The influence of different surface-modification treatments on biomass-based carbons and their effects on adsorption of carbon dioxide

Surface modification of biomass-based carbon with nitrogen-containing functional groups is performed by the different modification method, including the thermal and chemical methods. We also investigate the effect of the different reaction parameters on their pore structure using the Brunauer–Emmett–Teller surface area and adsorption performance based on methylene blue value. Fourier transforms infrared spectroscopy methods are performed to confirm the presence of N-containing groups. Based on above results, the comparison effect of different modification methods on physico-chemical propriety and adsorption properties of biomass-based carbon materials are carried out. In conclusion, all modification methods could enhance CO₂ adsorption capability. However, the carbon materials treated with ammonia using thermal method show the best performance.     

Adsorption of carbon dioxide using impregnated activated carbon promoted by Zinc

The effect of impregnation of activated carbon with Cr₂O and Fe₂O₃ and promotion by Zn²⁺ on its adsorptive properties of carbon dioxide was studied using a volumetric adsorption apparatus at ambient temperature and low pressures. Slurry and solution impregnation methods were used to compare CO₂ capture capacity of the impregnated activated carbon promoted by Zinc. The obtained adsorption isotherms showed that amount of CO₂ adsorbed on the samples impregnated by Cr₂O was increased about 20% in compare to raw activated carbon. The results also showed that Fe₂O₃ was not an effective impregnating species for activated carbon modification. Moreover slurry impregnation method showed higher CO₂ adsorption capacity in comparison with solution impregnation method. Samples prepared by co-impregnation of two metal species showed more adsorption capacity than samples impregnated by just one metal species individually. Washing the impregnated samples by metal oxide resulted in 15% increase in CO₂ adsorption capacities of activated carbons which can be attributed to the metal oxides removal covering the adsorption surface. Decreasing impregnation temperature from 95 to 25 °C in solution method showed a significant increase in CO₂ adsorption capacity. Sips equation was found a suitable model fitting to the adsorption data in the range studied.     

Hollow fiber membrane separation process in the presence of gaseous and particle impurities for post-combustion CO2 capture

The membrane separation process for CO₂ capture can be interfered by the gaseous components and the fine particles in flue gas, especially in desulfurized flue gas. In this work, the pint-sized Polyimide(PI) hollow fiber membrane contactors were self-packed to investigate the membrane CO₂ separation from flue gas containing fine particles and gaseous contaminants (SO₂,SO₃,H₂O). First, the effects of SO₂, SO₃, water vapor, and gypsum particles on the CO₂ capture were studied independently and synergistically. The results showed that the effect of SO₂ on the membrane separation properties is indistinctive; however, the membrane performance was damaged seriously with the addition of SO₃. The high humidity promoted the CO₂ separation initially before inhibiting the PI membrane performance. Moreover, the decrease of the CO₂/N₂ selectivity and the permeation rate were accelerated with the coexistence of SO₂. The membrane performance showed an obvious deterioration in the presence of gypsum particles, with a 21% decrease in the CO₂/N₂ selectivity and 51% decrease in the permeation rate. Furthermore, the gypsum particles exerted dramatic damage. Under the WFGD conditions, the combined effects of SO₂, water vapor, and the gypsum particles influenced the stability of the membrane significantly. This tendency is mainly attributed to the deposition of fine particles and aerosol on the membrane surface, which occupied the effective area and enhanced the mass transfer resistance. This study of impurities’ influence could play an important role in further industrial application of membrane CO₂ capture.     

Study on the failure mechanism of potassium-based sorbent for CO2 capture and the improving measure

With thermogravimetric apparatus (TGA), X-ray diffraction (XRD) and barium sulfate gravimetric methods, the carbonation reactivities of K₂CO₃ and K₂CO₃/Al₂O₃ in the simulated flue gases with SO₂ are investigated and the reaction equations are inferred. Results show that there are KHCO₃ and K₂SO₃ generated. The generation K₂SO₃ reduces the utilization ratio of the sorbent. H₂O may accelerates the sulfation reaction of AR K₂CO₃ as K₄H₂(CO₃)₃·1.5H₂O is generated in the reaction among K₂CO₃, SO₂ and H₂O. K₂SO₃ is directly generated from sulfation reaction of K₂CO₃/Al₂O₃, because there are K₂CO₃·1.5H₂O and K₂SO₃ generated in the reaction among K₂CO₃/Al₂O₃, SO₂ and H₂O. K₂CO₃·1.5H₂O does not react with SO₂, and K₂CO₃·1.5H₂O/Al₂O₃ reacts with SO₂ slowly. Compare with the reaction process without H₂O pretreatment, the reaction rates of KAl30 increased after H₂O pretreatment and the failure ratio is about a half of that without H₂O pretreatment. So, K₂CO₃/Al₂O₃ shows good carbonation and anti-sulfation characteristic after H₂O pretreatment.     

Characterization of a limestone in a batch fluidized bed reactor for sulfur retention under oxy-fuel operating conditions

CO₂ and SO₂ are some of the main polluting gases emitted into atmosphere in combustion processes using fossil fuel for energy production. The former is one of the major contributors to build-up the greenhouse effect implicated in global climate change and the latter produces acid rain. Oxy-fuel combustion is a technology, which consists in burning the fuel with a mix of pure O₂ and recirculated CO₂. With this technology the CO₂ concentration in the flue gas may be enriched up to 95%, becoming possible an easy CO₂ recovery. In addition, oxy-fuel combustion in fluidized beds allows in situ desulfurization of combustion gases by supplying calcium based sorbent.In this work, the effect of the principal operation variables affecting the sulfation reaction rate in fluidized bed reactors (temperature, CO₂ partial pressure, SO₂ concentration and particle size) under typical oxy-fuel combustion conditions have been analyzed in a batch fluidized bed reactor using a limestone as sorbent. It has been observed that sulfur retention can be carried out by direct sulfation of the CaCO₃ or by sulfation of the CaO (indirect sulfation) formed by CaCO₃ calcination. Direct sulfation and indirect sulfation operating conditions depended on the temperature and CO₂ partial pressure. The rate of direct sulfation rose with temperature and the rate of indirect sulfation for long reaction times decreased with temperature. An increase in the CO₂ partial pressure had a negative influence on the sulfation conversion reached by the limestone due to a higher temperature was needed to work in conditions of indirect sulfation. Thus, it is expected that the optimum temperature for sulfur retention in oxy-fuel combustion in fluidized bed reactors be about 925–950 °C. Sulfation reaction rate rose with decreasing sorbent particle size and increasing SO₂ concentration.     

A statistical analysis of the carbon dioxide capture process

Post combustion carbon dioxide (CO₂) capture is one of the most commonly adopted technologies for reducing industrial CO₂ emissions, which is now an important goal given the widespread concern over global warming. Research on amine-based CO₂ capture has mainly focused on improving effectiveness and efficiency of the CO₂ capture process. Our research work focuses on studying the relationships among the significant parameters influencing CO₂ production because an enhanced understanding of the intricate relationships among the parameters involved in the process is critical for improving efficiency of the CO₂ capture process. This paper presents a statistical study that explores the relationships among parameters involved in the amine-based post combustion CO₂ capture process at the International Centre for CO₂ Capture (ITC) located in Regina, Saskatchewan of Canada. A multiple regression technique has been applied for analysis of data collected at the CO₂ capture pilot plant at ITC. The parameters have been carefully selected to avoid issues of multicollinearity, and four mathematical models among the key parameters identified have been developed. The models have been tested, and accuracy of the models is found to be satisfactory. The models developed in this study describe part of the CO₂ capture process and can help to predict performance of the CO₂ capture process at ITC under different conditions. Some results from a preliminary validation process will also be presented.     

Corrosion and polarization behavior of carbon steel in MEA-based CO2 capture process

This work reveals levels of corrosion rate and polarization behavior of carbon steel immersed in aqueous solutions of monoethanolamine (MEA) used in the absorption-based carbon dioxide (CO₂) capture process for greenhouse gas reduction from industrial flue gas streams. Such information was obtained from electrochemical-based corrosion experiments under a wide range of the CO₂ capture process conditions. The corrosion of carbon steel was evaluated in respect to process parameters including partial pressure of oxygen (O₂), CO₂ loading in solution, solution velocity, solution temperature, MEA concentration and metal surface condition. Results show that the aqueous MEA solution containing CO₂ provides a favorable condition for the corrosion of carbon steel to proceed. Corrosion rate is increased by all tested process parameters. These parametric effects were explained by the electrochemical kinetic data obtained from polarization curves and by the thermodynamic data obtained from Pourbaix diagram.     

Kinetics of sulfur dioxide- and oxygen-induced degradation of aqueous monoethanolamine solution during CO2 absorption from power plant flue gas streams

Studies of the kinetics of sulfur dioxide (SO₂)- and oxygen (O₂)-induced degradation of aqueous monoethanolamine (MEA) during the absorption of carbon dioxide (CO₂) from flue gases derived from coal- or natural gas-fired power plants were conducted as a function of temperature and the liquid phase concentrations of MEA, O₂, SO₂ and CO₂. The kinetic data were based on the initial rate which shows the propensity for amine degradation and obtained under a range of conditions typical of the CO₂ absorption process (3–7 kmol/m³ MEA, 6% O₂, 0–196 ppm SO₂, 0–0.55 CO₂ loading, and 328–393 K temperature). The results showed that an increase in temperature and the concentrations of MEA, O₂ and SO₂ resulted in a higher MEA degradation rate. An increase in CO₂ concentration gave the opposite effect. A semi-empirical model based on the initial rate, ?r_MEA = {6.74 × 10⁹ e^?(29,403/RT)[MEA]^0.02([O]^2.91 + [SO₂]^3.52)}/{1 + 1.18[CO₂]^0.18} was developed to fit the experimental data. With the higher order of reaction, SO₂ has a higher propensity to cause MEA to degrade than O₂. Unlike previous models, this model shows an improvement in that any of the parameters (i.e. O₂, SO₂, and CO₂) can be removed without affecting the usability of the model.     

Limitations for brine acidification due to SO2 co-injection in geologic carbon sequestration

Co-injection of sulfur dioxide during geologic carbon sequestration can cause enhanced brine acidification. The magnitude and timescale of this acidification will depend, in part, on the reactions that control acid production and on the extent and rate of SO₂ dissolution from the injected CO₂ phase. Here, brine pH changes were predicted for three possible SO₂ reactions: hydrolysis, oxidation, or disproportionation. Also, three different model scenarios were considered, including models that account for diffusion-limited release of SO₂ from the CO₂ phase. In order to predict the most extreme acidification potential, mineral buffering reactions were not modeled. Predictions were compared to the case of CO₂ alone which would cause a brine pH of 4.6 under typical pressure, temperature, and alkalinity conditions in an injection formation. In the unrealistic model scenario of SO₂ phase equilibrium between the CO₂ and brine phases, co-injection of 1% SO₂ is predicted to lead to a pH close to 1 with SO₂ oxidation or disproportionation, and close to 2 with SO₂ hydrolysis. For a scenario in which SO₂ dissolution is diffusion-limited and SO₂ is uniformly distributed in a slowly advecting brine phase, SO₂ oxidation would lead to pH values near 2.5 but not until almost 400 years after injection. In this scenario, SO₂ hydrolysis would lead to pH values only slightly less than those due to CO₂ alone. When SO₂ transport is limited by diffusion in both phases, enhanced brine acidification occurs in a zone extending only 5 m proximal to the CO₂ plume, and the effect is even less if the only possible reaction is SO₂ hydrolysis. In conclusion, the extent to which co-injected SO₂ can impact brine acidity is limited by diffusion-limited dissolution from the CO₂ phase, and may also be limited by the availability of oxidants to produce sulfuric acid.     

Gasification of Inferior Coal with High Ash Content under CO2 and O2/H2O Atmospheres

The gasification reaction of Nantong inferior coal was investigated in a laboratory fixed-bed reactor under CO₂ and O₂/H₂O atmospheres. The effects of the bed temperature and inlet-gas concentration on the yields of CO, H₂, and CH₄ were studied. The effects of coal ash and particle size on the fixed-carbon conversion were also investigated, and kinetic analysis was conducted with a homogeneous model. The product-gas-heating value and fixed-carbon conversion increased when the temperature was increased from 950 °C to 1100 °C under CO₂ atmosphere. When the inlet-CO₂ concentration was increased from 50 to 100 vol.%, the low heating value of the product gas and carbon conversion ratio slightly increased. During the gasification of inferior coal under the O₂/H₂O atmosphere, the CO concentration increased rapidly with increasing temperature. The H₂ and CH₄ concentrations increased initially and then decreased. The maximum gas heating value of 7934 kJ/m³ was obtained under the O₂ concentration of 70 vol.% at a bed temperature of 1050 °C. The cold-gas efficiency increased with increasing temperature and became 40.6% and 86.4% at 1100 °C under the CO₂ and O₂/H₂O atmospheres, respectively. The gasification reaction of the Nantong inferior coal strongly depended on the content of inherent inorganic matter. The gasification rates for both the CO₂ and O₂/H₂O atmospheres were independent of the particle size. The activation energy for the CO₂ and O₂/H₂O gasification reactions were 137 and 81 kJ/mol, respectively. The gasification reactions of the Nantong coal, which was performed under two different atmospheres, were compared and the reaction activity of the gasification reaction under CO₂ atmosphere was found to be much lower than that under the O₂/H₂O atmosphere.     

Molecular analysis of carbon dioxide adsorption processes on steel slag oxides

This review presents a summary of the main interactions that occur during the carbon dioxide (CO₂) adsorption at the surface of steel slags with basic (CaO, MgO), amphoteric (Al₂O₃, Cr₂O₃, TiO₂, MnO, iron oxides) and acidic (SiO₂) oxides. The high content of metal oxides in steel slags gives them a great potential to adsorb CO₂, reaching a saturation value of about 0.25 kg of CO₂/kg of slag. CO₂ is physisorbed and chemisorbed on the most of metal oxide types. Generally, the CO₂ physisorption on the basic and amphoteric metal oxides involves an electrostatic interaction between the CO₂ and the cation from the oxides while the CO₂ chemisorption rather implicates the basic sites that acts as the electron donor, and which are associated with O^2? ions localized at surface defects. These interactions result in the formation of carbonates (monodentates or unidentates and bidentates). The affinity of oxides for the CO₂ and the carbonate formation principally depend of the strength and number of basic sites at their surface and varies as following: basic oxides > amphoteric oxides > acidic oxides. The basic metal oxides generally represent the best electron donors and thus the best CO₂ adsorbents due to the high basicity and their great number of reaction sites. Hence, it appears that the surface structure of basic and amphoteric metal oxides which may favour their interaction with the CO₂, as well as their basicity is the determinant factor contributing to the formation of carbonate species. The molecular analysis of CO₂ adsorption on steel slag metal oxides will provide useful data to identify rate-controlling mechanisms and should be considered for the development of new effective methods for the capture of atmospheric CO₂ emissions released from industries.     

Environment and productivities in developed and developing countries: The case of carbon dioxide and sulfur dioxide

We propose a productivity index for undesirable outputs such as carbon dioxide (CO₂) and sulfur dioxide (SO₂) emissions and measure it using data from 51 developed and developing countries over the period 1971–2000. About half of the countries exhibit the productivity growth. The changes in the productivity index are linked with their respective per capita income using a semi-parametric model. Our results show technological catch up of low-income countries. However, overall productivities both of SO₂ and CO₂ show somewhat different results.     

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.     

An investigation of a heat pump system using CO2/propane mixture as a working fluid

In order to decrease the heat rejection pressure of heat pump using pure working fluid, CO₂ or R744, other natural component including hydrocarbons (R290, R600a, R600, R1270, R170, R601) and dimethyl ether (RE170) is added to CO₂, respectively, and then six binary mixtures are achieved. By environmental and thermodynamic comparisons, R290 is selected to be the most appropriate component candidate to mix with CO₂, and meanwhile to weaken the flammability and explosivity for pure R290. Then, the system performances of heat pump using mixture of CO₂ and R290 were experimentally studied when R290 is added to CO₂ with a small fraction, and compared with that of the pure CO₂. The experimental test rig is designed and set up for the transcritical heat pump system. When the refrigerant charge is variable, the heating coefficient performance, optimum heat rejection pressure, compressor power, mass flow rate of refrigerant, and total heat coefficient of gas cooler were researched. The variation ratios of heating coefficient performance and heating capacity with deviation from the optimum refrigerant charge were also investigated. The optimum refrigerant charge of CO₂/R290 is obtained and the research results show that the addition of R290 to CO₂ can efficiently reduce the heat rejection pressure and improve the system performance. The results in the present work could provide useful guidelines for the design and operation of heat pump system using CO₂-based mixture.     

Desorption of CO2 from activated carbon fibre–phenolic resin composite by electrothermal effect

CO₂ capture by electrothermal swing adsorption is considered superior over conventional adsorption approaches: temperature swing adsorption and pressure swing adsorption. In this work, the effects of electricity, preheating and flow rate were studied. An increase in energy input by electricity has been found able to improve desorption performance more significantly than an increase in current level. However, higher current level is recommended because it can minimise energy loss while passing electricity. Higher flow rate can also be beneficial due to the improved desorption rate and reduced desorption time. However, there is a drop in CO₂ concentration in the effluent gas. When desorption takes place at a high current level, preheating is not required as it extends desorption duration with no obvious improvement in desorption rate. CO₂ capture by electrothermal swing adsorption has also been tested with different concentrations of CO₂. It is found that electrothermal swing adsorption can be more energy efficient while dealing with higher concentration CO₂.     

Carbon flows and carbon use in the German anthroposphere: An inventory

Today, global climate change is one of the most urgent environmental problems. The atmospheric concentration of carbon dioxide (CO₂) has to be stabilised by significant reductions of CO₂ emissions in the next decades to keep the expected temperature rise within tolerable borders. Efforts exceeding the implemented measures to reduce CO₂ emissions in Germany are desirable. An important pre-condition for such measures is a scientific-based inventory of the sources, sinks, and use of carbon.In this paper, we present CarboMoG, i.e. Carbon Flow Model of Germany. CarboMoG is a carbon flow model covering carbon flows, carbon sources and sinks in Germany and the German anthroposphere, showing concurrent energy and non-energy use of carbon sources.The model consists of seven modules in German anthroposphere following the German classification of economic sectors. Carbon flows to and from atmosphere and lithosphere as well as imports and exports were included into the model. The model comprises roughly 220 material flows determined based on material flow procedures for the base year 2000.Main sources of carbon are fossil energy carriers from lithosphere and uptake of CO₂ by crops (52% resp. 48% of all carbon sources). The model calculations show that import of energy carriers dominates total carbon import to Germany (82%). Total non-energy use of carbon in Germany is significantly higher than energy use (386 Mt C and 230 Mt C, resp.). Carbon throughput of Industry is greatest (about 224 Mt C input), followed by Energy (about 129 Mt C input). Agriculture and Forestry & Industry show the highest figure for non-energy use of carbon, energy use of carbon is largest in the Energy sector. Emissions of CO₂ to atmosphere account for 94% of all carbon flows to sinks in Germany. Carbon accumulates in German anthroposphere 5 Mt C in 2000.     

Producing biodiesel from waste animal oil by modified ZnO

Biodiesel produced by transesterification of waste animal oil is a promising green fuel in the future. ZnO-Al₂O₃ and ZnO/Zn₂Al composition oxides were prepared by co-precipitation method and impregnation method, respectively. The above catalysts were characterized by X-ray diffraction (XRD), Brunauer--Emmett--Teller (BET) and CO₂ adsorption and temperature-programmed desorption (CO₂-TPD) and show that the high activity for the catalyst is attributed to its high alkalinity. The reaction parameters were optimized and the results show that the transesterification ratio of waste animal oil can reach 98.7% with 10% ZnO/Zn₂Al catalyst after 2 h. Moreover, 10%ZnO/Zn₂Al compound oxides can be active for the successive cycles. The glycerol as a predominant by-product after transesterification is of high purity with high use value.     

Reduction of CaSO4 oxygen carrier with coal in chemical-looping combustion: Effects of temperature and gasification intermediate

Chemical-looping combustion (CLC) has been suggested as an energy efficient method for the capture of carbon dioxide from combustion. Thermodynamics and kinetics of CaSO₄ reduction with coal via gasification intermediate in a CLC process were discussed in the paper, with respect to the CO₂ generating efficiency, the environmental factor and the surface morphology of oxygen carrier. Tests on the combined process of coal gasification and CaSO₄ reduction with coal syngas were conducted in a batch fluidized bed reactor at different reaction temperatures and with different gasification intermediates. The products were characterized by gas chromatograph, gas analyzers and scanning electron microscope. And the results showed that an increase in the reaction temperature aggravated the SO₂ emission. The CO₂ generating efficiency also increased with the temperature, but it decreased when the temperature exceeded 950 °C due to the sintering of oxygen carrier particles. The use of CO₂ as gasification intermediate in the fuel reactor had a positive effect on the sintering-resistant of oxygen carrier particles. However, increasing the steam/CO₂ ratio in gasification intermediate evidently enhanced CO₂ generating efficiency and reduced SO₂ environmental impact.     

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.