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.     

Solar-driven novel methane reforming with carbon looping for hydrogen production

As a renewable source, solar energy plays an important role in meeting energy demand for human beings and in relieving global warming. In this paper, the concentrated solar heat is utilized to drive the high-endothermic methane reforming with carbon looping. In so doing, the process increases the utilization of CO₂ and reduces the carbon emissions as well as saves the extra fuel consumption for combustion, leading to high efficiency of energy utilization. By optimizing this proposed system, the energy efficiency can reach approximate 67.13% with simultaneously reducing CO₂ emissions by 34.98% compared with SMR process. Exergy analysis is used to assess the location of irreversibility within process. The maximal part of exergy destroyer was localized in reformer with a contribution of 68%. In addition, the effects of hourly variation of direct normal irradiation on thermodynamic performance and methane conversion on the four typical days (spring equinox, summer solstice, autumn equinox, winter solstice) were analyzed in this work. The current work might be insightful for solar-hydrogen production field.     

Thermodynamic possibilities and constraints for pure hydrogen production by iron based chemical looping process at lower temperatures

Iron offers the possibility of transformation of a syngas or gaseous hydrocarbons into hydrogen by a cycling process of iron oxide reduction (e.g. by hydrocarbons) and release of hydrogen by steam oxidation. From the thermodynamic and chemical equilibrium point of view, the reduction of magnetite by hydrogen, CO, CH₄ and a model syngas (mixtures CO + H₂ or H₂ + CO + CO₂) and oxidation of iron by steam has been studied. Attention was concentrated not only on convenient conditions for reduction of Fe₃O₄ to iron at temperatures 400–800 K but also on the possible formation of undesired soot, Fe₃C and iron carbonate as precursors for carbon monoxide and carbon dioxide formation in the steam oxidation step. Reduction of magnetite at low temperatures requires a relatively high H₂/H₂O ratio, increasing with decreasing temperature. Reduction of iron oxide by CO is complicated by soot and Fe₃C formation. At lower temperatures and higher CO₂ concentrations in the reducing gas, the possibility of FeCO₃ formation must be taken into account. The purity of the hydrogen produced depends on the amount of soot, Fe₃C and FeCO₃ in the iron after the reduction step. Magnetite reduction is the more difficult stage in the looping process. Pressurized conditions during the reduction step will enhance formation of soot and carbon containing iron compounds.     

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.     

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 of hydrogen and power co-generation system based on chemical looping hydrogen generation of coal

An integrated hydrogen and power co-generation system based on slurry-feed coal gasification and chemical looping hydrogen generation (CLH) was proposed with Shenhua coal as fuel and Fe₂O₃/MgAl₂O₄ as an oxygen carrier. The sensitivity analyses of the main units of the system were carried out respectively to optimize the parameters. The syngas can be converted completely in the fuel reactor, and both of the fuel reactor and steam reactor can maintain heat balance. The purity of hydrogen produced after water condensation is 100%. The energy and exergy analyses of the proposed system were studied. Pinch technology was adopted to get a reasonable design of the heat transfer network, and it is found pinch point appears at the hot side temperature of 224.7 °C. At the given status of the proposed system, the hydrogen yield is 1040.11 kg·h⁻¹ and the CO₂ capture rate is 94.56%. At the same time, its energy and exergy efficiencies are 46.21% and 47.22%, respectively. According to exergy analysis, the degree of exergy destruction is ranked. The gasifier unit has the most serious exergy destruction, followed by chemical looping hydrogen generation unit and the heat recovery steam generator unit.     

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.     

Development and techno-economic analyses of a novel hydrogen production process via chemical looping

In this work, a novel hydrogen production process (Integrated Chemical Looping Water Splitting “ICLWS”) has been developed. The modelled process has been optimised via heat integration between the main process units. The effects of the key process variables (i.e. the oxygen carrier-to-fuel ratio, steam flow rate and discharged gas temperature) on the behaviour of the reducer and oxidiser reactors were investigated. The thermal and exergy efficiencies of the process were studied and compared against a conventional steam-methane reforming (SMR) process. Finally, the economic feasibility of the process was evaluated based on the corresponding CAPEX, OPEX and first-year plant cost per kg of the hydrogen produced. The thermal efficiency of the ICLWS process was improved by 31.1% compared to the baseline (Chemical Looping Water Splitting without heat integration) process. The hydrogen efficiency and the effective efficiencies were also higher by 11.7% and 11.9%, respectively compared to the SMR process. The sensitivity analysis showed that the oxygen carrier–to-methane and -steam ratios enhanced the discharged gas and solid conversions from both the reducer and oxidiser. Unlike for the oxidiser, the temperature of the discharged gas and solids from the reducer had an impact on the gas and solid conversion. The economic evaluation of the process indicated hydrogen production costs of $1.41 and $1.62 per kilogram of hydrogen produced for Fe-based oxygen carriers supported by ZrO₂ and MgAl₂O₄, respectively - 14% and 1.2% lower for the SMR process H₂ production costs respectively.     

Evaluation of iron based chemical looping for hydrogen and electricity co-production by gasification process with carbon capture and storage

Integrated Gasification Combined Cycle (IGCC) is one of power generation technologies having the highest potential for carbon capture with low penalties in efficiency and cost. Syngas produced by gasification can be decarbonised using chemical looping methods in which an oxygen carrier (usually a metallic oxide) is recycled between the syngas oxidation reactor (fuel reactor) and the chemical agent oxidation reactor (steam reactor). In this way, the resulted carbon dioxide is inherently separated from the other products of combustion and the syngas energy is transferred to an almost pure hydrogen stream suitable to be used not only for power generation but also for transport sector (PEM fuel cells).     

Chemical looping gasification for hydrogen production: A comparison of two unique processes simulated using ASPEN Plus

The research compares the simulations of two chemical looping gasification (CLG) types using the ASPEN Plus simulation software for the production of H₂. The simulated biomass type was poultry litter (PL). The first CLG type used in situ CO₂ capture utilizing a CaO sorbent, coupled with steam utilization for tar reforming, allowing for the production of a CO₂-rich stream for sequestration. Near-total sorbent recovery and recycle was achieved via the CO₂ desorption process. The second type utilized iron-based oxygen carriers in reduction–oxidation cycles to achieve 99.8% Fe₃O₄ carrier recovery and higher syngas yields. Temperature and pressure sensitivity analyses were conducted on the main reactors to determine optimal operating conditions. The optimal temperatures ranged from 500 to 1250 °C depending on the simulation and reactor type. Atmospheric pressure proved optimal in all cases except for the reducer and oxidizer in the iron-based CLG type, which operated at high pressure. This CLG simulation generated the most syngas in absolute terms (2.54 versus 0.79 kmol/kmol PL), while the CO₂ capture simulation generated much more H₂-rich syngas (92.45 mol-% compared to 62.94 mol-% H₂).     

Steam reforming of technical bioethanol for hydrogen production

Essentially all work on ethanol steam reforming so far has been carried out using simulated bioethanol feedstocks, which means pure ethanol mixed with water. However, technical bioethanol consists of a lot of different components including sugars, which cannot be easily vaporized and steam reformed. For ethanol steam reforming to be of practical interest, it is important to avoid the energy-intensive purification steps to fuel grade ethanol. Therefore, it is imperative to analyze how technical bioethanol, with the relevant impurities, reacts during the steam reforming process. We show how three different distillation fractions of technical 2nd generation bioethanol, produced in a pilot plant, influence the performance of nickel- and ruthenium-based catalysts during steam reforming, and we discuss what is required to obtain high activity and long catalyst lifetime. We conclude that the use of technical bioethanol will result in a faster catalyst deactivation than what is observed when using pure ethanol–water mixtures because of contaminants remaining in the feed. However, the initial activity of the catalysts are not affected by this, hence it is important to not only focus on catalyst activity but rather on the lifetime of the catalyst.     

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.     

Life cycle assessment of hydrogen production by methane decomposition using carbonaceous catalysts

Methane decomposition to yield hydrogen and carbon (CH₄ ? 2H₂ + C) is one of the cleanest alternatives, free of CO₂ emissions, for producing hydrogen from fossil fuels. This reaction can be catalyzed by metals, although they suffer a fast deactivation process, or by carbonaceous materials, which present the advantage of producing the catalyst from the carbon obtained in the reaction. In this work, the environmental performance of methane decomposition catalyzed by carbonaceous catalysts has been evaluated through Life Cycle Assessment tools, comparing it to other decomposition processes and steam methane reforming coupled to carbon capture systems. The results obtained showed that the decomposition using the autogenerated carbonaceous as catalyst is the best option when reaction conversions higher than 65% are attained. These were confirmed by 2015 and 2030 forecastings. Moreover, its environmental performance is highly increased when the produced carbon is used in other commercial applications. Thus, for a methane conversion of 70%, the application of 50% of the produced carbon would lead to a virtually zero-emissions process.     

Renewable hydrogen production concepts from bioethanol reforming with carbon capture

This paper is assessing the hydrogen production from bioethanol at industrial scale (100000 Nm³/h hydrogen equivalent to 300 MW thermal) with carbon capture. Three carbon capture designs were investigated, one based on pre-combustion capture using chemical gas–liquid absorption and two based on chemical looping (one based on syngas and one using direct bioethanol looping). The carbon capture options were compared with the similar designs without carbon capture. The designs were simulated to produce mass and energy balances for quantification of key performance indicators. A particular accent is put on assessment of reforming technologies (steam and oxygen-blown autothermal reforming) and chemical looping units, process integration issues of carbon capture step within the plant, modelling and simulation of whole plant, thermal and power integration of various plant sub-systems by pinch analysis. The results for chemical looping designs (either syngas-based or direct bioethanol) show promising energy efficiency coupled with total carbon capture rate.     

High-pressure hydrogen production with inherent sequestration of a pure carbon dioxide stream via fixed bed chemical looping

The proof of concept for the production of pure pressurized hydrogen from hydrocarbons in combination with the sequestration of a pure stream of carbon dioxide with the reformer steam iron cycle is presented. The iron oxide based oxygen carrier (95% Fe₂O₃, 5% Al₂O₃) is reduced with syngas and oxidized with steam at 1023 K. The carbon dioxide separation is achieved via partial reduction of the oxygen carrier from Fe₂O₃ to Fe₃O₄ yielding thermodynamically to a product gas only containing CO₂ and H₂O. By the subsequent condensation of steam, pure CO₂ is sequestrated. After each steam oxidation phase, an air oxidation was applied to restore the oxygen carrier to hematite level. Product gas pressures of up to 30.1 bar and hydrogen purities exceeding 99% were achieved via steam oxidations. The main impurities in the product gas are carbon monoxide and carbon dioxide, which originate from solid carbon depositions or from stored carbonaceous molecules inside the pores of the contact mass. The oxygen carrier samples were characterized using elemental analysis, BET surface area measurement, XRD powder diffraction, SEM and light microscopy. The maximum pressure of 95 bar was demonstrated for hydrogen production in the steam oxidation phase after the full oxygen carrier reduction, significantly reducing the energy demand for compressors in mobility applications.     

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%.     

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%.     

Effect of molar ratio of water / ethanol on hydrogen selectivity in catalytic production of hydrogen using steam reforming of ethanol

As fossil energy resources are shrinking, the increase in global energy needs and environmental pollution paved the way to the search for new and renewable energy resources. Therefore, the future of energy technology is being built on the use of hydrogen, which is one of the cleanest and most efficient renewable energy sources, and steam reforming is becoming the utmost method to produce hydrogen. This study focuses on the operation condition of steam reforming of ethanol on catalyst materials, which were shaped using active metals such as Ni, Cu and Cs and supporting materials which were activated by carbon and LiAlO₂. These catalyst materials were tested to produce hydrogen gas using different water/ethanol mole ratio at different temperatures and a constant feed flow rate. The evaluation regarding hydrogen selectivity results and the percentage of hydrogen in the products revealed that NiCuCs/LiAlO₂ catalyst showed the highest performance at all water/ethanol ratios and temperatures between 300 and 600 °C.     

Process simulation and techno-economic assessment of SER steam gasification for hydrogen production

In the SER (sorption enhanced reforming) gasification process a nitrogen-free, high calorific product gas can be produced. In addition, due to low gasification temperatures of 600–750 °C and the use of limestone as bed material, in-situ CO₂ capture is possible, leading to a hydrogen-rich and carbon-lean product gas. In this paper, results from a bubbling fluidised bed gasification model are compared to results of process demonstration tests in a 200 kW_th pilot plant.Based upon that, a concept for the hydrogen production via biomass SER gasification is studied in terms of efficiency and feasibility. Capital and operational expenditures as well as hydrogen production costs are calculated in a techno-economic assessment study. Furthermore, market framework conditions are discussed under which an economic hydrogen production via SER gasification is possible.