and CO₂ separators, fuel cell and O₂ generator. In the process C/O is equal to 0.5 while C/H determines the temperature level in the reactor. The reaction system includes combustion, steam reforming and water–gas shift reactions. The oxyforming process is found to be mass transport controlled with O₂ as the limiting reactant. It is emphasized that under MR conditions the decomposition of H₂/CO₂ by water–gas shift reaction is suppressed by means of CO/H₂O-enrichment and hence MR conditions allow for higher temperatures beneficial to endothermic steam reforming reaction. Under MR conditions the thermodynamic equilibrium limits are overcome and all reactions are forced to proceed to the completion which enables 100% selectivities to H₂ and CO₂. The effects of operation parameters such as temperature, flow rate, pressure and composition are examined. The derived S-terms enable for the concise interpretation of the effect of pressure on the concentration gradients transverse to the flow. The consistent control algorithm of the oxyforming reactor is provided.     

Economic assessment of membrane-assisted autothermal reforming for cost effective hydrogen production with CO2 capture

A recent techno-economic study (Spallina et al., Energy Conversion and Management 120: p. 257–273) showed that the membrane assisted chemical looping reforming (MA-CLR) technology can produce H₂ with integrated CO₂ capture at costs below that of conventional steam methane reforming. A key technical challenge related to MA-CLR is the achievement of reliable solids circulation between the air and fuel reactors at large scale under the high (>50 bar) operating pressures required for optimal performance. This work therefore presents process modelling and economic assessments of a simplified alternative; membrane assisted autothermal reforming (MA-ATR), that inherently avoids this technical challenge. The novelty of MA-ATR lies in replacing the MA-CLR air reactor with an air separation unit (ASU), thus avoiding the need for oxygen carrier circulation. The economic assessment found that H₂ production from MA-ATR is only 1.5% more expensive than MA-CLR in the base case. The calculated cost of hydrogen (compressed to 150 bar) in the base case was 1.55 €/kg with a natural gas price of €6/GJ and an electricity price of €60/MWh. Both concepts show continued performance improvements with an increase in reactor pressure and temperature, while an optimum cost is achieved at about 2 bar H₂ permeate pressure. Sensitivities to other variables such as financing costs, membrane costs, fuel and electricity prices are similar between MA-ATR and MA-CLR. Natural gas prices represent the most important sensitivity, while the sensitivity to membrane costs is relatively small at high reactor pressures. MA-ATR therefore appears to be a promising alternative to achieve competitive H₂ production with CO₂ capture if technical challenges significantly delay scale-up and deployment of MA-CLR technology. The key technical demonstration required before further MA-ATR scale-up is membrane longevity under the high reactor pressures and temperatures required to minimize the cost of hydrogen.     

Techno-economic analysis of the Ca-Cu process integrated in hydrogen plants with CO2 capture

In this work, a techno-economic analysis of a hydrogen production plant based on the Ca-Cu process has been carried out. The simulation of the whole hydrogen production plant has been performed, including the calculation of the Ca-Cu fixed bed reactors system using a sharp front modelling approach. From the analyses carried out, it has been demonstrated that the optimal operation point from the energy performance point of view is reached when fuel needed for sorbent regeneration is entirely supplied by the off-gas from the PSA hydrogen purification unit, which corresponds to operating the plant with the minimum steam-to-carbon ratio in the reforming step. Moreover, lowering the operating pressure of the Ca-Cu system results beneficial from the hydrogen production efficiency, but the CO₂ emissions and the economics worsen.The Ca-Cu based hydrogen production plant operating at a high pressure has been demonstrated to be cost efficient with respect to a benchmark hydrogen production plant based on conventional fired tubular reformer and CO₂ capture by MDEA absorption. A hydrogen production cost of 0.178 €/Nm³ and a CO₂ avoided cost of 30.96 €/ton have been calculated for this Ca-Cu hydrogen production plant, which are respectively 8% and 52% lower than the corresponding costs of the benchmark.     

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.