Application of TiO2 nanoparticles for eco-friendly biodiesel production from waste olive oil

An environmentally benign, simple, and efficient process has been developed for biodiesel production from waste olive oil in the presence of a catalytic amount of TiO₂ nanoparticles at 120°C with a conversion of 91.2% within 4 h. The present method affords nontoxic and noncorrosive medium, high yield of biodiesel, clean reaction, and simple experimental and isolation procedures. The catalyst can be recycled by simple filtration and reused without any significant reduction in its activity.     

A process model to estimate the cost of industrial scale biodiesel production from waste cooking oil by supercritical transesterification

This paper describes the conceptual design of a production process in which waste cooking oil is converted via supercritical transesterification with methanol to methyl esters (biodiesel).Since waste cooking oil contains water and free fatty acids, supercritical transesterification offers great advantage to eliminate the pre-treatment capital and operating cost.A supercritical transesterification process for biodiesel continuous production from waste cooking oil has been studied for three plant capacities (125,000; 80,000 and 8000 tonnes biodiesel/year). It can be concluded that biodiesel by supercritical transesterification can be scaled up resulting high purity of methyl esters (99.8%) and almost pure glycerol (96.4%) attained as by-product.The economic assessment of the biodiesel plant shows that biodiesel can be sold at US$ 0.17/l (125,000 tonnes/year), US$ 0.24/l (80,000 tonnes/year) and US$ 0.52/l for the smallest capacity (8000 tonnes/year).The sensitive key factors for the economic feasibility of the plant are: raw material price, plant capacity, glycerol price and capital cost.Overall conclusion is that the process can compete with the existing alkali and acid catalyzed processes.Especially for the conversion of waste cooking oil to biodiesel, the supercritical process is an interesting technical and economical alternative.     

Model prediction on the rise of pCO2 in uniform flows by leakage of CO2 purposefully stored under the seabed

A numerical study was conducted to predict pCO₂ change in the ocean on a continental shelf by the leakage of CO₂, which is originally stored in the aquifer under the seabed, in the case that a large fault connects the CO₂ reservoir and the seabed by an earthquake or other diastrophism. The leakage rate was set to be 6.025 × 10⁻⁴ kg/m²/sec from 2 m × 100 m fault band, which corresponds to 3800 t-CO₂/year, referring to the monitored seepage rate from an existing EOR field. The target space in this study was limited to the ocean above the seabed, the depth of which was 200 or 500 m. The computational domain was idealistically rectangular with the seabed fault-band perpendicular to the uniform flow. The CO₂ takes a form of bubbles or droplets, depending on the depth of water, and their behaviour and dissolution were numerically simulated during their rise in seawater flow. The advection–diffusion of dissolved CO₂ was also simulated. As a result, it was suggested that the leaked CO₂ droplets/bubbles all dissolve in the seawater before spouting up to the atmosphere, and that the increase in pCO₂ in the seawater was smaller than 500 μ atm.     

Thermodynamic and Economic Aspects of the Hard Coal Based Oxyfuel Cycle

The present study shows a new approach in modelling the hard coal fired Oxyfuel Cycle on the whole. The static process model comprises an Oxyfuel combustion principle applied to an existing state-of-the-art hard coal power plant located in Rostock, Germany. It includes the air separation unit and the flue gas liquefaction unit, which are modelled in detail. As one of the main advances to previous work, the closed simulation of all components in one model delivers a coherent solution with a significantly reduced number of assumptions. The model needs no interfaces between different stand alone simulation tools or manual iteration and transfer of internal variables. Results from a thermodynamic and economic feasibility study on this process are shown and areas relevant for future research are identified.

The present study shows the feasibility and prospective key figures of the technology under realistic, comparable and reproducible assumptions and boundary conditions. The basic engineering of the process with a detailed study of the necessary gas separation and flue gas handling technologies is undertaken in the effort to a first stage optimisation of the process.

The flowsheet tool Aspen Plus (TM) was used to simulate the overall process. This particular tool was chosen because it offers an advanced data library on chemical substances and allows the calculation of phase equilibria and real gas behaviour during air separation and flue gas liquefaction. Emissions, coal consumption and investment costs of the Oxyfuel power plant are compared to those of the original state-of-the-art hard coal power plant which is used as the reference case.     

The influence of the precursor and synthesis method on the CO2 capture capacity of carpet waste-based sorbents

Adsorption is one of the most promising technologies for reducing CO₂ emissions and at present several different types of sorbents are being investigated. The use of sorbents obtained from low-cost and abundant precursors (i.e. solid wastes) appears an attractive strategy to adopt because it will contribute to a reduction not only in operational costs but also in the amount of waste that is dumped and burned in landfills every year. Following on from previous studies by the authors, in this work several carbon-based adsorbents were developed from different carpet wastes (pre-consumer and post-consumer wastes) by chemical activation with KOH at various activation temperatures (600–900 °C) and KOH:char impregnation ratios (0.5:1 to 4:1). The prepared materials were characterised by chemical analysis and gas adsorption (N₂, −196 °C; CO₂, 0 °C), and tested for CO₂ adsorption at temperatures of 25 and 100 °C. It was found that both the type of precursor and the conditions of activation (i.e. impregnation ratios, and activation temperatures), had a huge influence on the microporosity of the resultant samples and their CO₂ capture capacities. The carbon-based adsorbent that presented the maximum CO₂ capture capacities at 25 and 100 °C (13.8 wt.% and 3.1 wt.%, respectively), was prepared from a pre-consumer carpet waste and was activated at 700 °C using a KOH:char impregnation ratio of 1:1. This sample showed the highest narrow microporosity volume (0.47 cm³ g⁻¹), thus confirming that only pores of less than 1 nm are effective for CO₂ adsorption at atmospheric pressure.     

CO2 transportation for carbon capture and storage: Sublimation of carbon dioxide from a dry ice bank

Climate change is being caused by greenhouse gases such as carbon dioxide (CO₂). Carbon capture and storage (CCS) is of interest to the scientific community as one way of achieving significant global reductions of atmospheric CO₂ emissions in the medium term. CO₂ would be captured from large stationary sources such as power plants and transported via pipelines under high pressure conditions to underground storage. If a downward leakage from a surface transportation system module occurs, the CO₂ would undergo a large temperature reduction and form a bank of “dry ice” on the ground surface; the sublimation of the gas from this bank represents an area source term for subsequent atmospheric dispersion, with an emission rate dependent on the energy balance at the bank surface. Gaseous CO₂ is denser than air and tends to remain close to the surface; it is an asphyxiant, a cerebral vasodilator and at high concentrations causes rapid circulatory insufficiency leading to coma and death. Hence a subliming bank of dry ice represents safety hazard. A model is presented for evaluating the energy balance and sublimation rate at the surface of a solid frozen CO₂ bank under different environmental conditions. The results suggest that subliming gas behaves as a proper dense gas (i.e. it remains close to the ground surface) only for low ambient wind speeds.     

Effects of thermal barrier coating on the performance and combustion characteristics of a diesel engine fueled with biodiesel produced from waste frying cottonseed oil and ultra-low sulfur diesel

In this study, the top surfaces of piston and valves of a four-strokes and direct-injection diesel engine have been coated—with no change in the compression ratio—with a 100 μm of NiCrAl lining layer via plasma spray method and this layer has later been coated with main coating material with a mixture of 88% of ZrO₂, 4% of MgO and 8% of Al₂O₃ (400 μm). Then, after the engine-coating process, ultra-low sulfur diesel (ULSD) as base fuels and its blend with used frying cottonseed oil derived biodiesel in proportion of 20%, volumetrically, have been tested in the coated engine and data of combustion and performance characteristics on full load and at different speeds have been noted. The results, which were compared with those obtained by uncoated-engine operation, showed that thermal efficiency increased, and engine noise reduced. Cylinder gas pressure values obtained from the diesel engine which has been coated with thermal barriers have been found to be somewhat higher than those of the uncoated-engine. Also, maximum pressure values measured in both engines and under the same experimental conditions through the use of test fuel have been obtained after TDC. Moreover, heat release rate and heat release have occurred earlier in the coated-engine. NOx emissions were increased while CO and HC emissions were remained almost the same with a little bit decrease.     

Comparison and application of different component municipal solid wastes based carbon on adsorption of carbon dioxide

The prepared different components municipal solid wastes based carbons were used to investigate the adsorption of CO₂. The optimum conditions for CO₂ adsorption were investigated firstly. And then, the CO₂ adsorption performance of different components based carbon adsorbents were compared with each other under the optimum parameters. The results illustrated that the triple components (pinewood, acrylic textile, and tire) based carbon exhibited the best adsorption performance, which is 1.522 mmol/g and its physical prosperity was also conducted to interpret the adsorption mechanism. Besides, to further approach to the actual gas, the influence of additional O₂ and SO₂ on CO₂ adsorption properties of ternary-component-based carbon was investigated. The results illustrate that O₂ concentration exerts little effect on adsorption capacity. SO₂ plays the dominated role in the competitive adsorption effect.     

Hydrogen production from biomass

The ‘hydrogen economy’ has received considerable attention in academic, industrial and political contexts. There are opportunities for vast reductions in greenhouse gas emissions, increased energy security and greater overall efficiency. However, if hydrogen is to become a fundamental energy source for electrical power generation, as well as a transportation fuel, novel generation pathways will be necessary to meet the increase in demand. A promising means for generating hydrogen is the thermochemical conversion of biomass to a synthesis gas, composed of a mixture of hydrogen, carbon monoxide, carbon dioxide and methane. In order to manipulate the composition and maximise the hydrogen output, a calcium-based carbon dioxide sorbent can be utilised in situ. The removal of carbon dioxide alters the reaction chemistry to preferentially produce hydrogen. In this work we report on the characterisation of a likely Ca-based carbon dioxide sorbent and demonstrate the merits of hydrogen production from biomass, with in situ carbon dioxide capture, on the basis of a thermodynamic study. Using this model we show that hydrogen output from biomass gasification can be increased from 40%-vol to 80%-vol (dry basis) when a carbon dioxide sorbent is used.     

Carbon dioxide flux as affected by tillage and irrigation in soil converted from perennial forages to annual crops

Among greenhouse gases, carbon dioxide (CO(2)) is one of the most significant contributors to regional and global warming as well as climatic change. A field study was conducted to (i) determine the effect of soil characteristics resulting from changes in soil management practices on CO(2) flux from the soil surface to the atmosphere in transitional land from perennial forages to annual crops, and (ii) develop empirical relationships that predict CO(2) flux from soil temperature and soil water content. The CO(2) flux, soil temperature (T(s)), volumetric soil water content (theta(v)) were measured every 1-2 weeks in no-till (NT) and conventional till (CT) malt barley and undisturbed soil grass-alfalfa (UGA) systems in a Lihen sandy loam soil (sandy, mixed, frigid Entic Haplustoll) under irrigated and non-irrigated conditions in western North Dakota. Soil air-filled porosity (epsilon) was calculated from total soil porosity and theta(v) measurements. Significant differences in CO(2) fluxes between land management practices (irrigation and tillage) were observed on some measurement dates. Higher CO(2) fluxes were detected in CT plots than in NT and UGA treatments immediately after rainfall or irrigation. Soil CO(2) fluxes increased with increasing soil moisture (R(2)=0.15, P<0.01) while an exponential relationship was found between CO(2) emission and T(s) (R(2)=0.59). Using a stepwise regression analysis procedure, a significant multiple regression equation was developed between CO(2) flux and theta(v), T(s) (CO(2) [Formula: see text] ; R(2)=0.68, P0.01). Not surprisingly, soil temperature was a driving factor in the equation, which accounted for approximately 59% in variation of CO(2) flux. It was concluded that less intensive tillage, such as no-till or strip tillage, along with careful irrigation management will reduce soil CO(2) evolution from land being converted from perennial forages to annual crops.     

Intermediate storage of carbon dioxide in geological formations: A technical perspective

Enhanced oil recovery (EOR) through CO₂ flooding has been practiced on a commercial basis for the last 35 years and continues today at several sites, currently injecting in total over 30 million tons of CO₂ annually. This practice is currently exclusively for economic gain, but can potentially contribute to the reduction of emissions of greenhouse gases provided it is implemented on a large scale. Optimal operations in distributing CO₂ to CO₂-EOR or enhanced gas recovery (EGR) projects (referred to here collectively as CO₂-EHR) on a large scale and long time span imply that intermediate storage of CO₂ in geological formations may be a key component. Intermediate storage is defined as the storage of CO₂ in geological media for a limited time span such that the CO₂ can be sufficiently reproduced for later use in CO₂-EHR. This paper investigates the technical aspects, key individual parameters and possibilities of intermediate storage of CO₂ in geological formations aiming at large scale implementation of carbon dioxide capture and storage (CCS) for deep emission reduction. The main parameters are thus the depth of injection and density, CO₂ flow and transport processes, storage mechanisms, reservoir heterogeneity, the presence of impurities, the type of the reservoirs and the duration of intermediate storage. Structural traps with no flow of formation water combined with proper injection planning such as gas-phase injection favour intermediate storage in deep saline aquifers. In depleted oil and gas fields, high permeability, homogeneous reservoirs with structural traps (e.g. anticlinal structures) are good candidates for intermediate CO₂ storage. Intuitively, depleted natural gas reservoirs can be potential candidates for intermediate storage of carbon dioxide due to similarity in storage characteristics.     

Highly siliceous MCM-48 from rice husk ash for CO2 adsorption

Mesoporous MCM-48 silica was synthesized using a cationic-neutral surfactant mixture as the structure-directing template and rice husk ash (RHA) as the silica source. The MCM-48 samples were characterized by X-ray powder diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), N₂ physisorption and SEM. X-ray diffraction pattern of the resulting MCM-48 revealed typical pattern of cubic Ia3d mesophase. BET results showed the MCM-48 to have a surface area of 1024 m²/g and FT-IR revealed a silanol functional group at about 3460 cm⁻¹. Breakthrough experiments in the presence of MCM-48 were also carried out to test the material's CO₂ adsorption capacity. The breakthrough time for CO₂ was found to decrease as the temperature increased from 298 K to 348 K. The steep slopes observed shows the CO₂ adsorption occurred very quickly, with only a minimal mass transfer effect and very fast kinetics. In addition, amine grafted MCM-48, APTS-MCM-48 (RHA), was prepared with the 3-aminopropyltriethoxysilane (APTS) to investigate the effect of amine functional group in CO₂ separation. An order of magnitude higher CO₂ adsorption capacity was obtained in the presence of APTS-MCM-48 (RHA) compared to that with MCM-48 (RHA). These results suggest that MCM-48 synthesized from rice husk ash could be usefully applied for CO₂ removal.     

Numerical parametric study on CO2 capture by indirect thermal swing adsorption

Post-combustion CO₂ capture remains one of the most-challenging issue to lower CO₂ emissions of existing power plants or heavy industry installations because of strong economy and energy efficiency aspects. The major issue comes from CO₂ dilution (4% for NGCC and 14% for PC) and the high flow rates to be treated. Furthermore, CO₂ purity has to be higher than 95% with recovery at 90%, to match the transportation/injection requirements.The MEA absorption process remains the reference today but its energy consumption (about 3 MJ/kg_CO2) and the amine consumption are still challenging drawbacks.The interest of CO₂ capture by indirect TSA (Temperature Swing Adsorption) was demonstrated experimentally in a previous work. The aim of this paper is to present the results of a numerical parametric study. Two main parameters are explored: the desorption temperature (100–200 °C) and the purge flow rate (0.1–0.5 Ndm³ min⁻¹). Four performance indicators are evaluated: CO₂ purity, recovery, productivity and specific energy consumption.Results show that purity above 95% can be achieved. Keeping the 95% target, it is possible to achieve recovery at 81% with productivity at 57.7 g_CO2/kg_ads h and a specific energy consumption of 3.23 MJ/kg_CO2, which is less than for the reference MEA process.Comparison with other adsorption processes exhibits that this process has good potential especially since some improvements are still expected from further research.     

Dissolution of a CO2 lake, modeled by using an advanced vertical turbulence mixing scheme

The dissolution of CO₂ from a CO₂ lake with and without a hydrate layer, located at a flat bottom at 3000 m depth has been modeled using the MIT General Circulation Model coupled with the General Ocean Turbulence Model (GOTM). The vertical turbulent mixing scheme takes into account density effects and should give more realistic results for the CO₂ plume than previously used constant eddy diffusivity models. The introduction of a third direction gives qualitatively different results for the spreading of the CO₂ plume than previous 2D results. The dissolution rate and near field dissolved CO₂ concentrations approach a steady state for a given far field ocean current within less than a day. The dissolution rate is highly dependent on the velocity of the ambient current and is reduced with 1.6 when a hydrate layer is introduced.     

Emission of CO2, CH4 and N2O from freshwater marsh in northeast of China

The wetlands play an important role in carbon storage, especially at high latitudes, at which they store nearly one-third of global soil carbons. However, few studies have investigated the emissions of CO(2), CH(4) and N(2)O in the long-term, especially effects of freeze-thaw cycles on these gases emissions in freshwater marsh ecosystems. In this paper, we collected greenhouse gas emission data from a freshwater marsh area in China for 4 years, evaluated their release variables and speculated on their potential atmospheric impact. For this paper, we report on the CO(2), CH(4) and N(2)O emission rates recorded from June 2002 to November 2005 in the Sanjiang Plain of northeast China. We measured their interannual variations and fluctuations, as well as factors affecting their emissions, and estimated their regulation and freeze-thaw cycle impacts. Our results revealed obvious CO(2) and CH(4) emission fluctuations during the winter months, and during the freeze-thaw cycle, and a strong interannual variation during the growing season. Overall, we documented a close relationship between the CO(2) and CH(4) emissions, implicating some regulatory commonality. We determined that the marsh was a N(2)O sink during the winter, but a significant source of N(2)O during the freeze-thaw cycle as the temperature increased, especially in early summer. During the thaw-freeze period, the N(2)O levels were positively correlated with the water depth. Additionally, water depth greatly governed the interannual variation of the N(2)O emissions from the marshes during the thaw-freeze period.     

Monitoring of the microbial community composition in saline aquifers during CO2 storage by fluorescence in situ hybridisation

This study reveals the first analyses of the composition and activity of the microbial community of a saline CO₂ storage aquifer. Microbial monitoring during CO₂ injection has been reported. By using fluorescence in situ hybridisation (FISH), we have shown that the microbial community was strongly influenced by the CO₂ injection. Before CO₂ arrival, up to 6 × 10⁶ cells ml⁻¹ were detected by DAPI staining at a depth of 647 m below the surface. The microbial community was dominated by the domain Bacteria that represented approximately 60% to 90% of the total cell number, with Proteobacteria and Firmicutes as the most abundant phyla comprising up to 47% and 45% of the entire population, respectively. Both the total cell counts as well as the counts of the specific physiological groups revealed quantitative and qualitative changes after CO₂ arrival. Our study revealed temporal outcompetition of sulphate-reducing bacteria by methanogenic archaea. In addition, an enhanced activity of the microbial population after five months CO₂ storage indicated that the bacterial community was able to adapt to the extreme conditions of the deep biosphere and to the extreme changes of these atypical conditions.     

SO2 gas adsorption by modified kaolin clays: influence of previous heating and time acid treatments

Modified kaolin clays were used as adsorbents for SO(2) gas adsorptions. The clays were heated up to 900 °C previous to acid treatments with 0.5 N sulfuric acid solutions at boiling temperature during different times up to 1440 min. Equilibrium adsorption at 25 °C and 0.1 MPa was carried out by using a volumetric apparatus. The samples were characterized by chemical analysis, X-ray diffraction and infrared analysis. The heating of the clays followed by acid treatment improved the adsorption capacity of the kaolin clays. The presence of amorphous silica and hydroxyl in the final products improved SO(2) adsorption capacity. Better properties for SO(2) adsorption were found in kaolin rich in not well ordered kaolinite clay mineral.     

Experimental measurement and modeling of the rate of absorption of carbon dioxide by aqueous ammonia

In this work, the rate of absorption of carbon dioxide by aqueous ammonia solvent has been studied by applying a newly built wetted wall column. The absorption rate in aqueous ammonia was measured at temperatures from 279 to 304 K for 1 to 10 wt% aqueous ammonia with loadings varying from 0 to 0.8 mol CO₂/mol NH₃. The absorption rate in 30 wt% aqueous mono-ethanolamine (MEA) was measured at 294 and 314 K with loadings varying from 0 to 0.4 as comparison.It was found that at 304 K, the rate of absorption of carbon dioxide by 10 wt% NH₃ solvent was comparable to the rates for 30 wt% MEA at 294 and 314 K (a typical absorption temperature for this process). The absorption rate using ammonia was however significantly lower at temperatures of 294 K and lower as applied in the Chilled Ammonia Process. However, at these low temperatures, the rate of absorption in ammonia has only a small temperature dependency.The rate of absorption decreases strongly with decreasing ammonia concentrations and increasing CO₂ loadings.The rate of absorption of carbon dioxide by aqueous ammonia solvent was modeled using the measurements of the unloaded solutions and the zwitter-ion mechanism. The model could successfully predict the experimental measurements of the absorption rate of CO₂ in loaded ammonia solutions.