Thermodynamic analysis of a membrane-assisted chemical looping reforming reactor concept for combined H2 production and CO2 capture

There is great consensus that hydrogen will become an important energy carrier in the future. Currently, hydrogen is mainly produced by steam reforming of natural gas/methane on large industrial scale or by electrolysis of water when high-purity hydrogen is needed for small-scale hydrogen plants. Although the conventional steam reforming process is currently the most economical process for hydrogen production, the global energy and carbon efficiency of this process is still relatively low and an improvement of the process is key for further implementation of hydrogen as a fuel source. Different approaches for more efficient hydrogen production with integrated CO₂ capture have been discussed in literature: Chemical Looping Combustion (CLC) or Chemical Looping Reforming (CLR) and membrane reactors have been proposed as more efficient alternative reactor concepts relative to the conventional steam reforming process. However, these systems still present some drawbacks. In the present work a novel hybrid reactor concept that combines the CLR technology with a membrane reactor system is presented, discussed and compared with several other novel technologies. Thermodynamic studies for the new reactor concept, referred to as Membrane-Assisted Chemical Looping Reforming (MA-CLR), have been carried out to determine the hydrogen recovery, methane conversion as well as global efficiency under different operating conditions, which is shown to compare quite favorably to other novel technologies for H₂ production with CO₂ capture.     

High capacity potassium-promoted hydrotalcite for CO2 capture in H2 production

This paper presents an experimental study for a newly modified K₂CO₃-promoted hydrotalcite material as a novel high capacity sorbent for in-situ CO₂ capture. The sorbent is employed in the sorption enhanced steam reforming process for an efficient H₂ production at low temperature (400–500 ^°C). A new set of adsorption data is reported for CO₂ adsorption over K-hydrotalcite at 400 °C. The equilibrium sorption data obtained from a column apparatus can be adequately described by a Freundlich isotherm. The sorbent shows fast adsorption rates and attains a relatively high sorption capacity of 0.95 mol/kg on the fresh sorbent. CO₂ desorption experiments are conducted to examine the effect of humidity content in the gas purge and the regeneration time on CO₂ desorption rates. A large portion of CO₂ is easily recovered in the first few minutes of a desorption cycle due to a fast desorption step, which is associated with a physi/chemisorption step on the monolayer surface of the fresh sorbent. The complete recovery of CO₂ was then achieved in a slower desorption step associated with a reversible chemisorption in a multi-layer surface of the sorbent. The sorbent shows a loss of 8% of its fresh capacity due to an irreversible chemisorption, however, it preserves a stable working capacity of about 0.89 mol/kg, suggesting a reversible chemisorption process. The sorbent also presents a good cyclic thermal stability in the temperature range of 400–500 °C.     

Chemical looping glycerol reforming for hydrogen production by Ni@ZrO2 nanocomposite oxygen carriers

The research describes the synthesis of nanocomposite Ni@ZrO₂ oxygen carriers (OCs) and lanthanide doping effect on maintaining the platelet-structure of the nanocomposite OCs. The prepared OCs were tested in chemical looping reforming of glycerol (CLR) process and sorption enhanced chemical looping reforming of glycerol (SE-CLR) process. A series of characterization techniques including N₂ adsorption-desorption, X-ray diffraction (XRD), inductively coupled plasma optical emission spectrometry (ICP-OES), high resolution transmission electron microscopy (HRTEM), H₂ temperature-programmed reduction (H₂-TPR), H₂ pulse chemisorption and O₂ temperature-programmed desorption (O₂-TPD) were used to investigate the physical properties of the fresh and used OCs. The results show that the platelet-stack structure of nanocomposite OCs could significantly improve the metal support interaction (MSI), thus enhancing the sintering resistance. The effect of lanthanide promotion on maintaining this platelet-stack structure increased with the lanthanide radius, namely, La³⁺ > Ce³⁺ > Pr³⁺ > Yb³⁺. Additionally, the oxygen mobility was also enhanced because of the coordination of oxygen transfer channel size by doping small radius lanthanide ions. The CeNi@ZrO₂ showed a moderate ‘dead time’ of 220 s, a high H₂ selectivity of 94% and a nearly complete glycerol conversion throughout a 50-cycle CLR test. In a 50-cycle SE-CLR stability test, the CeNi@ZrO₂CaO showed high H₂ purity of 96.3%, and an average CaCO₃ decomposition percentage of 53% without external heating was achieved.     

Enhanced multi-cycle CO2 capture and tar reforming via a hybrid CaO-based absorbent/catalyst: Effects of preparation,reaction conditions and application for hydrogen production

A hybrid CaO-based absorbent/catalyst (Ca–Al–Fe) for calcium looping gasification (CLG) is prepared by a two-step sol-gel method. The effects of preparation and “carbonation-calcination” conditions on cyclic carbonation performance of Ca–Al–Fe are investigated. Calcination temperature of 900 °C and calcination time of 4 h are suitable parameters for absorbent preparation. The CaO conversion of Ca–Al–Fe increases with increasing carbonation temperature below 750 °C. Under severe calcination conditions such as high temperature, high CO₂ concentration and long-term up to 40 cycles, Ca–Al–Fe still shows good cyclic CO₂ capture reactivity. Moreover, the effect of Ca–Al–Fe on tar removal enhancement is investigated in comparison with three candidate absorbents (Ca、Ca–Fe and Ca–Al). During five toluene reforming cycles, Ca–Al–Fe presents the highest average H₂ yield and the least deposited coke with an average hydrogen concentration of about 68.8%. The average toluene conversion with Ca–Al–Fe is about 26.41% higher than that using conventional CaO.     

Thermodynamic analysis of hydrogen production via glycerol steam reforming with CO2 adsorption

Thermodynamic equilibrium for glycerol steam reforming to hydrogen with carbon dioxide capture was investigated using Gibbs free energy minimization method. Potential advantage of using CaO as CO₂ adsorbent is to generate hydrogen-rich gas without a water gas shift (WGS) reactor for proton exchange membrane fuel cell (PEMFC) application. The optimal operation conditions are at 900 K, the water-to-glycerol molar ratio of 4, the CaO-to-glycerol molar ratio of 10 and atmospheric pressure. Under the optimal conditions, complete glycerol conversion and 96.80% H₂ and 0.73% CO concentration could be achieved with no coke. In addition, reaction conditions for coke-free and coke-formed regions are also discussed in glycerol steam reforming with or without CO₂ separation. Glycerol steam reforming with CO₂ adsorption has the higher energy efficiency than that without adsorption under the same reaction conditions.     

Design of an integrated process for simultaneous chemical looping hydrogen production and electricity generation with CO2 capture

This study was aimed at proposing a novel integrated process for co-production of hydrogen and electricity through integrating biomass gasification, chemical looping combustion, and electrical power generation cycle with CO₂ capture. Syngas obtained from biomass gasification was used as fuel for chemical looping combustion process. Calcium oxide metal oxide was used as oxygen carrier in the chemical looping system. The effluent stream of the chemical looping system was then transferred through a bottoming power generation cycle with carbon capture capability. The products achieved through the proposed process were highly-pure hydrogen and electricity generated by chemical looping and power generation cycle, respectively. Moreover, LNG cold energy was used as heat sink to improve the electrical power generation efficiency of the process. Sensitivity analysis was also carried out to scrutinize the effects of influential parameters, i.e., carbonator temperature, steam/biomass ratio, gasification temperature, gas turbine inlet stream temperature, and liquefied natural gas (LNG) flow rate on the plant performance. Overall, the optimum heat integration was achieved among the sub-systems of the plant while a high energy efficiency and zero CO₂ emission were also accomplished. The findings of the present study could assist future investigations in analyzing the performance of integrated processes and in investigating optimal operating conditions of such systems.     

Chemical looping steam reforming of ethanol without and with in-situ CO2 capture

Chemical looping steam reforming (CLSR) of ethanol using oxygen carriers (OCs) for hydrogen production has been considered a highly efficient technology. In this study, NiO/MgAl₂O₄ oxygen carriers (OCs) were employed for hydrogen production via CLSR with and without CaO sorbent for in-situ CO₂ removal (sorption enhanced chemical looping steam reforming, SE-CLSR). To find optimal reaction conditions of the CLSR process, including reforming temperatures, the catalyst mass, and the NiO loadings on hydrogen production performances were studied. The results reveal that the optimal temperature of OCs for hydrogen production is 650 °C. In addition, 96% hydrogen selectivity and a 'dead time' (the reduced time of OCs) less than 1 minute is obtained with the 1 g 20NiO/MgAl₂O₄ catalysts. The superior catalytic activity of 20NiO/MgAl₂O₄ is due to the maximal quantity of NiO loadings providing the most Ni active surface centers. High purity hydrogen is successfully produced via CLSR coupling with CaO sorbent in-situ CO₂ removal (SE-CLSR), and the breakthrough time of CaO is about 20 minutes under the condition that space velocity was 1.908 h^?1. Stability CLSR experiments found that the hydrogen production and hydrogen selectivity decreased obviously from 207 mmol to 174 mmol and 95%–85% due to the inevitable OCs sintering and carbon deposition. Finally, stable hydrogen production with the purity of 89%～87% and selectivity of 96%～93% was obtained in the modified stability SE-CLSR experiments.     

The calcium looping cycle for large-scale CO2 capture

The reversible reaction between CaO and CO₂ is an extremely promising method of removing CO₂ from the exhaust of a power station, generating a pure stream of CO₂ ready for geological sequestration. The technology has attracted a great deal of attention recently, owing to a number of its advantages: the relatively small efficiency penalty which it imposes upon a power station (estimated at 6–8 percentage points, including compression of the CO₂); its potential use in large-scale circulating fluidised beds (a mature technology, as opposed to the vastly upscaled solvent scrubbing towers which would be required for amine scrubbing); its excellent opportunity for integration with cement manufacture (potentially decarbonising both industries) and its extremely cheap sorbent (crushed limestone).     

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.     

Characterization of Fe2O3/CeO2 oxygen carriers for chemical looping hydrogen generation

Fe₂O₃ is currently the most proper active metal oxide for chemical looping hydrogen generation (CLHG). However, supports are necessary to improve the reactivity and redox stability. CeO₂ can enhance the oxygen mobility, leading to high redox reactivity and carbon deposition resistance, which can be an excellent alternative support for oxygen carriers. In this paper, Fe₂O₃/CeO₂ oxygen carriers prepared by the co-precipitation method with different Fe₂O₃ loadings were investigated on a batch fluidized bed regarding the hydrogen yield and purity, redox reactivity and stability in CLHG with CO as fuel. The results showed that Fe6Ce4 is the best given comprehensive performance with no CO or CO₂ observed in the obtained hydrogen (detection limit 0.01% in volume). The oxygen mobility property for the reducible support CeO₂ and the physical contact between un-integrated Fe₂O₃ and CeO₂ could improve the reduction of Fe₂O₃. In addition, the formation of the hematite-like solid solution and perovskite-type CeFeO₃ could bring about abundant oxygen vacancies and promote the oxygen mobility, which contributes to the elimination of carbon deposition, counteracts the negative effect of serious sintering and guarantees the reactivity and redox stability of the Fe₂O₃/CeO₂ oxygen carriers. The Fe₂O₃/CeO₂ oxygen carriers were characterized by carbon monoxide temperature-programmed reduction measurement and X-ray diffraction patterns, and Fe6Ce4 was also selected to be characterized by scanning electron microscopy images and energy dispersive X-ray spectrometer analysis.     

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.     

Comparative analysis on sorption enhanced steam reforming and conventional steam reforming of hydroxyacetone for hydrogen production: Thermodynamic modeling

The chemical thermodynamics of sorption enhanced steam reforming (SESR) of hydroxyacetone for hydrogen production were investigated and contrasted with hydroxyacetone steam reforming (SR) by means of Gibbs free energy minimization principle and response reactions (RERs) method. Hydrogen is mainly derived methane steam reforming reaction from and water gas shift reaction. The former reaction contributes more than the latter one to hydrogen production below 550 °C and at higher temperature the latter one tends to dominate. The maximum hydrogen concentration is 70% in SR, which is far below hydrogen purities required by fuel cells. In SESR, hydrogen purities are over 99% in 525–550 °C with a WHMR greater than 8 and a CHMR of 6. The optimum temperature for SESR is approximately 125 °C lower than that for SR. In comparison with SR, SESR has the advantage of almost complete inhibition of coke formation in 200–1200 °C for WHMR ≥ 3.     

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%.     

Chemical looping reforming of ethanol-containing organic wastewater for high ratio H2/CO syngas with iron-based oxygen carrier

This work focused on chemical looping reforming (CLR) of ethanol-containing wastewater using iron-based oxygen carrier for high ratio H₂/CO syngas. Effects of various operating parameters on CLR experiments have been investigated. High temperature promotes the reactivity of oxygen carrier and release more lattice oxygen for CLR of ethanol-containing wastewater to realize maximum carbon conversion. 5% ethanol-containing wastewater, closed to the actual concentration of alcohol distillery wastewater, favors syngas yield. Ethanol-containing wastewater CLR processes could be divided into three stages, including the catalytic cracking, combination of catalytic cracking and reforming, and mainly catalytic reforming of ethanol, corresponding to three reduction periods Fe₂O₃ → Fe₃O₄, Fe₃O₄ → Fe₂O_2.45, and Fe₂O_2.45 → FeO, respectively. The whole process of ethanol-containing organic wastewater CLR is exothermic. Reaction heat released from the oxidation process of the reduced oxygen carrier can meet heat demand for CLR process. Ethanol-containing organic wastewater CLR opens up a new direction for hydrogen generation and waste treatment.     

A novel hybrid iron-calcium catalyst/absorbent for enhanced hydrogen production via catalytic tar reforming with in-situ CO2 capture

An iron-calcium hybrid catalyst/absorbent (Ca–Al–Fe) is developed by a two-step sol-gel method to enhance tar conversion, cyclic CO₂ capture and mechanical strength of absorbent for hydrogen production in calcium looping gasification. The developed catalyst/absorbent consists of CaO and brownmillerite (Ca₂Fe₂O₅) with mayenite (Ca₁₂Al₁₄O₃₃) as inert support. Comparing with three candidate absorbents without Ca₂Fe₂O₅ or Ca₁₂Al₁₄O₃₃, cyclic carbonation reactivity and mechanical strength of Ca–Al–Fe are largely promoted. Meanwhile, Ca–Al–Fe approaches the maximum conversion rate of 1-methyl naphthalene (1-MN) with enhanced hydrogen yield around 0.15 mol/(h·g) under reforming conditions of present study. Ca–Al–Fe also shows the largest CO₂ absorption and lowest coke deposition. Influences of operation variables on 1-MN reforming are evaluated and recommended conditions can be iron to CaO mass ratio of 10%, reaction temperature of 800 °C and steam to carbon in 1-MN mole ratio of 2.0. Ca–Al–Fe hybrid catalyst/absorbent presents good potential to be applied in future.     

Techno-economic assessment of the novel gas switching reforming (GSR) concept for gas-fired power production with integrated CO2 capture

The focus of this study is to carry out techno-economic analysis of a pre-combustion capture method in Natural Gas based power plants with a novel reactor concept, Gas Switching Reforming (GSR). This reactor concept enables auto thermal natural gas reforming with integrated CO₂ capture. The process analysed integrates GSR, Water Gas Shift (WGS), and Pressure Swing Adsorption (PSA) into a Natural Gas based combined cycle power plant. The overall process is defined as GSR-CC. Sensitivity studies have been carried out to understand the performance of the GSR-CC process by changing the oxygen carrier utilization and Steam/Carbon ratio in GSR. The net electrical efficiency of the GSR-CC lies between 45.1% and 46.2% and the levelised cost of electricity lies between 124.4 and 128.1 $/MWh (at European natural gas prices) for the parameter space assumed in this study. By eliminating the WGS step from the process, the net electrical efficiency improves to 47.4% and the levelised cost of electricity reduces to 120.7 $/MWh. Significant scope exists for further efficiency improvements and cost reductions from the GSR-CC system. In addition, the GSR-CC process achieves high CO₂ avoidance rates (>95%) and offers the possibility to produce pure H₂ during times of low electricity demands.     

Low temperature sugar cane bagasse pyrolysis for the production of high purity hydrogen through steam reforming and CO2 capture

Biomass pyrolysis offers a fast route to produce elevated yields towards highly valued liquid products. This research aims the determination of optimal experimental conditions for a slow and low temperature pyrolysis to produce the highest yield towards condensable (CVM) and non-condensable (NCVM) volatile matter from Mexican cane bagasse and to quantify and characterize the compounds that constitute CVM and NCVM obtained. Results indicate that yield towards volatiles is strongly dependent on temperature. The highest yield was achieved at temperatures greater than 500 °C at a heating rate of 10 °C/min, residence time of 60 min and a particle size between of 420 and 840 μm. Product quantification under isothermal conditions determined that at 550 °C the NCVM, CVM and solid residue was of 26, 57 and 16%, respectively. Preliminary thermodynamic analysis of steam reforming and CO₂ absorption reactions using one of the main CVM products resulted in a potential high hydrogen production yield.     

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%.     

Techno-economic analysis: Ethane steam reforming in a membrane reactor with H2 selectivity effect and profitability analysis

With the increased production of shale gas through a new drilling technology of hydraulic fracturing, much attention has been directed to various utilization methods for ethane accounting for about 7% of shale gas. As an efficient utilization method for ethane, ethane steam reforming in a membrane reactor is proposed in this paper to provide improved reactant conversions and product yields thus leading to a reduced operating temperature. To assess techno-economic feasibility of ethane steam reforming in a membrane reactor, parametric studies focusing on a H₂ selectivity and economic analysis predicting profitability from cash flow diagrams based on a purified hydrogen in Korea were performed simultaneously providing very useful design and economic guidelines to implement a membrane reactor for ethane steam reforming.     

Techno-economic evaluation of the evaporative gas turbine cycle with different CO2 capture options

The techno-economic evaluation of the evaporative gas turbine (EvGT) cycle with two different CO₂ capture options has been carried out. Three studied systems include a reference system: the EvGT system without CO₂ capture (System I), the EvGT system with chemical absorption capture (System II), and the EvGT system with oxyfuel combustion capture (System III). The cycle simulation results show that the system with chemical absorption has a higher electrical efficiency (41.6% of NG LHV) and a lower efficiency penalty caused by CO₂ capture (10.5% of NG LHV) compared with the system with oxyfuel combustion capture. Based on a gas turbine of 13.78 MW, the estimated costs of electricity are 46.1 $/MW h for System I, while 70.1 $/MW h and 74.1 $/MW h for Systems II and III, respectively. It shows that the cost of electricity increment of chemical absorption is 8.7% points lower than that of the option of oxyfuel combustion. In addition, the cost of CO₂ avoidance of System II which is 71.8 $/tonne CO₂ is also lower than that of System III, which is 73.2 $/tonne CO₂. The impacts of plant size have been analyzed as well. Results show that cost of CO₂ avoidance of System III may be less than that of System II when a plant size is larger than 60 MW.