Investigation of NiO/NiAl2O4 oxygen carriers for chemical-looping combustion produced by spray-drying

Chemical-looping combustion is a novel combustion technology with inherent separation of the greenhouse gas CO₂. The technology uses circulating oxygen carriers to transfer oxygen from the combustion air to the fuel. In this paper, oxygen carriers based on commercially available NiO and α-Al₂O₃ were prepared using the industrial spray-drying method, and compared with particles prepared by freeze-granulation. The materials were investigated under alternating oxidizing and reducing conditions in a laboratory fluidized bed, thus simulating the cyclic conditions of a chemical-looping combustion system. The particles produced by spray-drying displayed a remarkable similarity to the freeze-granulated oxygen carriers, with high reactivity when the bed was fluidized and similar physical properties when sintered at the same temperature. This is an important result as it shows that the scaling-up from a laboratory production method, i.e. freeze-granulation, to a commercial method suitable for large-scale production, i.e. spray-drying, did not involve any unexpected difficulties. A difference noticed between the spray-dried and freeze-granulated particles was the sphericity. Whereas the freeze-granulated particles showed near perfect sphericity, a large portion of the spray-dried particles had hollow interiors. Defluidization was most likely to occur for highly reduced particles, at low gas velocities. The apparent density and crushing strength of the oxygen carriers could be increased either by increasing the sintering temperature or by increasing the sintering time. However, the fuel conversion was fairly unchanged when the sintering temperature was increased but was clearly improved when the sintering time was increased.     

Avoidance of death and injury through mionitoring of dams and flood evacuation in Essex, Connecticut, June 1982

During a period of heavy ranfall in Essex, Connecticut, on 4th and 5th June 1982, dams in the town along the Fall River were monitored for signs of braks. The observation of water spilling over one of teh dams at 10 p.m. in 5th June ld to the decision to evacuate community rsidents. The notification and avacuation process was conducted by the cvolunteer fire department over a two-hour periopd. At 12.30 a.m 6th June, the upper dam on the Fall River gave way, rsulting in a rapidly moving floodwave which sequentially destroyed four additional dams along the river. Although there was extensive property damage, gthere were no serious injuries and no deaths. The responsible actons of the town officials in monitoring the dams during the period of heavy rainfall permitted the evacuation order to be given in sufficient time to evacuate the residnts. The success of the evacuation was the result of good communication, trust, and co-operation between town officials and the community.     

Leachability testing of sludge from street gullies.

Sludge from gullies, on two types of streets with different traffic intensity, was investigated using two recommended EU methods for leachability testing of waste: a two-stage batch test and an up-flow percolation test. The main purpose of this investigation was to gain more knowledge about these leaching test methods to be able to make future decisions on the general applicability of the proposed tests. A number of parameters were determined in the sludge as well as in the eluates obtained from the two leaching tests. These include pH, conductivity, dissolved organic carbon and inorganic ions as chloride ions. A number of metals as Cd, Cr, Cu, Hg, Ni and Zn, were determined by inductive coupled plasmamass spectrometry and organic compounds were screened by high performance liquid chromatography-diode array UV detection and gas chromatography-mass spectrometry. It was found that the concentrations of metals and organic compounds in the sludge were several orders of magnitudes higher than the actual eluate concentrations. For all metals the concentrations were well below the proposed limit values for non-hazardous waste included in the Council decision document 2003/33/EC. Generally, concentrations obtained in batch test were equal or higher than from percolation tests. The repeatability of the percolation and the batch test were in average 28 and 17%, respectively.     

Chemical-looping with oxygen uncoupling for combustion of solid fuels

Chemical-looping with oxygen uncoupling (CLOU) is a novel method to burn solid fuels in gas-phase oxygen without the need for an energy intensive air separation unit. The carbon dioxide from the combustion is inherently separated from the rest of the flue gases. CLOU is based on chemical-looping combustion (CLC) and involves three steps in two reactors, one air reactor where a metal oxide captures oxygen from the combustion air (step 1), and a fuel reactor where the metal oxide releases oxygen in the gas-phase (step 2) and where this gas-phase oxygen reacts with a fuel (step 3). In other proposed schemes for using chemical-looping combustion of solid fuels there is a need for an intermediate gasification step of the char with steam or carbon dioxide to form reactive gaseous compounds which then react with the oxygen carrier particles. The gasification of char with H₂O and CO₂ is inherently slow, resulting in slow overall rates of reaction. This slow gasification is avoided in the proposed process, since there is no intermediate gasification step needed and the char reacts directly with gas-phase oxygen. The process demands an oxygen carrier which has the ability to react with the oxygen in the combustion air in the air reactor but which decomposes to a reduced metal oxide and gas-phase oxygen in the fuel reactor. Three metal oxide systems with suitable thermodynamic properties have been identified, and a thermal analysis has shown that Mn₂O₃/Mn₃O₄ and CuO/Cu₂O have suitable thermodynamic properties, although Co₃O₄/CoO may also be a possibility. However, the latter system has the disadvantage of an overall endothermic reaction in the fuel reactor. Results from batch laboratory fluidized bed tests with CuO and a gaseous and solid fuel are presented. The reaction rate of petroleum coke is approximately a factor 50 higher using CLOU in comparison to the reaction rate of the same fuel with an iron-based oxygen carrier in normal CLC.     

Energy efficiency of substance and energy recovery of selected waste fractions

In order to reduce the ecological impact of resource exploitation, the EU calls for sustainable options to increase the efficiency and productivity of the utilization of natural resources. This target can only be achieved by considering resource recovery from waste comprehensively. However, waste management measures have to be investigated critically and all aspects of substance-related recycling and energy recovery have to be carefully balanced. This article compares recovery methods for selected waste fractions with regard to their energy efficiency.Whether material recycling or energy recovery is the most energy efficient solution, is a question of particular relevance with regard to the following waste fractions: paper and cardboard, plastics and biowaste and also indirectly metals. For the described material categories material recycling has advantages compared to energy recovery. In accordance with the improved energy efficiency of substance opposed to energy recovery, substance-related recycling causes lower emissions of green house gases.For the fractions paper and cardboard, plastics, biowaste and metals it becomes apparent, that intensification of the separate collection systems in combination with a more intensive use of sorting technologies can increase the extent of material recycling. Collection and sorting systems must be coordinated. The objective of the overall system must be to achieve an optimum of the highest possible recovery rates in combination with a high quality of recyclables.The energy efficiency of substance related recycling of biowaste can be increased by intensifying the use of anaerobic technologies. In order to increase the energy efficiency of the overall system, the energy efficiencies of energy recovery plants must be increased so that the waste unsuitable for substance recycling is recycled or treated with the highest possible energy yield.     

Negative emissions of carbon dioxide through chemical-looping combustion (CLC) and gasification (CLG) using oxygen carriers based on manganese and iron

Carbon capture and storage (CCS) is an economically attractive strategy for avoiding carbon dioxide (CO₂) emissions from, e.g., power plants to the atmosphere. The combination of CCS and biomass combustion would result in a reduction of atmospheric CO₂, or net negative emissions, as plant growth is a form of sequestration of atmospheric carbon. Carbon capture can be achieved in a variety of ways, one of which is chemical looping. Chemical-looping combustion (CLC) and chemical looping gasification (CLG) are two promising technologies for conversion of biomass to heat and power or syngas/methane with carbon capture. There have been significant advances made with respect to CLC in the last two decades for all types of fuel, with much less research on the gasification technology. CLG offers some interesting opportunities for production of biofuels together with carbon capture and may have several advantages with respect to the bench mark indirect gasification process or dual-bed fluidized bed (DFBG) in this respect. In CLG, an oxygen carrier is used as a bed material instead of sand, which is common in indirect gasification, and this could have several advantages: (i) all generated CO₂ is present together with the syngas or methane in the fuel reactor outlet stream, thus in a concentrated stream, viable for separation and capture; (ii) the air reactor (or combustion chamber) should largely be free from trace impurities, thus preventing corrosion and fouling in this reactor; and (iii) the highly oxidizing conditions in the fuel reactor together with solid oxide surfaces should be advantageous with respect to limiting formation of tar species. In this study, two manganese ores and an iron-based waste material, LD slag, were investigated with respect to performance in these chemical-looping technologies. The materials were also impregnated with alkali (K) in order to gauge possible catalytic effects and also to establish a better understanding of the general behavior of oxygen carriers with alkali, an important component in biomass and biomass waste streams and often a precursor for high-temperature corrosion. The viability of the oxygen carriers was investigated using a synthetic biogas in a batch fluidized bed reactor. The conversion of CO, H₂, CH₄, and C₂H₄ was investigated in the temperature interval 800–950 °C. The reactivity, or oxygen transfer rate, was highest for the manganese ores, followed by the LD slag. The conversion of C₂H₄ was generally high but could largely be attributed to thermal decomposition. The K-impregnated samples showed enhanced reactivity during combustion conditions, and the Mangagran-K sample was able to achieve full conversion of benzene. The interaction of the solid material with alkali showed widely different behavior. The two manganese ores retained almost all alkali after redox testing, albeit exhibiting different migration patterns inside the particles. LD slag lost most alkali to the gas phase during testing, although some remained, possibly explaining a small difference in reactivity. In summary, the CLC and CLG processes could clearly be interesting for production of heat, power, or biofuel with negative CO₂ emissions. Manganese ores are most promising from this study, as they could absorb alkali, giving a better conversion and perhaps also inhibiting or limiting corrosion mechanisms in a combustor or gasifier.

     

Biomass-based negative emission technology options with combined heat and power generation

Biomass-based combined heat and power (CHP) generation with different carbon capture approaches is investigated in this study. Only direct carbon dioxide (CO₂) emissions are considered. The selected processes are (i) a circulating fluidized bed boiler for wood chips connected to an extraction/condensation steam cycle CHP plant without carbon capture; (ii) plant (i), but with post-combustion CO₂ capture; (iii) chemical looping combustion (CLC) of solid biomass connected to the steam cycle CHP plant; (iv) rotary kiln slow pyrolysis of biomass for biochar soil storage and direct combustion of volatiles supplying the steam cycle CHP plant with the CO₂ from volatiles combustion escaping to the atmosphere; (v) case (iv) with additional post-combustion CO₂ capture; and (vi) case (iv) with CLC of volatiles. Reasonable assumptions based on literature data are taken for the performance effects of the CO₂ capture systems and the six process options are compared. CO₂ compression to pipeline pressure is considered. The results show that both bioenergy with carbon capture and storage (BECCS) and biochar qualify as negative emission technologies (NETs) and that there is an energy-based performance advantage of BECCS over biochar because of the unreleased fuel energy in the biochar case. Additional aspects of biomass fuels (ash content and ash melting behavior) and sustainable soil management (nutrient cycles) for biomass production should be quantitatively considered in more detailed future assessments, as there may be certain biomass fuels, and environmental and economic settings where biochar application to soils is indicated rather than the full conversion of the biomass to energy and CO₂.

     

Variation in levels of reactive oxygen species is explained by maternal identity, sex and body-size-corrected clutch size in a lizard

Many organisms show differences between males and females in growth rate and crucial life history parameters, such as longevity. Considering this, we may expect levels of toxic metabolic by-products of the respiratory chain, such as reactive oxygen species (ROS), to vary with age and sex. Here, we analyse ROS levels in female Australian painted dragon lizards (Ctenophorus pictus) and their offspring using fluorescent probes and flow cytometry. Basal level of four ROS species (singlet oxygen, peroxynitrite, superoxide and H₂O₂) measured with a combined marker, and superoxide measured specifically, varied significantly among families but not between the sexes. When blood cells from offspring were chemically encouraged to accelerate the electron transport chain by mitochondrial uncoupling, net superoxide levels were three times higher in daughters than sons (resulting in levels outside of the normal ROS range) and varied among mothers depending on offspring sex (significant interaction between maternal identity and offspring sex). In offspring, there were depressive effects on ROS of size-controlled relative clutch size, which relies directly on circulating levels of vitellogenin, a confirmed antioxidant in some species. Thus, levels of reactive oxygen species varies among females, offspring and in relation to reproductive investment in a manner that makes its regulatory processes likely targets of selection.