Microwave-mediated noncatalytic synthesis of ethyl levulinate: A green process for fuel additive production

This study developed a new catalyst-free process for producing ethyl levulinate, a biofuel additive. Noncatalytic levulinic acid esterification with ethanol using microwave irradiation (MW) was compared with that using traditional heating (TH) under different reaction conditions. The results demonstrated that the esterification process using MW was more effective than that using TH. A reaction conversion of 90.38% was obtained for the esterification using MW at 473 K and reaction time of 3 hours. Moreover, this study established a model for depicting the kinetics of levulinic acid esterification using MW and TH. A good fit to the data (R² of >.9999) was achieved, indicating the validity of the developed model. The rate constants and pre-exponential factor obtained for the esterification using MW were greater than those obtained using TH. Consequently, the microwave-assisted noncatalytic synthesis is a green and promising method for preparing ethyl levulinate.     

Implications of system expansion for the assessment of well‐to‐wheel CO2 emissions from biomass‐based transportation

In this paper we show the effects of expanding the system when evaluating well‐to‐wheel (WTW) CO₂ emissions for biomass‐based transportation, to include the systems surrounding the biomass conversion system. Four different cases are considered: DME via black liquor gasification (BLG), methanol via gasification of solid biomass, lignocellulosic ethanol and electricity from a biomass integrated gasification combined cycle (BIGCC) used in a battery‐powered electric vehicle (BPEV). All four cases are considered with as well as without carbon capture and storage (CCS). System expansion is used consistently for all flows. The results are compared with results from a conventional WTW study that only uses system expansion for certain co‐product flows. It is shown that when expanding the system, biomass‐based transportation does not necessarily contribute to decreased CO₂ emissions and the results from this study in general indicate considerably lower CO₂ mitigation potential than do the results from the conventional study used for comparison. It is shown that of particular importance are assumptions regarding future biomass use, as by expanding the system, future competition for biomass feedstock can be taken into account by assuming an alternative biomass usage. Assumptions regarding other surrounding systems, such as the transportation and the electricity systems are also shown to be of significance. Of the four studied cases without CCS, BIGCC with the electricity used in a BPEV is the only case that consistently shows a potential for CO₂ reduction when alternative use of biomass is considered. Inclusion of CCS is not a guarantee for achieving CO₂ reduction, and in general the system effects are equivalent or larger than the effects of CCS. DME from BLG generally shows the highest CO₂ emission reduction potential for the biofuel cases. However, neither of these options for biomass‐based transportation can alone meet the needs of the transport sector. Therefore, a broader palette of solutions, including different production routes, different fuels and possibly also CCS, will be needed. Copyright © 2009 John Wiley & Sons, Ltd.     

A review of recent developments in carbon capture utilizing oxy‐fuel combustion in conventional and ion transport membrane systems

Fossil fuels provide a significant fraction of the global energy resources, and this is likely to remain so for several decades. Carbon dioxide (CO₂) emissions have been correlated with climate change, and carbon capture is essential to enable the continuing use of fossil fuels while reducing the emissions of CO₂ into the atmosphere thereby mitigating global climate changes. Among the proposed methods of CO₂ capture, oxyfuel combustion technology provides a promising option, which is applicable to power generation systems. This technology is based on combustion with pure oxygen (O₂) instead of air, resulting in flue gas that consists mainly of CO₂ and water (H₂O), that latter can be separated easily via condensation, while removing other contaminants leaving pure CO₂ for storage. However, fuel combustion in pure O₂ results in intolerably high combustion temperatures. In order to provide the dilution effect of the absent nitrogen (N₂) and to moderate the furnace/combustor temperatures, part of the flue gas is recycled back into the combustion chamber. An efficient source of O₂ is required to make oxy‐combustion a competitive CO₂ capture technology. Conventional O₂ production utilizing the cryogenic distillation process is energetically expensive. Ceramic membranes made from mixed ion‐electronic conducting oxides have received increasing attention because of their potential to mitigate the cost of O₂ production, thus helping to promote these clean energy technologies. Some effort has also been expended in using these membranes to improve the performance of the O₂ separation processes by combining air separation and high‐temperature oxidation into a single chamber. This paper provides a review of the performance of combustors utilizing oxy‐fuel combustion process, materials utilized in ion‐transport membranes and the integration of such reactors in power cycles. The review is focused on carbon capture potential, developments of oxyfuel applications and O₂ separation and combustion in membrane reactors. The recent developments in oxyfuel power cycles are discussed focusing on the main concepts of manipulating exergy flows within each cycle and the reported thermal efficiencies. Copyright © 2010 John Wiley & Sons, Ltd.     

Insights into low-carbon hydrogen production methods: Green,blue and aqua hydrogen

The primary aim of this study is to provide insights into different low-carbon hydrogen production methods. Low-carbon hydrogen includes green hydrogen (hydrogen from renewable electricity), blue hydrogen (hydrogen from fossil fuels with CO₂ emissions reduced by the use of Carbon Capture Use and Storage) and aqua hydrogen (hydrogen from fossil fuels via the new technology). Green hydrogen is an expensive strategy compared to fossil-based hydrogen. Blue hydrogen has some attractive features, but the CCUS technology is high cost and blue hydrogen is not inherently carbon free. Therefore, engineering scientists have been focusing on developing other low-cost and low-carbon hydrogen technology. A new economical technology to extract hydrogen from oil sands (natural bitumen) and oil fields with very low cost and without carbon emissions has been developed and commercialized in Western Canada. Aqua hydrogen is a term we have coined for production of hydrogen from this new hydrogen production technology. Aqua is a color halfway between green and blue and thus represents a form of hydrogen production that does not emit CO₂, like green hydrogen, yet is produced from fossil fuel energy, like blue hydrogen. Unlike CCUS, blue hydrogen, which is clearly compensatory with respect to carbon emissions as it captures, uses and stores produced CO₂, the new production method is transformative in that it does not emit CO₂ in the first place. In order to promote the development of the low-carbon hydrogen economy, the current challenges, future directions and policy recommendations of low-carbon hydrogen production methods including green hydrogen, blue hydrogen, and aqua hydrogen are investigated in the paper.     

Applicability of a TSA/ZrO2 catalytic membrane for the production of ethyl levulinate as raw material of gamma-valerolactone

The aim of this study is to synthesize of ethyl levulinate as raw material by the green catalytic membrane process for the produce of gamma-valerolactone by hydrogenation. Production of zirconium oxide supported tungstosilicic acid loaded hydroxyethyl cellulose catalytic membrane was done by solution casting method. Zirconium oxide supported tungstosilicic acid, which used as the catalyst, was prepared by the wet impregnation method in the laboratory. Catalyst and catalytic membrane were characterized by XRD and SEM. The reaction was carried out in the batch reactor by using catalytic membrane pieces as the catalyst. Optimum conditions were determined as the reaction temperature of 75 °C, molar feed ratio of 6:1, catalyst concentration of 2 wt.% and catalytic membrane amount of 4 wt.%. The conversion value of levulinic acid to ethyl levulinate was obtained as 86% under these conditions and catalytic membrane was used for five times without losing catalytic activity. As a result of the study, catalytic membrane was found as an efficient catalyst for the synthesis of ethyl levulinate.     

Comprehensive evaluation of a CO2‐capturing high‐efficiency power generation system for utilizing waste heat from factories

It is becoming more important to realize CO₂‐capturing power generation systems (PGSs) for drastically decreasing an amount of CO₂ emission into the atmosphere. However, net power generation efficiency (NPGE) of a CO₂‐capturing system has been considered to be greatly deteriorated, since capturing CO₂ requires extra energy. This paper proposes a new CO₂‐capturing PGS that has a high‐efficient NPGE by utilizing waste heat from factories. As an example of a waste heat, exhaust gas with temperature 200°C from refuse incinerator plants is adopted. In the proposed system, the temperature of saturated steam produced by utilizing the waste heat is raised by combusting fuel with the use of pure oxygen in a combustor, and is used as the main working fluid of a gas turbine PGS. It is estimated that the proposed system has a fuel‐to‐electricity NPGE of 59.3%, when turbine inlet temperature (TIT) is assumed to be 1000°C. The economics of the proposed system is also evaluated and the CO₂ reduction cost is estimated to be small; 4.16 U.S. $ t⁻¹ CO₂ compared with 32.1 U.S. $ t⁻¹ CO₂ for a conventional steam turbine PGS. It is shown that CO₂‐capturing is not cost consuming but becomes to be profitable owing to improved power generation characteristics, when its TIT is increased from 1000 to 1200°C. Copyright © 2009 John Wiley & Sons, Ltd.     

Multifracture response to supercritical CO2‐EGS and water‐EGS based on thermo‐hydro‐mechanical coupling method

Hydraulic‐fracturing treatments have become an essential technology for the development of deep hot dry rocks (HDRs). The deep rock formation often contains natural fractures (NFs) at micro and macroscales. In the presence of the NF, the hydraulic‐fracturing process may form a complex fracture network caused by the interaction between hydraulic fractures and NF. In this study, analysis of carbon dioxide (CO₂)‐based enhanced geothermal system (EGS) and water‐based EGS in complex fracture network was performed based on the thermo‐hydro‐mechanical (THM) coupling method, with various rock constitutive models. The complexity of the fracture geometry influences the fluid flow path and heat transfer efficiency of the thermal reservoir. Compared with CO₂‐based EGS, water‐based EGS had an earlier thermal breakthrough with a rapid decline in production temperature. CO₂ can easily gain heat rising its temperature thus reducing the effect of a premature thermal breakthrough. Both CO₂‐based EGS and water‐based EGS are affected by in‐situ stress; the increase in stress ratio improved the fracture permeability but resulted in an early cold thermal breakthrough. When the same injection rate is applied to water‐based EGS and CO₂‐based EGS, water‐based EGS displayed higher injection pressure buildup. Water‐based EGS had higher reservoir deformation area than CO₂‐based EGS, and thermoelastic constitutive model for water‐based EGS showed larger deformed area ratio than thermo‐poroelastic rock model. Furthermore, higher values of rock modulus accelerated the reservoir deformation for water‐based EGS. This study established a novel discussion investigating the performance of CO₂‐based EGS and water‐based EGS in a complex fractured reservoir. The findings from this study will help in deepening the understanding of the mechanisms involved when using CO₂ or water as a working fluid in EGS.     

Nanometallic fuels for transportation: a well‐to‐wheels analysis

Nanometallic iron and aluminium, along with hydrogen and electricity, are among the proposed alternatives to the petroleum‐based fuels for future transportation. The advantages of the metallic fuels appear to be high volumetric energy densities and zero greenhouse gas emissions during the operation of the vehicle. However, nanometallic fuels do not exist in nature, and a well‐to‐wheel analysis of the fuel manufacture‐utilization system is required to quantify the energy consumption and assess the true environmental impact of the proposed alternative. The three‐component nanometallic fuel system consisting of a metal production process, a nanoparticle formulation process and the metal combustion process is analysed in this paper. The energy balance and the environmental impact are estimated for nanometallic iron and aluminium based systems. The sustainability of once‐through systems that do not involve recycle of combustion products is questionable because of resource limitations. A viable system for satisfying the transportation fuel demands will involve the reduction and recycle of the combustion products. A comparison of these nanometallic fuels with gasoline and hydrogen indicates that nanometallic fuels are the least efficient, with primary energy consumption greater than 11 MJ km^?1 compared to 0.625 MJ km^?1 for gasoline and 8.6 MJ km^?1 for hydrogen. The nanometallic fuels will also have the most severe impact of the three, with CO₂‐equivalent emissions of 13.44 billion tons year^?1 for iron and 21.1 billion tons year^?1 for aluminium as compared to approximately 0.8 billion tons year^?1 for gasoline. These emissions from nanometallic fuels are at least an order‐of‐magnitude higher than those for gasoline and hydrogen. The results of the analysis emphasize the need for well‐to‐wheel assessment for determining the true impact of technologies proposed as replacements for the current technologies. Copyright © 2006 John Wiley & Sons, Ltd.     

Ethyl levulinate: A potential bio-based diluent for biodiesel which improves cold flow properties

Biodiesel, defined as mono-alkyl esters of long-chain fatty acids derived from vegetable oils or animal fats, is an attractive renewable fuel alternative to conventional petroleum diesel fuel. Biodiesel produced from oils such as cottonseed oil and poultry fats suffer from extremely poor cold flow properties because of their high saturated fatty acid content. In the current study, Ethyl Levulinate (ethyl 4-oxopentanoate) was investigated as a novel, bio-based cold flow improver for use in biodiesel fuels. The cloud (CP), pour (PP), and cold filter plugging points (CFPP) of biodiesel fuels prepared from cottonseed oil and poultry fat were improved upon addition of ethyl levulinate at 2.5, 5.0, 10.0, and 20.0% (vol). Reductions of 4-5 °C in CP, 3-4 °C in PP and 3 °C in CFPP were observed at 20 vol % ethyl levulinate. The influence of ethyl levulinate on acid value, induction period, kinematic viscosity and flash point was determined. The kinematic viscosities and flash points decreased with increasing content of ethyl levulinate. All samples (≤15 vol % ethyl levulinate) satisfied the ASTM D6751 limit with respect to flash point, but none of the 20 vol % blends were acceptable when compared to the higher EN 14214 specification. Acid value and oxidative stability were essentially unchanged upon addition of ethyl levulinate. In summary, ethyl levulinate appears acceptable as a diluent for biodiesel fuels with high saturated fatty acid content.     

Numerical study of hydrogen‐enriched methane–air combustion under ultra‐lean conditions

The demand for gas turbines that accept a variety of fuels has continuously increased over the last decade. Understanding the effects of varying fuel compositions on combustion characteristics and emissions is critical to designing fuel‐flexible combustors. In this study, the combustion characteristics and emissions of methane and hydrogen‐enriched methane were both experimentally and numerically investigated under ultra‐lean conditions (Ø ≤ 0.5). This study was performed using global mechanisms with a one‐step mechanism by Westbrook and Dryer and a two‐step mechanism with an irreversible and reversible CO/CO₂ step (2sCM1 and 2sCM2). Results show that the 2sCM2 mechanism under‐predicted the temperature, major species, and NO_x by more than 100% under ultra‐lean conditions; thus, we proposed a modified‐2sCM2 mechanism to better simulate the combustion characteristics. The mechanisms of Westbrook, 2sCM1, and modified 2sCM2 predicted the temperature and the CO₂ emission with an average deviation of about 5% from the experimental values. Westbrook and 2sCM1, however, over‐predicted the NO_x emission by approximately 81% and 152%, respectively, as compared with an average under‐prediction of 11% by the modified‐2sCM2 mechanism. The numerical results using the proposed modified‐2sCM2 mechanism shows that the presence of hydrogen in the fuel mixture inhibits the oxidation of methane that led to the formation of unburned hydrocarbons in the flame. We also showed that for any given fuel compositions of H₂/CH₄, there is an optimum equivalence ratio at which the pollutant emissions (CO and NO_x) from the combustor are minimal. Zero CO and 5 ppm NO_x emissions were observed at the optimal equivalence ratio of 0.45 for a fuel mixture containing 30% H₂. The present study provides a basis for ultra‐lean combustion toward achieving zero emissions from a fuel‐flexible combustor. Copyright © 2016 John Wiley & Sons, Ltd.     

Assessment of CO2 storage potential and carbon capture,utilization and storage prospect in China

Carbon capture, utilization and storage (CCUS) is regarded as a very promising technology to reduce CO₂ emission in China, which could improve the contradiction between economic development and environment protection. In order to study the CO₂ storage potential for deploying CCUS projects in China, considering China's special geological features and current national conditions, a new evaluation method of CO₂ storage capacity was proposed using the mass balance approach combined with various CO₂ storage mechanisms in different formations, and the CO₂ storage capacity was calculated in saline aquifer for CO₂-EWR, oil reservoir for CO₂-EOR and coal bed for CO₂-ECBM respectively. The result shows that China has great CO₂ storage potential, which is estimated to be over 1841 Gt. The different features and application prospect of CO₂-EWR, CO₂-EOR and CO₂-ECBM in China were analyzed, which give guidance on critical technologies breakthrough and costs reduction along the CCUS chain. With the joint effort and support by policy and finance, CCUS will make great contribution to the development of low carbon economy for China and the world.     

Oxy‐fuel combustion characteristics and kinetics of microalgae and its mixture with rice straw using thermogravimetric analysis

The thermal behavior of rice straw, microalgae, and their mixture was studied by thermogravimetric analysis (TGA). Co‐combustion of rice straw and microalgae broadened the temperature range of combustion, facilitated ignition, and promoted burnout. The blend ratio of microalgae should be less than or equal to 10% in a 20%O₂/80%N₂ atmosphere and 30% in a 20%O₂/80%CO₂ atmosphere to reach a higher comprehensive combustion index (CCI) value than the individual fuels. The co‐combustion with a small ratio of microalgae could remedy partial negative effects on combustion performance caused by the replacement of N₂ using CO₂. The interaction of blends depended on the atmosphere and temperature range. The prediction of the combustion performance of blends by a weighted sum of individual fuels worked better in an O₂/CO₂ atmosphere at low temperatures, while better in an O₂/N₂ atmosphere at high temperatures. The simulation using the model which contained 2 parallel multi‐order reactions matched with the thermogravimetric curves well, and blending reduced activation energies of the second stage.     

The role of policy instruments for promoting combined heat and power production with low CO2 emissions in district heating systems

Policy instruments clearly influence the choice of production technologies and fuels in large energy systems, including district heating networks. Current Swedish policy instruments aim at promoting the use of biofuel in district heating systems, and at promoting electric power generation from renewable energy sources. However, there is increasing pressure to harmonize energy policy instruments within the EU. In addition, natural gas based combined cycle technology has emerged as the technology of choice in the power generation sector in the EU. This study aims at exploring the role of policy instruments for promoting the use of low CO₂ emissions fuels in high performance combined heat and power systems in the district heating sector. The paper presents the results of a case study for a Swedish district heating network where new large size natural gas combined cycle (NGCC) combined heat and power (CHP) is being built. Given the aim of current Swedish energy policy, it is assumed that it could be of interest in the future to integrate a biofuel gasifier to the CHP plant and co‐fire the gasified biofuel in the gas turbine unit, thereby reducing usage of fossil fuel. The goals of the study are to evaluate which policy instruments promote construction of the planned NGCC CHP unit, the technical performance of an integrated biofuelled pressurized gasifier with or without dryer on plant site, and which combination of policy instruments promote integration of a biofuel gasifier to the planned CHP unit. The power plant simulation program GateCycle was used for plant performance evaluation. The results show that current Swedish energy policy instruments favour investing in the NGCC CHP unit. The corresponding cost of electricity (COE) from the NGCC CHP unit is estimated at 253 SEK MWh^?1, which is lower than the reference power price of 284 SEK MWh^?1. Investing in the NGCC CHP unit is also shown to be attractive if a CO₂ trading system is implemented. If the value of tradable emission permits (TEP) in such as system is 250 SEK tonne^?1, COE is 353 SEK MWh^?1 compared to the reference power price of 384 SEK MWh^?1. It is possible to integrate a pressurized biofuel gasifier to the NGCC CHP plant without any major re‐design of the combined cycle provided that the maximum degree of co‐firing is limited to 27–38% (energy basis) product gas, depending on the design of the gasifier system. There are many parameters that affect the economic performance of an integrated biofuel gasifier for product gas co‐firing of a NGCC CHP plant. The premium value of the co‐generated renewable electricity and the value of TEPs are very important parameters. Assuming a future CO₂ trading system with a TEP value of 250 SEK tonne^?1 and a premium value of renewable electricity of 200 SEK MWh^?1 COE from a CHP plant with an integrated biofuelled gasifier could be 336 SEK MWh^?1, which is lower than both the reference market electric power price and COE for the plant operating on natural gas alone. Copyright © 2005 John Wiley & Sons, Ltd.     

Lignite‐fired air‐blown IGCC systems with pre‐combustion CO2 capture

Detailed analyses based on mass and energy balances of lignite‐fired air‐blown gasification‐based combined cycles with CO₂ pre‐combustion capture are presented and discussed in this work. The thermodynamic assessment is carried out with a proprietary code integrated with Aspen Plus^® to carefully simulate the selective removal of both H₂S and CO₂ in the acid gas removal station. The work focuses on power plants with two combustion turbines, with lower and higher turbine inlet temperatures, respectively, as topping cycle. A high‐moisture lignite, partially dried before feeding the air‐blown gasification system, is used as fuel input. Because the raw lignite presents a very low amount of sulfur, a particular technique consisting of an acid gas recycle to the absorber, is adopted to fulfill the requirements related to the presence of H₂S in the stream to the Claus plant and in the CO₂‐rich stream to storage. Despite the operation of the H₂S removal section representing a significant issue, the impact on the performance of the power plant is limited. The calculations show that a significant lignite pre‐drying is necessary to achieve higher efficiency in case of CO₂ capture. In particular, considering a wide range (10–30 wt.%) of residual moisture in the dried lignite, higher heating value (HHV) efficiency presents a decreasing trend, with maximum values of 35.15% and 37.12% depending on the type of the combustion turbine, even though the higher the residual moisture in the dried coal, the lower the extraction of steam from the heat recovery steam cycle. On the other hand, introducing the specific primary energy consumption for CO₂ avoided (SPECCA) as a measure of the energy cost related to CO₂ capture, lower values were predicted when gasifying dried lignite with higher residual moisture content. In particular, a SPECCA value as low as 2.69 MJ/kg_CO2 was calculated when gasifying lignite with the highest (30 wt.%) residual moisture content in a power plant with the advanced combustion turbine. Ultimately, focusing on the power plants with the advanced combustion turbine, air‐blown gasification of lignite brings about a reduction in HHV efficiency equal to almost 1.5 to 2.8 percentage points, depending on the residual moisture in the dried lignite, if compared with similar cases where bituminous coal is used as fuel input. Copyright © 2016 John Wiley & Sons, Ltd.     

Evaluation of Mg‐MOF‐74 for post‐combustion carbon dioxide capture through pressure swing adsorption

This paper presents a computational study of an energy‐efficient technique for post‐combustion CO₂ capture using novel material, namely, Mg‐MOF‐74, using pressure swing adsorption (PSA) processes. A detailed one‐dimensional, transient mathematical model has been formulated to include the heat and mass transfer, the pressure drop and multicomponent mass diffusion. The PSA model has been further extended by incorporating a heat regenerating process to enhance CO₂ sequestration. The heat dissipated during adsorption is stored in packed sand bed and released during desorption step for heating purpose. The model has been implemented on a MATLAB program using second‐order discretization. Validation of the model was performed using a complete experimental data set for CO₂ sequestration using zeolite 13X. Simulation of the PSA experiment on fixed bed has been carried out to evaluate the capacity of Mg‐MOF‐74 for CO₂ capture with varying feed gas temperature of 28 and 100 °C, varying pressurization and purge times and heat regeneration. It was discovered that the PSA process with heat regeneration system might be advantageous because it achieves equivalent amount of CO₂ sequestration in fewer PSA cycles compared with PSA without heat regeneration system. Based on the simulated conditions, CO₂ recovery with Mg‐MOF‐74 gives high percentage purity (above 98%) for the captured CO₂. Copyright © 2015 John Wiley & Sons, Ltd.     

The green metric evaluation and synthesis of diesel-blend compounds from biomass derived levulinic acid in supercritical carbon dioxide

Levulinate compounds are the biomass derived important energy products which are primarily used as diesel-blending components. These levulinates are the oxygenated fuel additive which promote complete combustion of fuel and reduces emission of pollutants like particulate matters and nitrogen oxides. In the present study, we have investigated sustainable synthesis of biomass derived levulinate compounds catalyzed by Cal B lipase in supercritical carbon dioxide (SC-CO₂) as a green biocatalyst in green reaction media which provided an excellent mass yield. Various reaction parameters were optimized in details such as butanol, levulinic acid, biocatalyst, co-solvent, temperature and pressure to obtain 99% mass yield of the desired product. Moreover various green metric parameters (e.g. E-factor, carbon efficiency and mass productivity) of present methodology were evaluated. The green metrics evaluation suggested that developed procedure is a promising and a greener alternative as compared to various reported conventional synthetic protocols. The biocatalyst was efficiently recycled up to the five cycles. Moreover, the developed protocol can be used for synthesis of various industrially important levulinate compounds which also provided excellent mass yield. Thus, the present protocol demonstrated (i) robust biocatalytic application for transformation of renewable biomass derived levulinic acid (LVA) into value added chemicals and (ii) various green metric evaluation study for the sustainability.     

Oxy‐fuel combustion technology: current status,applications, and trends

The increased level of emissions of carbon dioxide into the atmosphere due to burning of fossil fuels represents one of the main barriers toward the reduction of greenhouse gases and the control of global warming. In the last decades, the use of renewable and clean sources of energies such as solar and wind energies has been increased extensively. However, due to the tremendously increasing world energy demand, fossil fuels would continue in use for decades which necessitates the integration of carbon capture technologies (CCTs) in power plants. These technologies include oxycombustion, pre‐combustion, and post‐combustion carbon capture. Oxycombustion technology is one of the most promising carbon capture technologies as it can be applied with slight modifications to existing power plants or to new power plants. In this technology, fuel is burned using an oxidizer mixture of pure oxygen plus recycled exhaust gases (consists mainly of CO₂). The oxycombustion process results in highly CO₂‐concentrated exhaust gases, which facilitates the capture process of CO₂ after H₂O condensation. The captured CO₂ can be used for industrial applications or can be sequestrated. The current work reviews the current status of oxycombustion technology and its applications in existing conventional combustion systems (including gas turbines and boilers) and novel oxygen transport reactors (OTRs). The review starts with an introduction to the available CCTs with emphasis on their different applications and limitations of use, followed by a review on oxycombustion applications in different combustion systems utilizing gaseous, liquid, and coal fuels. The current status and technology readiness level of oxycombustion technology is discussed. The novel application of oxycombustion technology in OTRs is analyzed in some details. The analyses of OTRs include oxygen permeation technique, fabrication of oxygen transport membranes (OTMs), calculation of oxygen permeation flux, and coupling between oxygen separation and oxycombustion of fuel within the same unit called OTR. The oxycombustion process inside OTR is analyzed considering coal and gaseous fuels. The future trends of oxycombustion technology are itemized and discussed in details in the present study including: (i) ITMs for syngas production; (ii) combustion utilizing liquid fuels in OTRs; (iii) oxy‐combustion integrated power plants and (iv) third generation technologies for CO₂ capture. Techno‐economic analysis of oxycombustion integrated systems is also discussed trying to assess the future prospects of this technology. Copyright © 2017 John Wiley & Sons, Ltd.     

3D graphene from CO2 and K as an excellent counter electrode for dye‐sensitized solar cells

3D graphene, which was synthesized directly from CO₂ via its exothermic reaction with liquid K, exhibited excellent performance as a counter electrode for a dye‐sensitized solar cell (DSSC). The DSSC has achieved a high power conversion efficiency of 8.25%, which is 10 times larger than that (0.74%) of a DSSC with a counter electrode of the regular graphene synthesized via chemical exfoliation of graphite. The efficiency is even higher than that (7.73%) of a dye‐sensitized solar cell with an expensive standard Pt counter electrode. This work provides a novel approach to utilize a greenhouse gas for DSSCs.     

Clean hydrogen generation and storage strategies via CO2 utilization into chemicals and fuels: A review

Hydrogen becomes one of the most clean energy sources. The major issues on hydrogen are lack of practical clean and high‐temperature processes and possible practical storage of clean hydrogen. An energy intensive of clean hydrogen storage via chemical and liquid fuel production route is the current demand. This article reviewed the most recent research for hydrogen (H₂) production by using several methods, such as thermochemical process, thermal decomposition, biological approaches, electrolysis, and photocatalytic method. H₂ storage types, including physical and chemical approaches, were also reviewed. The produced H₂ was stored as valuable chemicals and fuels via CO₂ hydrogenation reaction. Reactor designs are the illustrated number of design ranging from the fixed bed to the continuous stirred tank reactor. Catalyst type, catalytic system, and the related mechanism of CO₂ hydrogenation reaction to form alcohol, alkanes, and carboxylic acid were also discussed in detail.     

CO2 gasification characteristics of nascent pyrolyzed particles from coals and oil shale

In this work, the co‐pyrolysis characteristics of oil shale with two typical coals, bitumite and lignite, and the co‐gasification characteristics of the mixture pyrolyzed fuels were studied via thermo‐gravimetric analysis. The individual fuels and mixture fuels were first pyrolysis in N₂ atmosphere to specified temperature (450, 550, and 620 °C) at the heating rate of 20, 30 and 40 °C/min, respectively, and then maintained at the given temperature for 20 min before converted to CO₂ ambient to conduct the CO₂ gasification tests. The kinetic behavior and effects of both fuel types and pyrolysis temperature were investigated. The shoulder peak at around 550 °C observed in the derivative of weight loss derivative thermogravimetry analysis (DTG) curve during the pyrolysis of oil shale has confirmed the existence of specific reactions of oil shale at around 550 °C that leads to a sharp trough in the differential curves of co‐pyrolysis with coals and the unusual change in activation energies of gasification. In isothermal pyrolysis stage, oil shale lost its vast majority of organic matters at the temperature lower than 550 °C. The escape of pyrolysis gas and liquids in the coals is much harder than that in oil shale. The interaction between oil shale and bitumite was too weak to discriminate both in the pyrolysis and CO₂ gasification process. The variation of the particle surface structure caused by the releasing of volatile gases is strongly affected by the reaction rate and temperature. Quick volatile decomposition and gas releasing lead to the increase of surface area, decrease of the average pore diameter as well as the uniformization of the pore structure, while the higher temperature results in the blockade and merging of fine pores. The two factors lead to the greatest mass loss rate in the pyrolyzed particles obtained at 550 °C in temperature programmed CO₂ gasification stage. Two model‐free methods, Friedman method and Flynn–Wall–Ozawa method, were used to extract kinetic parameters from the experimentally determined pyrolyzed fuel conversions. The volatile contend has a significant influence on the fixed carbon conversion during the partially pyrolyzed particles' CO₂ gasification. In this study, significant interactions existed in co‐thermal utilization, both pyrolysis and CO₂ gasification, of oil shale and lignite. It is therefore surmised that co‐gasification of pyrolyzed lignite and oil shale may represent a feasible, practical route to high‐efficiency utilization of these fuels. Copyright © 2017 John Wiley & Sons, Ltd.