A new, fast response CO2 sensor

The inability of emissions reduction methods to meet upcoming legislation without an unacceptable increase in vehicle cost is a major problem of automobile manufacturer. This work aims to develop a cost-effective reduction of automobile emissions. A prototype CO2 sensor with 5 msec response time was built and bench tested, then used on an engine. The sensor design was based on standard emissions measurement technology using non-dispersive IR absorption. An improved sensor has now been completed with significant improvements in terms of signal to noise ratio and long-term stability. The improved sensor will be used to measure CO2 concentrations on three different engines. The results will then be used to validate engine and catalyst models and to propose control strategies aimed at reducing overall emissions. A brief description of the sensor itself was presented. Original is an abstract.

Assessing the potential of yield improvements, through process scrap reduction, for energy and CO2 abatement in the steel and aluminium sectors

Targets to cut 2050 CO2 emissions in the steel and aluminium sectors by 50%, whilst demand is expected to double, cannot be met by energy efficiency measures alone, so options that reduce total demand for liquid metal production must also be considered. Such reductions could occur through reduced demand for final goods (for instance by life extension), reduced demand for material use in each product (for instance by lightweight design) or reduced demand for material to make existing products. The last option, improving the yield of manufacturing processes from liquid metal to final product, is attractive in being invisible to the final customer, but has had little attention to date. Accordingly this paper aims to provide an estimate of the potential to make existing products with less liquid metal production. Yield ratios have been measured for five case study products, through a series of detailed factory visits, along each supply chain. The results of these studies, presented on graphs of cumulative energy against yield, demonstrate how the embodied energy in final products may be up to 15 times greater than the energy required to make liquid metal, due to yield losses. A top-down evaluation of the global flows of steel and aluminium showed that 26% of liquid steel and 41% of liquid aluminium produced does not make it into final products, but is diverted as process scrap and recycled. Reducing scrap substitutes production by recycling and could reduce total energy use by 17% and 6% and total CO 2 emissions by 16% and 7% for the steel and aluminium industries respectively, using forming and fabrication energy values from the case studies. The abatement potential of process scrap elimination is similar in magnitude to worldwide implementation of best available standards of energy efficiency and demonstrates how decreasing the recycled content may sometimes result in emission reductions. Evidence from the case studies suggests that whilst most companies are aware of their own yield ratios, few, if any, are fully aware of cumulative losses along their whole supply chain. Addressing yield losses requires this awareness to motivate collaborative approaches to improvement. © 2011 Elsevier B.V. All rights reserved.

An investigation of the kinetics of CO2 uptake by a synthetic calcium based sorbent

This study examines the kinetics of carbonation by CO2 at temperatures of ca. 750 °C of a synthetic sorbent composed of 15 wt% mayenite (Ca12Al14O33) and CaO, designated HA-85-850, and draws comparisons with the carbonation of a calcined limestone. In-situ XRD has verified the inertness of mayenite, which neither interacts with the active CaO nor does it significantly alter the CaO carbonation–calcination equilibrium. An overlapping grain model was developed to predict the rate and extent of carbonation of HA-85-850 and limestone. In the model, the initial microstructure of the sorbent was defined by a discretised grain size distribution, assuming spherical grains. The initial input to the model – the size distribution of grains – was a fitted parameter, which was in good agreement with measurements made with mercury porosimetry and by the analysis of SEM images of sectioned particles. It was found that the randomly overlapping spherical grain assumption offered great simplicity to the model, despite its approximation to the actual porous structure within a particle. The model was able to predict the performance of the materials well and, particularly, was able to account for changes in rate and extent of reaction as the structure evolved after various numbers of cycles of calcination and carbonation.

A 5-step reduced mechanism for combustion of CO/H2/H2O/CH4/CO2 mixtures with low hydrogen/methane and high H2O content

In this study a 5-step reduced chemical kinetic mechanism involving nine species is developed for combustion of Blast Furnace Gas (BFG), a multi-component fuel containing CO/H2/CH4/CO2, typically with low hydrogen, methane and high water fractions, for conditions relevant for stationary gas-turbine combustion. This reduced mechanism is obtained from a 49-reaction skeletal mechanism which is a modified subset of GRI Mech 3.0. The skeletal and reduced mechanisms are validated for laminar flame speeds, ignition delay times and flame structure with available experimental data, and using computational results with a comprehensive set of elementary reactions. Overall, both the skeletal and reduced mechanisms show a very good agreement over a wide range of pressure, reactant temperature and fuel mixture composition. © 2012 The Combustion Institute..

A high performance oxygen storage material for chemical looping processes with CO2 capture

Chemical looping combustion (CLC) is a novel combustion technology that involves cyclic reduction and oxidation of oxygen storage materials to provide oxygen for the combustion of fuels to CO2 and H2O, whilst giving a pure stream of CO2 suitable for sequestration or utilisation. Here, we report a method for preparing of oxygen storage materials from layered double hydroxides (LDHs) precursors and demonstrate their applications in the CLC process. The LDHs precursor enables homogeneous mixing of elements at the molecular level, giving a high degree of dispersion and high-loading of active metal oxide in the support after calcination. Using a Cu-Al LDH precursor as a prototype, we demonstrate that rational design of oxygen storage materials by material chemistry significantly improved the reactivity and stability in the high temperature redox cycles. We discovered that the presence of sodium-containing species were effective in inhibiting the formation of copper aluminates (CuAl2O4 or CuAlO 2) and stabilising the copper phase in an amorphous support over multiple redox cycles. A representative nanostructured Cu-based oxygen storage material derived from the LDH precursor showed stable gaseous O2 release capacity (∼5 wt%), stable oxygen storage capacity (∼12 wt%), and stable reaction rates during reversible phase changes between CuO-Cu 2O-Cu at high temperatures (800-1000 °C). We anticipate that the strategy can be extended to manufacture a variety of metal oxide composites for applications in novel high temperature looping cycles for clean energy production and CO2 capture. © The Royal Society of Chemistry 2013.

The roles of energy and material efficiency in meeting steel industry CO2 targets.

Identifying strategies for reducing greenhouse gas emissions from steel production requires a comprehensive model of the sector but previous work has either failed to consider the whole supply chain or considered only a subset of possible abatement options. In this work, a global mass flow analysis is combined with process emissions intensities to allow forecasts of future steel sector emissions under all abatement options. Scenario analysis shows that global capacity for primary steel production is already near to a peak and that if sectoral emissions are to be reduced by 50% by 2050, the last required blast furnace will be built by 2020. Emissions reduction targets cannot be met by energy and emissions efficiency alone, but deploying material efficiency provides sufficient extra abatement potential.

Experimental investigation of dynamic response of acoustically forced turbulent premixed CH4/CO2/air flames

Increasing demand for energy and continuing increase in environmental as well as financial cost of use of fossil fuels drive the need for utilization of fuels from sustainable sources for power generation. Development of fuel-flexible combustion systems is vital in enabling the use of sustainable fuels. It is also important that these sustainable combustion systems meet the strict governmental emission legislations. Biogas is considered as one of the viable sustainable fuels that can be used to power modern gas turbines: However, the change in chemical, thermal and transport properties as well as change in Wobbe index due to the variation of the fuel constituents can have a significant effect on the performance of the combustor. It is known that the fuel properties have strong influence on the dynamic flame response; however there is a lack of detailed information regarding the effect of fuel compositions on the sensitivity of the flames subjected to flow perturbations. In this study, we describe an experimental effort investigating the response of premixed biogas-air turbulent flames with varying proportions of CH4 and CO2 to velocity perturbations. The flame was stabilized using a centrally placed conical bluff body. Acoustic perturbations were imposed to the flow using loud speakers. The flame dynamics and the local heat release rate of these acoustically excited biogas flames were studied using simultaneous measurements of OH and H2CO planar laser induced fluorescence. OH* chemiluminescence along with acoustic pressure measurements were also recorded to estimate the total flame heat release modulation and the velocity fluctuations. The measurements were carried out by keeping the theoretical laminar flame speed constant while varying the bulk velocity and the fuel composition. The results indicate that the flame sensitivity to perturbations increased with increased dilution of CH4 by CO2 at low amplitude forcing, while at high amplitude forcing conditions the magnitude of the flame response was independent of dilution.

Fast response CO2 sensor for automotive exhaust gas analysis

A fast response sensor for measuring carbon dioxide concentration has been developed for laboratory research and tested on a spark ignition engine. The sensor uses the well known infra-red absorption technique with a miniaturized detection system and short capillary sampling tubes, giving a time constant of approximately 5 milliseconds; this is sufficiently fast to observe changes in CO2 levels on a cycle-by-cycle basis under normal operating conditions. The sensor is easily located in the exhaust system and operates continuously. The sensor was tested on a standard production four cylinder spark-ignition engine to observe changes in CO2 concentration in exhaust gas under steady state and transient operating conditions. The processed sensor signal was compared to a standard air-to-fuel ratio (AFR) sensor in the exhaust stream and the results are presented here. The high frequency response CO2 measurements give new insights into both engine and catalyst transient operation. Copyright © 1999 Society of Automotive Engineers, Inc.

Reversible CO2 absorption by the 6H perovskite Ba 4Sb2O9

A novel compound for carbon capture and storage (CCS) applications, the 6H perovskite Ba4Sb2O9, was found to be able to absorb CO2 through a chemical reaction at 873 K to form barium carbonate and BaSb2O6. This absorption was shown to be reversible through the regeneration of the original Ba4Sb 2O9 material upon heating above 1223 K accompanied by the release of CO2. A combined synchrotron X-ray diffraction, thermogravimetric, and microscopy study was carried out to characterize first the physical absorption properties and then to analyze the structural evolution and formation of phases in situ. Importantly, through subsequent carbonation and regeneration of the material over 100 times, it was shown that the combined absorption and regeneration reactions proceed without any significant reduction in the CO2 absorption capacity of the material. After 100 cycles the capacity of Ba4Sb2O9 was ∼0.1 g (CO 2)/g (sorbent), representing 73% of the total molar capacity. This is the first report of a perovskite-type material showing such good properties, opening the way for studies of new classes of inorganic oxide materials with stable and flexible chemical compositions and structures for applications in carbon capture. © 2013 American Chemical Society.

Impacts of CO2 enrichment on growth and photosynthesis in freshwater and marine diatoms

The physiological responses of Nitzschia palea Kutzing, a freshwater diatom, to elevated CO2 were investigated and compared with those of a marine diatom, Chaetoceros muelleri Lemmermann previously reported. Elevated CO2 concentration to 700 mu l/L increased the dissolved inorganic carbon (DIC) and lowered the pH in the cultures of N. palea, thus enhancing the growth by 4%-20% during the whole growth period. High CO2-grown N. palea cells showed lower levels of dark respiration rates and higher I (k) values. Light-saturated photosynthetic rates and photosynthetic efficiencies decreased in N. palea with the doubling CO2 concentration in airflow to the bottom of cultures, although the doubling CO2 concentration in airflow to the surface cultures had few effects on these two photosynthetic parameters. N. palea cells were found to be capable of using HCO3 (-) in addition to gaseous CO2, and the CO2 enrichment decreased their affinity for HCO3 (-) and CO2. Although doubled CO2 level would enhance the biomass of N. palea and C. muelleri to different extents, compared with the marine diatom, it had a significant effect on the specific growth rates of N. palea. In addition, the responses of photosynthetic parameters of N. palea to doubled CO2 concentration were almost opposite to those of C. muelleri.

In-Situ grown carbon nanotubes for enhanced CO2 detection in non-dispersive-infra-red system

Non-dispersive-infra-red (NDIR) sensors are believed to be one of the most selective and robust solutions for CO2 detection, though cost prohibits their broader integration. In this paper we propose a commercially viable silicon-on-insulator (SOI) complementary metal-oxide (CMOS) micro-electro-mechanical (MEMS) technology for an IR thermal emitter. For the first time, vertically aligned multi walled carbon nanotubes (VA-MWCNTs) are suggested as a possible coating for the enhancement of the emission intensity of the optical source of a NDIR system. VA-MWCNTs have been grown in situ by chemical vapour deposition (CVD) exclusively on the heater area. Optical microscopy, scanning electron microscopy and Raman spectroscopy have been used to verify the quality of the VA-MWCNTs growth. The CNT-coated emitter demonstrated an increased response to CO2 of approx. 60%. Furthermore, we show that the VA-MWCNTs are stable up to temperatures of 500°C for up to 100 hours. © 2013 IEEE.

Nitrite utilization by Chaetoceros muelleri under elevated CO2 concentration

Chaetoceros muelleri (Lemn.) was cultured with nitrite (NO2-) or nitrate (NO3-) as the sole nitrogen source and aerated with air or with CO2-enriched air. Cells of C. muelleri excreted into the medium nitrite produced by reduction of nitrate when grown with 100 mu M NaNO3 as nitrogen source. Accordingly, NO2- concentration reached 10.4 mu M after 95 h at the low CO2 condition (aerated with air); while the maximum NO2- concentration was only around 2.0 mu M at the high CO2 condition (aerated with 5% CO2 in air), furthermore, after 30 h it decreased to no more than 1.0 mu M. NO2- was almost assimilated in 80 h when C. muelleri was cultured at the high CO2 condition with 100 mu M NaNO2 as sole nitrogen source. At the high CO2 condition, after 3 h the activity of nitrite reductase was as much as 50% higher than that at the low CO2 condition. It was indicated that enriched CO2 concentration could inhibit nitrite excretion and enhance nitrite assimilation by cells. Therefore, aeration with enriched CO2 might be an effective way to control nitrite content in aquaculture systems.

Daily timing of emersion and elevated atmospheric CO2 concentration affect photosynthetic performance of the intertidal macroalga Ulva lactuca (Chlorophyta) in sunlight

The lunar day differs in length from the solar day so that times of low tide vary from day to day. Thus, aerial exposure of intertidal seaweeds may be during the day or during the night. We measured photosynthetic CO, assimilation rates of the intertidal green macroalga Ulva lactuca during exposures of varied daily timings during sunny days of summer to establish how photosynthetic performance responds to emersion timing under varied CO2 levels [at ambient (360 ppmv) and 2x ambient (720 ppmv) atmospheric CO2 concentrations]. There was an increase in net photosynthetic rates following some duration of exposure when the initial timing of exposure occurred during early morning (06.30 h) and late afternoon (17.15 h). In contrast, net rates exhibited a sharp decline with exposure duration when the initial timing of exposure occurred at 09.30 h, 15.30 h and especially at noon (12.30 h), implying the occurrence of a severe photoinhibition resulting from mid-day insolation. Doubled atmospheric CO2 concentration significantly enhanced the emersed photosynthetic rates, indicating that the emersed photosynthesis is CO2-limited at ambient CO2 levels. However, increasing CO2 barely stimulates the emersed photosynthetic rates during mid-day insolation.