Investigation of hydrogen and power co-generation based on direct coal chemical looping systems

This paper evaluates hydrogen and power co-generation based on direct coal chemical looping systems with total decarbonization of the fossil fuel. As an illustrative example, an iron-based chemical looping system was assessed in various plant configurations. The designs generate 300–450 MW net electricity with flexible hydrogen output in the range of 0–200 MW_th (LHV). The capacity of evaluated plant concepts to have a flexible hydrogen output is an important aspect for integration in modern energy conversion systems. The carbon capture rate of evaluated concepts is almost total (>99%). The paper presents in details evaluated plant configurations, operational aspects as well as mass and energy integration issues. For comparison reason, a syngas-based chemical looping concept and Selexol^®-based pre-combustion capture configuration were also presented. Direct coal chemical looping configuration has significant advantages compared with syngas-based looping systems as well as solvent-based carbon capture configurations, the more important being higher energy efficiency, lower (or even zero) oxygen consumption and lower plant complexity. The results showed a clear increase of overall energy efficiency in comparison to the benchmark cases.     

Hydrogen production from fossil fuels with carbon capture and storage based on chemical looping systems

This paper analyzes innovative processes for producing hydrogen from fossil fuels conversion (natural gas, coal, lignite) based on chemical looping techniques, allowing intrinsic CO₂ capture. This paper evaluates in details the iron-based chemical looping system used for hydrogen production in conjunction with natural gas and syngas produced from coal and lignite gasification. The paper assesses the potential applications of natural gas and syngas chemical looping combustion systems to generate hydrogen. Investigated plant concepts with natural gas and syngas-based chemical looping method produce 500 MW hydrogen (based on lower heating value) covering ancillary power consumption with an almost total decarbonisation rate of the fossil fuels used.The paper presents in details the plant concepts and the methodology used to evaluate the performances using critical design factors like: gasifier feeding system (various fuel transport gases), heat and power integration analysis, potential ways to increase the overall energy efficiency (e.g. steam integration of chemical looping unit into the combined cycle), hydrogen and carbon dioxide quality specifications considering the use of hydrogen in transport (fuel cells) and carbon dioxide storage in geological formation or used for EOR.     

Techno-economic and environmental performances of glycerol reforming for hydrogen and power production with low carbon dioxide emissions

This paper is evaluating from the conceptual design, thermal integration, techno-economic and environmental performances points of view the hydrogen and power generation using glycerol (as a biodiesel by-product) reforming processes at industrial scale with and without carbon capture. The evaluated hydrogen plant concepts produced 100,000 Nm³/h hydrogen (equivalent to 300 MW_th) with negligible net power output for export. The power plant concepts generated about 500 MW net power output. Hydrogen and power co-generation was also assessed. The CO₂ capture concepts used alkanolamine-based gas–liquid absorption. The CO₂ capture rate of the carbon capture unit is at least 90%, the carbon capture rate of the overall reforming process being at least 70%. Similar designs without carbon capture have been developed to quantify the energy and cost penalties for carbon capture. The various glycerol reforming cases were modelled and simulated to produce the mass & energy balances for quantification of key plant performance indicators (e.g. fuel consumption, energy efficiency, ancillary energy consumption, specific CO₂ emissions, capital and operational costs, production costs, cash flow analysis etc.). The evaluations show that glycerol reforming is promising concept for high energy efficiency processes with low CO₂ emissions.     

Techno-economical evaluations of decarbonized hydrogen production based on direct biogas conversion using thermo-chemical looping cycles

Hydrogen production by biogas conversion represent a promising solution for reduction of fossil CO₂ emissions. In this work, a detailed techno-economic analysis was performed for decarbonized hydrogen production based on biogas conversion using calcium and chemical looping cycles. All evaluated concepts generate 100,000 Nm³/h high purity hydrogen. As reference cases, the biogas steam reforming design without decarbonization and with CO₂ capture by gas-liquid chemical absorption were also considered. The results show that iron-based chemical looping design has higher energy efficiency compared with the gas-liquid absorption case by 2.3 net percentage points as well as a superior carbon capture rate (99% vs. 65%). The calcium looping case shows a lower efficiency than chemical scrubbing, with about 2.5 net percentage points, but the carbon capture rate is higher (95% vs. 65%). The hydrogen production cost increases with decarbonization, the calcium looping shows the most favourable situation (37.14 €/MWh) compared to the non-capture steam reforming case (33 €/MWh) and MDEA and iron looping cases (about 42 €/MWh). The calcium looping case has the lowest CO₂ avoidance cost (10 €/t) followed by iron looping (20 €/t) and MDEA (31 €/t) cases.     

Optimization of hydrogen production from three reforming approaches of glycerol via using supercritical water with in situ CO2 separation

A pathway for hydrogen production from supercritical water reforming of glycerol integrated with in situ CO₂ removal was proposed and analyzed. The thermodynamic analysis carried out by the minimizing Gibbs free energy method of three glycerol reforming processes for hydrogen production was investigated in terms of equilibrium compositions and energy consumption using AspenPlus™ simulator. The effect of operating condition, i.e., temperature, pressure, steam to glycerol (S/G) ratio, calcium oxide to glycerol (CaO/G) ratio, air to glycerol (A/G) ratio, and nickel oxide to glycerol (NiO/G) ratio on the hydrogen production was investigated. The optimum operating conditions under maximum H₂ production were predicted at 450 °C (only steam reforming), 400 °C (for autothermal reforming and chemical looping reforming), 240 atm, S/G ratio of 40, CaO/G ratio of 2.5, A/G ratio of 1 (for autothermal reforming), and NiO/G ratio of 1 (for chemical looping reforming). Compared to three reforming processes, the steam reforming obtained the highest hydrogen purity and yield. Moreover, it was found that only autothermal reforming and chemical looping reforming were possible to operate under the thermal self-sufficient condition, which the hydrogen purity of chemical looping reforming (92.14%) was higher than that of autothermal reforming (52.98%). Under both the maximum H₂ production and thermal self-sufficient conditions, the amount of CO was found below 50 ppm for all reforming processes.     

Evaluation of power generation schemes based on hydrogen-fuelled combined cycle with carbon capture and storage (CCS)

IGCC is a power generation technology in which the solid feedstock is partially oxidized to produce syngas. In a modified IGCC design for carbon capture, there are several technological options which are evaluated in this paper. The first two options involve pre-combustion arrangements in which syngas is processed, either by shift conversion or chemical looping, to maximise the hydrogen level and to concentrate the carbon species as CO₂. After CO₂ capture by gas-liquid absorption or chemical looping, the hydrogen-rich gas is used for power generation. The third capture option is based on post-combustion arrangement using chemical absorption.Investigated coal-based IGCC case studies produce 400-500 MW net power with more than 90% carbon capture rate. Principal focus of the paper is concentrated on evaluation of key performance indicators for investigated carbon capture options, the influence of various gasifiers on carbon capture process, optimisation of energy efficiency by heat and power integration, quality specification of captured CO₂. The capture option with minimal energy penalty is based on chemical looping, followed by pre-combustion and post-combustion.     

Evaluation of syngas-based chemical looping applications for hydrogen and power co-generation with CCS

This paper evaluates hydrogen and power co-generation based on coal-gasification fitted with an iron-based chemical looping system for carbon capture and storage (CCS). The paper assess in details the whole hydrogen and power co-production chain based on coal gasification. Investigated plant concepts of syngas-based chemical looping generate about 350–450 MW net electricity with a flexible output of 0–200 MW_th hydrogen (based on lower heating value) with an almost total decarbonisation rate of the coal used.     

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.     

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.     

Environmental evaluation of hydrogen production employing innovative chemical looping technologies – A Romanian case study

A cradle-to-gate life cycle assessment is carried out to evaluate the environmental impact of producing 1 kg of hydrogen implementing innovative chemical looping technologies: chemical looping hydrogen production (CLH), sorption enhanced reforming (SER), and sorption enhanced chemical looping reforming (SECLR). The performance of the looping technologies is compared against conventional hydrogen production without and with CO₂ capture, as well as against green hydrogen production in order to determine the more environmentally-friendly option. Comparing the looping technologies with the reference blue hydrogen production it shows that CLH has a lower environmental burden, presenting smaller values in 9 out of 12 environmental impact indicators. If we confront the looping technologies against each other, CLH shows better performance in 11 out of 12 environmental indicators. As expected, green hydrogen has a much smaller overall environmental impact with the exception of human toxicity, terrestrial ecotoxicity and mineral depletion.     

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.     

Capturing and using CO2 as feedstock with chemical looping and hydrothermal technologies

Chemical looping technology for capturing and hydrothermal processes for conversion of carbon are discussed with focused and critical assessments. The fluidized and stationary reactor systems using solid, including biomass, and gaseous fuels are considered in chemical looping combustion, gasification, and reforming processes. Sustainability is emphasized generally in energy technology and in two chemical looping simulation case studies using coal and natural gas. Conversion of captured carbon to formic acid, methanol, and other chemicals is also discussed in circulating and stationary reactors in hydrothermal processes. This review provides analyses of the major chemical looping technologies for CO₂ capture and hydrothermal processes for carbon conversion so that the appropriate clean energy technology can be selected for a particular process. Combined chemical looping and hydrothermal processes may be feasible and sustainable in carbon capture and conversion and may lead to clean energy technologies using coal, natural gas, and biomass. Copyright © 2014 John Wiley & Sons, Ltd.     

Experimental investigation of hydrogen production integrated methanol steam reforming with middle-temperature solar thermal energy

Developing a hydrogen production method that utilizes solar thermal energy in an effective manner is a great challenge. In this paper we propose a new approach to solar hydrogen production with the integration of methanol steam reforming and middle-temperature solar thermal energy. An experiment on hydrogen production is conducted using a 5-kW solar reactor at 150−300 °C under atmosphere pressure. The 5-kW solar receiver/reactor is fabricated and positioned along the focal line of one-tracking parabolic trough concentrator. As a result, the chemical conversion of methanol can reach levels higher than 90%, and the volumetric concentration of hydrogen in the gas products can account for 66−74% above the solar flux of 580 W/m². The obtained maximum hydrogen yield per mole of methanol is 2.65−2.90 mol, approaching the theoretical maximum value, and the experimentally obtained thermochemical efficiency of solar thermal energy converted into chemical energy is in the range of 30−50%, which is competitive with other high-temperature solar thermochemical processes. A kinetic model of solar-driven methanol steam reforming related to solar flux is also derived based on the experimental data. The promising results demonstrate that this solar-driven hydrogen production method can be feasible in practical applications.     

Assessment of calcium-based chemical looping options for gasification power plants

This paper evaluates various calcium-based chemical looping concepts to be applied in Integrated Gasification Combined Cycle (IGCC) plants for decarbonised energy vectors poly-generation (with emphasis on power generation and hydrogen and power co-generation). Two calcium-based chemical looping configurations were analysed. The first concept is based on post-combustion capture using the flue gases resulted from the power block (combined cycle gas turbine). The second concept is based on pre-combustion capture, the calcium-based chemical looping systems being used simultaneous to capture carbon dioxide (by sorbent enhanced water gas shift) and to concentrate the syngas energy in the form of hydrogen-rich gas.     

Thermodynamic evaluation of hydrogen production from methane

Exergetic and energetic analysis has been utilized to estimate the effect of process design and conditions on the hydrogen purity and yield, exergetic efficiencies and CO₂ avoided. Methane was chosen as a model compound for evaluating single stage separation. Simple steam reforming was considered as the base – case system. The other chemical processes that were considered were steam reforming with CO₂ capture with and without chemical looping of a reactive carbon dioxide removal agent, and steam gasification with both the Boudouard reaction catalyst and the reactive carbon dioxide removal agent with and without the solids regeneration. The information presented clearly demonstrates the differences in efficiencies between the various chemical looping processes for hydrogen generation. The incremental changes in efficiencies as a function of process parameters such as temperature, steam amount, chemical type and amount were estimated. Energy and exergy losses associated with generation of syngas, separation of hydrogen from CO_x as well as exergetic loss associated with emissions are presented. The optimal conditions for each process by minimizing these losses are presented. The majority of the exergy destruction occurs due to the high irreversibility of chemical reactions. The results of this investigation demonstrate the utility of exergy analysis. The paper provides a procedure for the comparison of various technologies for the production of hydrogen from carbon based materials based on First and Second Law Analysis. In addition, two figures of merit, namely the comparative advantage factor and the sustainable advantage factor have been proposed to compare the various hydrogen production methods using carbonaceous fuels.     

A combined thermodynamic and experimental study on chemical‐looping ethanol reforming with carbon dioxide capture for hydrogen generation

Chemical‐looping ethanol reforming with carbon dioxide capture is proposed. It combines chemical‐looping reforming and carbon dioxide capture for pure hydrogen generation from ethanol with inherent separation of carbon dioxide. A thermal analysis of the process using NiO oxygen carrier is performed by simulating reactions using the Gibbs energy minimization method. The promising systems are investigated further with respect to temperature, NiO/C₂H₅OH molar ratio, CaO/C₂H₅OH molar ratio and pressure changes as well as possible carbon formation in the reformer. Favorable operation conditions in the presence of CaO are: pressures around 3 atm, reactor temperatures around 850 K, NiO/C₂H₅OH molar ratio = 3 and CaO/C₂H₅OH = 3. The H₂ yield and thermal efficiency with CaO addition are higher than that without CaO addition, showing that the addition of a CO₂ sorbent in the process increases the H₂ production. Copyright © 2012 John Wiley & Sons, Ltd.     

Hydrogen production from bio-oil: A thermodynamic analysis of sorption-enhanced chemical looping steam reforming

The steam reforming of pyrolysis bio-oil is one proposed route to low carbon hydrogen production, which may be enhanced by combination with advanced steam reforming techniques. The advanced reforming of bio-oil is investigated via a thermodynamic analysis based on the minimisation of Gibbs Energy. Conventional steam reforming (C-SR) is assessed alongside sorption-enhanced steam reforming (SE-SR), chemical looping steam reforming (CLSR) and sorption-enhanced chemical looping steam reforming (SE-CLSR). The selected CO₂ sorbent is CaO(s) and oxygen transfer material (OTM) is Ni/NiO. PEFB bio-oil is modelled as a surrogate mixture and two common model compounds, acetic acid and furfural, are also considered. A process comparison highlights the advantages of sorption-enhancement and chemical looping, including improved purity and yield, and reductions in carbon deposition and process net energy balance.The operating regime of SE-CLSR is evaluated in order to assess the impact of S/C ratio, NiO/C ratio, CaO/C ratio and temperature. Autothermal operation can be achieved for S/C ratios between 1 and 3. In autothermal operation at 30 bar, S/C ratio of 2 gives a yield of 11.8 wt%, and hydrogen purity of 96.9 mol%. Alternatively, if autothermal operation is not a priority, the yield can be improved by reducing the quantity of OTM. The thermodynamic analysis highlights the role of advanced reforming techniques in enhancing the potential of bio-oil as a source of hydrogen.     

Assessment of flexible energy vectors poly-generation based on coal and biomass/solid wastes co-gasification with carbon capture

This paper evaluates biomass and solid wastes co-gasification with coal for energy vectors poly-generation with carbon capture. The evaluated co-gasification cases were evaluated in term of key plant performance indicators for generation of totally or partially decarbonized energy vectors (power, hydrogen, substitute natural gas, liquid fuels by Fischer–Tropsch synthesis). The work streamlines one significant advantage of gasification process, namely the capability to process lower grade fuels on condition of high energy efficiency. Introduction in the evaluated IGCC-based schemes of carbon capture step (based on pre-combustion capture) significantly reduces CO₂ emissions, the carbon capture rate being higher than 90% for decarbonized energy vectors (power and hydrogen) and in the range of 47–60% for partially decarbonized energy vectors (SNG, liquid fuels). Various plant concepts were assessed (e.g. 420–425 MW net power with 0–200 MW_th flexible hydrogen output, 800 MW_th SNG, 700 MW_th liquid fuel, all of them with CCS). The paper evaluates fuel blending for optimizing gasification performance. A detailed techno-economic evaluation for hydrogen and power co-generation with CCS was also presented.     

Comparative study of fuel gas production for SOFC from steam and supercritical-water reforming of bioethanol

Theoretical study of fuel gas (H₂ + CO) production for SOFC from bioethanol was carried out to compare performances between two reforming technologies, including steam reforming (SR) and supercritical-water reforming (SCWR). It demonstrates that the fuel gas productions are comparable among the two reforming systems; however, SCWR requires the operation at much higher temperature and pressure than SR. The maximum hydrogen yield can be obtained at 850 K, atmospheric pressure, ethanol to water molar feed ratio of 1:20 for SR system and at 1300 K, 22.1 MPa, and ethanol to water feed ratio of 1:20 for SCWR. The use of a distillation column to purify the bioethanol feed was proven to improve the fuel conversion efficiency of both systems. The analysis reveals that SCWR is a promising system for fuel production for SOFC when a gas turbine is incorporated to the system for energy recovery. Further, it is not necessary to distil bioethanol to obtain too high ethanol recovery (i.e. >90%) as higher energy consumption at the distillation column could lead to lower overall thermal efficiency.     

Investigation of coal gasification hydrogen and electricity co-production plant with three-reactors chemical looping process

This paper analyzes a novel process for producing hydrogen and electricity from coal, based on chemical looping combustion (CLC) and gas turbine combined cycle, allowing for intrinsic capture of carbon dioxide. The core of the process consists of a three-reactors CLC system, where iron oxide particles are circulated to: (i) oxidize syngas in the fuel reactor (FR) providing a CO₂ stream ready for sequestration after cooling and steam vapor condensation, (ii) reduce steam in the steam reactor (SR) to produce hydrogen, (iii) consume oxygen in the air reactor (AR) from air releasing heat to sustain the thermal balance of the CLC system and to generate electricity. A compacted fluidized bed, composed of two fuel reactors, is proposed here for full conversion of fuel gases in FR. The gasification CLC combined cycle plant for hydrogen and electricity cogeneration with Fe₂O₃/FeAl₂O₄ oxygen carriers was simulated using ASPEN^® PLUS software. The plant consists of a supplementary firing reactor operating up to 1350 °C and three-reactors SR at 815 °C, FR at 900 °C and AR at 1000 °C. The results show that the electricity and hydrogen efficiencies are 14.46% and 36.93%, respectively, including hydrogen compression to 60 bar, CO₂ compression to 121 bar, The CO₂ capture efficiency is 89.62% with a CO₂ emission of 238.9 g/kWh. The system has an electricity efficiency of 10.13% and a hydrogen efficiency of 41.51% without CO₂ emission when supplementary firing is not used. The plant performance is attractive because of high energy conversion efficiency and low CO₂ emission. Key parameters that affect the system performance are also discussed, including the conversion of steam to hydrogen in SR, supplementary firing temperature of the oxygen depleted air from AR, AR operation temperature, the flow of oxygen carriers, and the addition of inert support material to the oxygen carrier.