Conversion of fossil and biomass fuels to electric power and transportation fuels by high efficiency integrated plasma fuel cell (IPFC) energy cycle

The IPFC is a high efficiency energy cycle, which converts fossil and biomass fuel to electricity and co-product hydrogen and liquid transportation fuels (gasoline and diesel). The cycle consists of two basic units, a hydrogen plasma black reactor (HPBR) which converts the carbonaceous fuel feedstock to elemental carbon and hydrogen and CO gas. The carbon is used as fuel in a direct carbon fuel cell (DCFC), which generates electricity, a small part of which is used to power the plasma reactor. The gases are cleaned and water gas shifted for either hydrogen or syngas formation. The hydrogen is separated for production or the syngas is catalytically converted in a Fischer–Tropsch (F–T) reactor to gasoline and/or diesel fuel. Based on the demonstrated efficiencies of each of the component reactors, the overall IPFC thermal efficiency for electricity and hydrogen or transportation fuel is estimated to vary from 70 to 90% depending on the feedstock and the co-product gas or liquid fuel produced. The CO₂ emissions are proportionately reduced and are in concentrated streams directly ready for sequestration. Preliminary cost estimates indicate that IPFC is highly competitive with respect to conventional integrated combined cycle plants (NGCC and IGCC) for production of electricity and hydrogen and transportation fuels.     

Surface modification of carbon fuels for direct carbon fuel cells

The direct carbon fuel cell (DCFC) is a promising power-generation device that has much higher efficiency (80%) and less emissions than conventional coal-fired power plants. Two commercial carbons (activated carbon and carbon black) pre-treated with HNO₃, HCl or air plasma are tested in a DCFC. The correlation between the surface properties and electrochemical performance of the carbon fuels is explored. The HNO₃-treated carbon fuels have the highest electrochemical reactivity in the DCFC due to the largest degree of surface oxygen functional groups. The overall effect on changing the electrochemical reactivity of carbon fuels is in the order HNO₃ > air plasma ≈ HCl. Product gas analysis indicates that complete oxidation of carbon to CO₂ can be achieved at 600–700 °C.     

Recent insights concerning DCFC development: 1998–2012

We present an overview of recent developments of the Direct Carbon Fuel Cell (DCFC) cell and system technology which we believe are key to the worldwide renewal of interest in the DCFC during the last ten years. The importance of understanding and exploiting the co-production of CO and CO₂ are examined. A distinction must be made between, on the one hand, the tendency toward chemical and electrochemical equilibrium and on the other hand the complex effects of chemical and electrochemical inhibition. The tendency toward equilibrium may be very active in the DCFC anode, resulting in high CO/CO₂ ratios at high temperature and/or at low current density, consistent with the Boudouard equilibrium. The complex inhibitive effects tend to produce predominantly CO₂ at moderate temperature and moderate current density. If the DCFC anode is allowed to come close to equilibrium, electrochemical production of CO may result. It is accompanied by a large increase in entropy compensated by absorption of thermal energy. This approach to equilibrium may be desirable, for example, in energy conversion systems where the absorption of thermal energy can be ensured via solar collectors. In that case, the product CO may be electrochemically converted or used for chemical or heating value. Such systems can reach an efficiency of greater than 80%. On the other hand, by inhibiting the Boudouard equilibrium either within the reaction mechanism or in the gas product in contact with carbon, it is possible to promote, even at relatively high temperature (700–750 °C), the 4-electron conversion of carbon to CO₂, resulting in very high conversion efficiency (70–80%). Recent work has pinpointed the conditions under which a DCFC operating at high Coulombic efficiency can be realized. Such a power source of very high energy density, provided it also has sufficient power density, may compete with commercially available batteries and fuel cells in electrical storage and conversion applications. The molecular structure characteristics and kinetics yielding favorable conditions for this type of operation are discussed in detail, together with the optimal operating conditions for this mode of DCFC application.     

Electrochemical oxidation of graphite in an intermediate temperature direct carbon fuel cell based on two-phases electrolyte

As a promising intermediate temperature fuel cell, Direct Carbon Fuel Cell (DCFC) with composite electrolyte composed of Samarium-Doped Ceria (SDC) and a binary carbonate phase (67 mol% Li₂CO₃/33 mol% Na₂CO₃) has a much higher efficiency compared with conventional power suppliers. In the present work, SDC powder has been synthesized by an oxalate co-precipitation process and used as solid support matrix for the composite electrolyte. Single cell with composite electrolyte layer is fabricated by a dry-pressing technique using LiNiO₂/Li₂Na₂CO₃/SDC as cathode and 1:9 (weight ratio) graphite mixture with 67 mol% Li₂CO₃/33 mol% Na₂CO₃ molten carbonate as anode. The cell is tested at 600–750 °C using electrolytical graphite mixture as fuel and O₂/CO₂ mixture as oxidant. A relatively good performance with high power density of 58 mW cm⁻² at 700 °C is achieved for a DCFC using 0.8 mm thick composite electrolyte layer. The sensibility of the 1 cm² DCFC single cell performance to the anode gas nature is also investigated. At temperatures higher than 700 °C, both carbon (C) and carbon monoxide (CO) can be considered as reacting fuel for the DCFC system.     

Enhancing triple-phase boundary at fuel electrode of direct carbon fuel cell using a fuel-filled ceria-coated porous anode

A new type of high-temperature fuel cell using solid carbon as a fuel, which is called a direct carbon fuel cell (DCFC), recently attracts scientific and industrial attention due to its excellent electrochemical efficiency, less production of CO₂, and no need of CO₂ separation. However, the state-of-the-art technology on the DCFC still stays in an idea developing stage, mainly because of fuel-related difficulties: a discontinuous fuel supply and a very limited formation of triple phase boundary. In this study, we focused on how to enhance the formation of triple phase boundary at the fuel electrode: using a porous Ni anode filled with carbon particles to enhance the fuel-electrode physical contact and making the porous anode wettable by ceria coating the anode. We demonstrated for the first time that the two ideas are quite successful, leading to 700% increase in a maximal power density and 500% increase in a maximal current density with respect to the standard case.     

Comparative analysis of energy requirements of CO2 removal from metallurgical fuel gases

The paper presents preliminary results of the analysis concerning a CO₂ removal process, applied to metallurgical fuel gases: blast-furnace gas and Corex gas. The CO₂ removal is realised by the physical absorption process with the Selexol solvent as the absorbing liquid. The analysis is focused on the energy consumption in the case of such installations, when blast-furnace gas or Corex gas are supposed to be treated. The CO₂ removal from metallurgical gases can be attractive from both technological and environmental points of view. Decreased CO₂ content in the gases and increased lower heating value (LHV) results in better conditions for its utilisation e.g. in a gas turbine-based combined heat and power (CHP) plant or direct utilisation within the process, e.g. as an auxiliary fuel or reducing gas in a blast furnace. As the composition, flow rate and LHV of the raw blast furnace and Corex gases differ strongly, the physical absorption installation has different requirements and operation parameters in the two cases. The optimisation leads to minimal energy consumption with the assumed CO₂ removal efficiency. The results indicate which technology of pig-iron production has greater potential in the field of mitigation of greenhouse gas emissions, with respect to the technological possibilities of utilisation of the treated fuel gases.     

Dealing with fuel contaminants in biogas-fed solid oxide fuel cell (SOFC) and molten carbonate fuel cell (MCFC) plants: Degradation of catalytic and electro-catalytic active surfaces and related gas purification methods

Fuel cell and hydrogen technologies are re-gaining momentum in a number of sectors including industrial, tertiary and residential ones. Integrated biogas fuel cell plants in wastewater treatment plants and other bioenergy recovery plants are nowadays on the verge of becoming a clear opportunity for the market entry of high-temperature fuel cells in distributed generation (power production from a few kW to the MW scale).High-temperature fuel cell technologies like molten carbonate fuel cells (MCFCs) and solid oxide fuel cells (SOFCs) are especially fit to operate with carbon fuels due to their (direct or indirect) internal reforming capability. Especially, systems based on SOFC technology show the highest conversion efficiency of gaseous carbon fuels (e.g., natural gas, digester gas, and biomass-derived syngas) into electricity when compared to engines or gas turbines. Also, lower CO₂ emissions and ultra-low emissions of atmospheric contaminants (SO_X, CO, VOC, especially NO_X) are generated per unit of electricity output. Nonetheless, stringent requirements apply regarding fuel purity. The presence of contaminants within the anode fuel stream, even at trace levels (sometimes ppb levels) can reduce the lifetime of key components like the fuel cell stack and reformer. In this work, we review the complex matrix (typology and amount) of different contaminants that is found in different biogas types (anaerobic digestion gas and landfill gas). We analyze the impact of contaminants on the fuel reformer and the SOFC stack to identify the threshold limits of the fuel cell system towards specific contaminants. Finally, technological solutions and related adsorbent materials to remove contaminants in a dedicated clean-up unit upstream of the fuel cell plant are also reviewed.     

A parametric study of fuel cell system efficiency under full and part load operation

Fuel cell technology is an emerging, environmentally friendly energy conversion technology for use in mobile and stationary applications. A contribution to the understanding of fuel cell system efficiency and operation under full and part load is presented in this paper. An analytical, three-parameter model, independent of specific fuel cell system, is developed and important performance parameters defined and discussed. Three useful properties of fuel cells are documented: (i) their ability to produce electric energy with constant — or even increased — efficiency at reduced power (enhanced part power efficiency), (ii) their ability to respond instantaneously to changes in power delivery demands (instantaneous load-following properties), and (iii) their theoretical ability to deliver an exhaust gas consisting of almost pure CO₂ (intrinsic CO₂ separation).     

Mixed ionic electronic conducting perovskite anode for direct carbon fuel cells

The conversion of carbonaceous materials to electricity in a Direct Carbon Fuel Cell (DCFC) offers the most efficient process with theoretical electric efficiency close to 100%. One of the key issues for fuel cells is the continuous availability of the fuel at the triple phase boundaries between fuel, electrode and electrolyte. While this can be easily achieved with the use of a porous fuel electrode (anode) in the case of gaseous fuels, there are serious challenges for the delivery of solid fuels to the triple junctions. In this paper, a novel concept of using mixed ionic electronic conductors (MIEC) as anode materials for DCFCs has been discussed. The lanthanum strontium cobalt ferrite, La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ (LSCF) was chosen as the first generation anode material due to its well known high mixed ionic and electronic conductivities in air. This material has been investigated in detail with respect to its conductivity, phase and microstructural stability in DCFC operating environments. When used both as the anode and cathode in a DCFC, power densities in excess of 50 mW/cm² were obtained at 804 °C in electrolyte supported small button cells with solid carbon as the fuel. The concept of using the same anode and cathode material has also been evaluated in electrolyte supported thick wall tubular cells where power densities around 25 mW/cm² were obtained with carbon fuel at 820 °C in the presence of helium as the purging gas. The concept of using a mixed ionic electronic conducting anode for a solid fuel, to extend the reaction zone for carbon oxidation from anode/electrolyte interface to anode/solid fuel interface, has been demonstrated.     

High efficiency chemical energy conversion system based on a methane catalytic decomposition reaction and two fuel cells: Part I. Process modeling and validation

A highly efficient integrated energy conversion system is built based on a methane catalytic decomposition reactor (MCDR) together with a direct carbon fuel cell (DCFC) and an internal reforming solid oxide fuel cell (IRSOFC). In the MCDR, methane is decomposed to pure carbon and hydrogen. Carbon is used as the fuel of DCFC to generate power and produce pure carbon dioxide. The hydrogen and unconverted methane are used as the fuel in the IRSOFC. A gas turbine cycle is also used to produce more power output from the thermal energy generated in the IRSOFC. The output performance and efficiency of both the DCFC and IRSOFC are investigated and compared by development of exact models of them. It is found that this system has a unique loading flexibility due to the good high-loading property of DCFC and the good low loading property of IRSOFC. The effects of temperature, pressure, current densities, and methane conversion on the performance of the fuel cells and the system are discussed. The CO₂ emission reduction is effective, up to 80%, can be reduced with the proposed system.     

Performance of direct carbon fuel cell

A direct carbon fuel cell (DCFC) is a variation of the molten carbonate fuel cell (MCFC) which converts the chemical energy of carbon directly into electrical energy. Thus, the energy conversion efficiency is very high and correspondingly CO₂ emission is very low for given power output. DCFC as a high temperature fuel cell performs better at elevated temperatures (>800 °C) but because of the corrosive nature of the molten carbonates at elevated temperatures the degradation of cell components becomes an issue when DCFC is operated for an extended period of time.We explored the DCFC performance at lower temperatures (at 700 °C and less) using different sources of carbon, different compositions of electrolytes and some additives on the cathode surface to increase catalytic activity. Experiments showed that with petroleum coke as a fuel at low temperatures the ternary eutectic (43.4 mol % Li₂CO₃ - 31.2 mol% Na₂CO₃ - 25.4 mol % K₂CO₃) spiked by 20 wt % Cs₂CO₃ performed better than any binary or ternary eutectics described in the published work by other researchers. Maximum power output achieved at 700 °C was 49 mW/cm² at a current density of 78 mA/cm² when modified cathode was fed with O₂/CO₂ gases.     

Cycle analysis of low and high H2 utilization SOFC/gas turbine combined cycle for CO2 recovery

A major factor in global warming is CO₂ emission from thermal power plants, which burn fossil fuels. One technology proposed to prevent global warming is CO₂ recovery from combustion flue gas and the sequestration of CO₂ underground or near the ocean bed. Solid oxide fuel cell (SOFC) can produce highly concentrated CO₂, because the reformed fuel gas reacts with oxygen electrochemically without being mixed with air in the SOFC. We therefore propose to operate multi-staged SOFCs with high utilization of reformed fuel to obtain highly concentrated CO₂. In this study, we estimated the performance of multi-staged SOFCs considering H₂ diffusion and the combined cycle efficiency of a multi-staged SOFC/gas turbine/CO₂ recovery power plant. The power generation efficiency of our CO₂ recovery combined cycle is 68.5%, whereas the efficiency of a conventional SOFC/GT cycle with the CO₂ recovery amine process is 57.8%.     

The effects of fuel variability on the electrical performance and durability of a solid oxide fuel cell operating on biohythane

Biohythane is typically composed of 60/30/10 vol% CH₄/CO₂/H₂ and can be produced via two-stage anaerobic digestion of renewable and low carbon biomass with much greater efficiency compared with CH₄/CO₂ biogas. This work investigates the effects of fuel variability on the electrical performance and fuel processing of a commercially available anode supported solid oxide fuel cell (SOFC) operating on biohythane mixtures at 750 °C. Cell electrical performance was characterised using current-voltage curves and electrochemical impedance spectroscopy. Fuel processing was characterised using quadrupole mass spectroscopy. It is shown that when H₂/CO₂ is blended with CH₄ to make biohythane, the SOFC efficiency is significantly increased, high SOFC durability is achieved, and there are considerable savings in CH₄ consumption. Enhanced electrical performance was due to the additional presence of H₂ and promotion of CH₄ dry reforming, the reverse Boudouard and reverse water-gas shift reactions. These processes alleviated carbon deposition and promoted electrochemical oxidation of H₂ as the primary power production pathway. Substituting 50 vol% CH₄ with 25/75 vol% H₂/CO₂ was shown to increase cell power output by 81.6% at 0.8 V compared with pure CH₄. This corresponded to a 3.4-fold increase in the overall energy conversion efficiency and a 72% decrease in CH₄ consumption. A 260 h durability test demonstrated very high cell durability when operating on a typical 60/30/10 vol% CH₄/CO₂/H₂ biohythane mixture under high fuel utilisation due to inhibition of carbon deposition. Overall, this work suggests that decarbonising gas grids by substituting natural gas with renewably produced H₂/CO₂ mixtures (rather than pure H₂ derived from fossil fuels), and utilising in SOFC technology, gives considerable gains in energy conversion efficiency and carbon emissions savings.     

Electrochemical study of composite materials for coal-based direct carbon fuel cell

The efficient conversion of solid carbon fuels into energy by reducing the emission of harmful gases is important for clean environment. In this regards, direct carbon fuel cell (DCFC) is a system that converts solid carbon directly into electrical energy with high thermodynamic efficiency (100%), system efficiency of 80% and half emission of gases compared to conventional coal power plants. This can generate electricity from any carbonaceous fuel such as charcoal, carbon black, carbon fiber, graphite, lignite, bituminous coal and waste materials. In this paper, ternary carbonate-samarium doped ceria (LNK-SDC) electrolyte has been synthesized via co-precipitation technique, while LiNiCuZnFeO (LNCZFO) electrode has been prepared using solid state reaction method. Due to significant ionic conductivity of electrolyte LNK-SDC, it is used in DCFC. Three types of solid carbon (lignite, bituminous, sub-bituminous) are used as fuel to generate power. The X-ray diffraction confirmed the cubic crystalline structure of samarium doped ceria, whereas XRD pattern of LNCZFO showed its composite structure.The proximate and ultimate coal analysis showed that fuel (carbon) with higher carbon content and lower ash content was promising fuel for DCFC. The measured ionic conductivity of LNK-SDC is 0.0998 Scm^?1 and electronic conductivity of LNCZFO is 10.1 Scm^?1 at 700 °C, respectively. A maximum power density of 58 mWcm^?2 is obtained using sub-bituminous fuel.     

Biomass to power conversion in a direct carbon fuel cell

Direct carbon fuel cells (DCFC) offer clear advantages over conventional power generation systems including higher conversion efficiency, low emissions and production of a near pure CO₂ exit stream which can be easily captured for storage. When operated on biomass-derived fuels and combined with carbon capture and storage they have the potential to be a carbon negative technology. Currently most studies relating to DCFC's focus on the use of synthetic high purity fuels. Although of significant academic interest, the high energy requirements for the production of such fuels and high cost would negate the advantages offered by DCFCs over conventional combustion technologies that can produce power from lower-grade fuels. A number of industrial processes (such as pyrolysis or gasification) can produce high carbon containing and low cost chars from biomass sources. This paper describes the operation of a novel solid state direct carbon fuel cell operated on two such commercially available bio-mass derived chars, an agricultural waste derived bio-char used for soil enrichment and coconut char used for the processing of ceramics. Chemical analysis (ICP, XRF), X-ray diffraction and thermo-gravimetric analysis have been used to characterise the fuels. Testing on small button cells showed that it is possible to operate fuel cells directly on low grade unprocessed chars. Although initial power densities were low, significant improvements to cell materials and designs can lead to practical devices. Overall the stability of the fuel cell materials in contact with bio-chars appeared to be good with no phase decomposition of any material observed.     

Effect of contact type between anode and carbonaceous fuels on direct carbon fuel cell reaction characteristics

The contact between the anode and the carbonaceous fuel has a strong effect on the direct carbon fuel cell (DCFC) reaction characteristics. These effects are experimentally investigated by measuring the electrochemical behavior of a detached anode, an anode in physical contact with the fuel and an anode with carbon deposited on the surface in a DCFC. The results show that for the detached type DCFC, the reaction characteristics are closely related to the anode gas. In an Ar atmosphere, the main anode reactions are the electrochemical reaction to produce O₂ and the carbon gasification with the formed O₂. In a CO₂ atmosphere, the main anode reactions are the carbon gasification with CO₂ and the electrochemical oxidization of the formed CO. For the physical contact type DCFC, the anode reaction mechanisms are the same as for the detached type DCFC with no electrochemical oxidization of carbon at the physical contact interface between the carbonaceous fuel and the anode. Thus, the increased contact does not result in better performance. The carbon-deposited type DCFC has better performance with a significant activation polarization due to the electrochemical oxidization of the deposited carbon.     

关于直接碳燃料电池燃料碳的探讨

直接碳燃料电池（Direct Carbon Fuel Cell,DCFC）采用碳作为阳极燃料,热效率远高于氢燃料电池,产物二氧化碳无需提纯就可工业应用或隔离存放,具有转化效率高、清洁、燃料适应性广的特点。文中对直接碳燃料电池的燃料碳进行了探讨,系统地分析了碳的结晶紊乱程度、表面含氧官能团、导电性、灰分、硫分、颗粒尺寸、比表面积以及孔结构对电池性能的影响。     

Investigation of direct carbon conversion at the surface of a YSZ electrolyte in a SOFC

Fuel cells offer a promising way to produce electricity efficiently. In this work, a direct carbon fuel cell (DCFC) based on a solid oxide fuel cell (SOFC) has been investigated, in which solid carbon has been used as fuel in form of a pellet. The DCFC is an interesting technology because it offers the possibility to use, as fuel source, available and abundant raw materials with only minor pretreatment. Moreover, the thermodynamic efficiency slightly exceeds 100% in a wide temperature range due to the positive near-zero value of reaction entropy change. As pure carbon dioxide is produced at the anode, it can be easily captured and sequestered. Direct carbon conversion is competed by the Boudouard reaction, which produces carbon monoxide at high operating temperatures. This reaction is endothermic and leads to a fuel loss. The present paper relates to the contribution of both reactions by a long-term run over about 12 h with a non-porous anode layer.     

Environmental impact of alternative fuel mix in electricity generation in Malaysia

The Fuel Diversification Strategy was incorporated into the Malaysian National Energy Policy in order to achieve a more balanced consumption of fuel, namely gas, hydro, coal and petroleum. The objective of this paper is to evaluate changes in CO_2, SO₂ and NO_x emission due to changes in the fuel mix specified in the Fuel Diversification Strategy. Using the environmental extended Leontief's input–output framework it was found that the fuel mix as envisioned by the Fuel Diversification Strategy generates higher CO_2, SO₂ and NO_x emissions. As such, to ensure a sustainable energy policy, the proposed fuel mix must be accompanied by efficiency gain so that the negative impact on the environment could be mitigated.     

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.