Design and operation of pilot plant for CO2 capture from IGCC flue gases by combined cryogenic and hydrate method

This project is a trial conducted under contract with CO₂CRC, Australia of a new CO₂ capture technology that can be applied to integrated gasification combined cycle power plants and other industrial gasification facilities. The technology is based on combination of two low temperature processes, namely cryogenic condensation and the formation of hydrates, to remove CO₂ from the gas stream. The first stage of this technology is condensation at −55 °C where CO₂ concentration is expected to be reduced by up to 75 mol%. Remaining CO₂ is captured in the form of solid hydrate at about 1 °C reducing CO₂ concentration down to 7 mol% using hydrate promoters. This integrated cryogenic condensation and CO₂ hydrate capture technology hold promise for greater reduction of CO₂ emissions at lower cost and energy demand. Overall, the process produced gas with a hydrogen content better than 90 mol%. The concentrated CO₂ stream was produced with 95-97 mol% purity in liquid form at high pressure and is available for re-use or sequestration. The enhancement of carbon dioxide hydrate formation and separation in the presence of new hydrate promoter is also discussed. A laboratory scale flow system for the continuous production of condensed CO₂ and carbon dioxide hydrates is also described and operational details are identified.     

Gas hydrate formation from hydrogen/carbon dioxide and nitrogen/carbon dioxide gas mixtures

Gas hydrates from CO₂/N₂ and CO₂/H₂ gas mixtures were formed in a semi-batch stirred vessel at constant pressure and temperature of 273.7 K. These mixtures are of interest to CO₂ separation and recovery from flue gas and fuel gas, respectively. During hydrate formation the gas uptake was determined and the composition changes in the gas phase were obtained by gas chromatography. The rate of hydrate growth from CO₂/H₂ mixtures was found to be the fastest. In both mixtures CO₂ was found to be preferentially incorporated into the hydrate phase. The observed fractionation effect is desirable and provides the basis for CO₂ capture from flue gas or fuel gas mixtures. The separation from fuel gas is also a source of H₂. The impact of tetrahydrofuran (THF) on hydrate formation from the CO₂/N₂ mixture was also observed. THF is known to substantially reduce the equilibrium formation conditions enabling hydrate formation at much lower pressures. THF was found to reduce the induction time and the rate of hydrate growth.     

Separation and capture of carbon dioxide from CO2/H2 syngas mixture using semi-clathrate hydrates

The relation between anthropogenic emissions of CO₂ and its increased levels in the atmosphere with global warming and climate change has been well established and accepted. Major portion of carbon dioxide released to the atmosphere, originates from combustion of fossil fuels. Integrated gasification combined cycle (IGCC) offers a promising fossil fuel technology considered as a clean coal-based process for power generation particularly if accompanied by precombustion capture. The latter includes separation of carbon dioxide from a synthesis gas mixture containing 40 mol% CO₂ and 60 mol% H₂.A novel approach for capturing CO₂ from the above gas mixture is to use gas hydrate formation. This process is based on selective partition of CO₂ between hydrate phase and gas phase and has already been studied with promising results. However high-pressure requirement for hydrate formation is a major problem.We have used semiclathrate formation from tetrabutylammonium bromide (TBAB) to experimentally investigate CO₂ capture from a mixture containing 40.2 mol% of CO₂ and 59.8 mol% of H₂. The results shows that in one stage of gas hydrate formation and dissociation, CO₂ can be enriched from 40 mol% to 86 mol% while the concentration of CO₂ in equilibrium gas phase is reduced to 18%. While separation efficiency of processes based on hydrates and semi-clathrates are comparable, the presence of TBAB improves the operating conditions significantly. Furthermore, CO₂ concentration could be increased to 96 mol% by separating CO₂ in two stages.     

Dynamic measurements of hydrate based gas separation in cooled silica gel

Hydrate based gas separation is a promising method for carbon dioxide capture. The purpose of this study is to analyze hydrates formation and dissociation characters when gas mixture flows through cooled silica gel. The additives mixture (THF/SDS) was used to saturate the silica gel partly, and gas mixture (CO₂/H₂) was injected into it to form hydrates. Magnetic resonance imaging (MRI) images were obtained using fast spin echo multi-slice pulse sequence. Hydrates saturations were calculated quantitatively using MRI data. The experimental results showed that the optimal initial solution saturation was 34.2% in this investigation. The gas component was analyzed to assess the separation efficiency. For hydrates dissociation processes at 1 atmospheric pressure, CO₂ concentrations increased obviously. Half of the six cycles showed that more than 85.00 mol% CO₂ contained in the capture gas, and the lowest CO₂ concentration was 64.83 mol%. Hydrate blockages appeared frequently, which restricted the contact of gas and solution and caused the incomplete transformations of residual solution to hydrates. It was a key restricted factor for hydrate based CO₂ capture.     

Study on the influence of SDS and THF on hydrate-based gas separation performance

Hydrate additives can be used to mitigate hydrate formation conditions, promote hydrate growth rate and improve separation efficiency. CO₂ + N₂ and CO₂ + CH₄ systems with presence of sodium dodecyl sulfate (SDS) or tetrahydrofuran (THF) are studied to analyze the effect of hydrate additives on gas separation performance. The experiment results show that CO₂ can be selectively enriched in the hydrate phase. SDS can speed up the hydrate growth rate by facilitating gas molecules solubilization. When SDS concentration increases, split and loss fraction increase initially and then decrease slightly, resulting in a decreased separation factor. The optimum concentration of SDS exists at the range of 100–300 ppm. As THF can be easily encaged in hydrate cavities, hydrate formation condition can be mitigated greatly with its existence. Additionally, THF can also strengthen hydrate formation. The THF effect on separation performance is related to feed gas components. CO₂ occupies the small cavities of type II hydrate prior to N₂. But the competitiveness of CO₂ and CH₄ to occupy cavities are quite fair. The variations of split fraction, loss fraction and separation factor depend on the concentration of THF added. The work in this paper has a positive role in flue gas CO₂ capture and natural gas de-acidification.     

A Single Stage Membrane Process for CO2 Capture from Flue Gas by a Facilitated Transport Membrane

Carbon dioxide is the most important anthropogenic greenhouse gas and it accounts for about 80% of all greenhouse gases (GHG). The global atmospheric CO₂ concentrations have been increased significantly and have become the major source responsible for global warming; the greatest environmental challenge the world is facing now. The efforts to control the GHG emissions include the recovery of CO₂ from flue gas. In this work, feasibility analysis, based on a single stage membrane process, has been carried out with an in-house membrane program interfaced within process simulation program (AspenHysys) to investigate the influence of process parameters on the energy demand and flue gas processing cost. A novel CO₂-selective membrane with the facilitated transport mechanism has been employed to capture CO₂ from the flue gas mixtures. The results show that a membrane process using the facilitated transport membrane can also be considered as an alternative CO₂ capture process and it is possible to achieve more than 90% CO₂ recovery and 90% CO₂ purity in the permeate with reasonable energy consumption compared to amine absorption and other capture techniques.     

Structure and thermal expansion of natural gas clathrate hydrates

We report on the structural properties of natural gas hydrate crystals from the Sea of Okhotsk. Using powder X-ray diffraction (PXRD), it was determined that sediments from four locations contained type I gas hydrate, which encage mostly methane (96-98%) and a small amount of carbon dioxide. For all hydrates, the lattice constant was estimated to be at 113 K, which approximately equals that of pure methane hydrate. The result is in good agreement with the structure of artificially synthesized methane + carbon dioxide mixed-gas hydrates. These results suggest that the lattice constant of the natural gas hydrate does not change due to a change of CO₂ gas content. In addition, the thermal expansion of the sampled hydrate was measured for the temperature range of 83-173 K, and the resulting density of the hydrate crystal at 273 K was estimated to be . These results are essential for applying natural gas hydrates as an alternative natural fuel resources.     

Quantitative analysis of CO2 hydrate formation in porous media by proton NMR

Gas hydrate is a nonstoichiometric crystal compound formed from water and gas. Most nonvisual studies on gas hydrate are unable to detect how much water is converted to hydrates, and thus, the hydrate stoichiometry calculations are inaccurate. This study investigated the CO₂ hydrate formation process in porous media directly and quantitatively. The characteristics of the time-variable consumption of hydrate formation indicated a two-stage formation, hydrate enclathration and continuous occupancy. The enclathration stage occurred in the first 20 min of the formation when considerable heat is released. The continuous occupancy stage lasted longer than the hydrate enclathration because the empty cages in previously formed hydrates would also be occupied. The higher formation pressures can accelerate water consumption and increase cage occupancy. The compositions of completely formed CO₂ hydrates at 2.7, 3.0, and 3.3 MPa and 275.15 K were determined as CO₂·6.90H₂O, CO₂·6.70H₂O, and CO₂·6.49H₂O, respectively.     

Experimental and theoretical investigations on the carbon dioxide gas hydrate formation kinetics at the onset of turbidity regarding CO2 capture and sequestration processes

The carbon dioxide gas hydrate formation kinetics at the onset of turbidity is experimentally and theoretically investigated. It is shown that the time-dependent heterogeneous nucleation and growth kinetics are simultaneously governing the hydrate formation process at the onset of turbidity. A new approach is also presented for determination of gas hydrate-liquid interfacial tension. The CO₂ hydrate-liquid interfacial tension according to the suggested heterogeneous nucleation mechanism is found to be about 12.7 mJ/m². The overall average absolute deviation between predicted and measured CO₂ molar consumption is about 0.61%, indicating the excellent accuracy of the proposed model for studying the hydrate-based CO₂ capture and sequestration processes over wide ranges of pressures and temperatures.     

Prediction of carbon dioxide gas hydrate formation conditions in aqueous electrolyte solutions

A methodology for predicting the incipient equilibrium conditions for carbon dioxide gas hydrates in the presence of electrolytes such as NaCl, KCl and CaCl₂ is presented. The method utilizes the statistical thermodynamics model of van der Waals and Platteeuw (1959) to describe the solid hydrate phase. Three different models were examined for the representation of the liquid phase: Chen and Evans (1986), Zuo and Guo (1991), and Aasberg-Petersen et al. (1991). It was found that the model of Zuo and Guo (1991) gave the best results for predicting incipient CO₂ gas hydrate conditions in aqueous single salt solutions. The model was then extended for prediction of CO₂ gas hydrates in mixed salts solutions. The predictions agree very well with experimental data.     

Metastable states during dissociation of carbon dioxide hydrates below 273 K

In this study, the dissociation of isolated carbon dioxide hydrate particles of sizes in the range 0.25–2.5 mm was investigated. It was found that below the ice melting point, the hydrates dissociated into supercooled water (metastable liquid) and gas. The formation of the liquid phase during CO₂ hydrate dissociation was visually observed, and the pressures of the hydrate dissociation into supercooled water and gas were measured in the temperature range 249–273 K. These pressures agreed well with the calculated data for the supercooled water–hydrate–gas metastable equilibrium (Istomin et al., 2006). In the P–T area on the phase diagram bounded by the ice–hydrate–gas equilibrium curve and the supercooled water–hydrate–gas metastable equilibrium curve, hydrates could exist for a long time because the metastable phase and their stability are not connected to the self-preservation effect. The growth of the metastable CO₂ hydrate film on the surface of supercooled water droplets formed during the hydrate dissociation was observed at pressure above the three-phase supercooled water–hydrate–gas metastable equilibrium pressure but still below the three-phase ice–hydrate–gas equilibrium pressure. It was found that the growth rate of the metastable CO₂ hydrate film was higher by a factor of 25 and 50 than that for methane hydrate and propane hydrate, respectively.     

Results from trialling aqueous NH3 based post-combustion capture in a pilot plant at Munmorah power station: Absorption

Australia's Commonwealth Scientific and Industrial Research Organization (CSIRO) and Delta Electricity have developed, commissioned and operated an A$7 million aqueous NH₃ based post-combustion capture (PCC) pilot plant at the Munmorah black coal fired power station in Australia. The results from the pilot plant trials will be used to address the gap in know-how on application of aqueous NH₃ for post-combustion capture of CO₂ and other pollutants in the flue gas and explore the potential of the NH₃ process for application in the Australia power sector. This paper is one of a series of publications to report and discuss the experimental results obtained from the pilot plant trials and primarily focuses on the absorption section.The pilot plant trials have confirmed the technical feasibility of the NH₃ based capture process. CO₂ removal efficiency of more than 85% can be achieved even with low NH₃ content of up to 6 wt%. The NH₃ process is effective for SO₂ but not for NO in the flue gas. More than 95% of SO₂ in the flue gas is removed in the pre-treatment column using NH₃. The mass transfer coefficients for CO₂ in the absorber as functions of CO₂ loading and NH₃ concentration have been obtained based on pilot plant data.     

Phase behavior of gas hydrates in nanoporous materials: Review

A precise understanding of phase behavior for a variety of both artificial and natural processes is essential to achieving scientific and technological goals. There has been growing research interest in gas hydrates confined in nanoporous media aiming to simulate and analyze the unique behavior of natural gas hydrates in sediments. Moreover, the appearance of peculiar properties due to the confinement effect stimulates research on gas hydrate technology for gas separation, such as CO₂ capture from versatile pre/post combustion emissions. In spite of their importance, reliable phase equilibrium data on gas hydrates confined at a nanoscale are scattered throughout the literature, while those in bulk state are abundant. Accordingly, we surveyed the previous studies on the phase behavior of gas hydrates in various nanoporous materials to include and provide valuable information and knowledge for start-up researchers in various gas hydrate fields.     

Comparison of solvent performance for CO2 capture from coal-derived flue gas: A pilot scale study

The performance of a proprietary solvent (CAER-B2), an amine-carbonate blend, for the absorption of CO₂ from coal-derived flue gas is evaluated and compared with state-of-the-art 30 wt% monoethanolamine (MEA) under similar experimental conditions in a 0.1 MWth pilot plant. The evaluation was done by comparing the carbon capture efficiency, the overall mass transfer rates, and the energy of regeneration of the solvents. For similar carbon loadings of the solvents in the scrubber, comparable mass transfer rates were obtained. The rich loading obtained for the blend was 0.50 mol CO₂/mol amine compared to 0.44 mol CO₂/mol amine for MEA. The energy of regeneration for the blend was about 10% lower than that of 30 wt% MEA. At optimum conditions, the blend shows promise in reducing the energy penalty associated with using industry standard, MEA, as a solvent for CO₂ capture.     

Phase and kinetic behavior of the mixed methane and carbon dioxide hydrates

Large amounts of CH₄ are stored as hydrates on continental margins and permafrost regions. If the CH₄ hydrates could be converted into CO₂ hydrate, they would serve double duty as CH₄ sources and CO₂ storage sites in the deep ocean sediments. As preliminary investigations, both the phase behavior of CH₄ hydrates and kinetic behavior of CO₂ hydrate were measured at versatile conditions that can simulate actual marine sediments. When measuring three-phase equilibria (H-LW-V) containing CH₄ hydrate, we also closely examined pore and electrolyte effects of clay and NaCl on hydrate formation. These two effects inhibited hydrate nucleation and thus made the hydrate equilibrium line shift to a higher pressure region. In addition, the kinetic data of CO₂ hydrate in the mixtures containing clay and NaCl were determined at 2.0 MPa and 274.15 K. Clay mineral accelerated an initial formation rate of CO₂ hydrate by inducing nucleation as initiator, but total amount of formed CO₂, of course, decreased due to the capillary effect of clay pores. Also, the addition of NaCl in sample mixtures made both initial formation rate and total amount of CO₂ consumption decrease.     

Extraction of methane hydrate energy by carbon dioxide injection-key challenges and a paradigm shift

Significant effort including field work has been devoted to develop a natural gas extraction technology from natural gas hydrate reservoirs through the injection of carbon dioxide. Natural gas hydrate is practically methane hydrate. The hypothesis is that carbon dioxide will be stored as hydrate owing to its favorable stability conditions compared to methane hydrate. Although the dynamics of the CO₂/CH₄ exchange process are not entirely understood it is established that the exchange process is feasible. The extent is limited but even if the CH₄ recovery is optimized there is a need for a CH₄/CO₂ separation plant to enable a complete cyclic sequence of CO₂ capture, injection and CH₄ recovery. In this paper we propose an alternative paradigm to the Inject (CO₂)/Exchange with (CH₄)/Recover (CH₄) one namely Recover (CH₄) first and then Inject (CO₂) for Storage.     

Modification of ABS Membrane by PEG for Capturing Carbon Dioxide from CO2/N2 Streams

Carbon dioxide capture and storage (CCS) has been propounded as an important issue in greenhouse gas emissions control. In this connection, in the present article, the advantages of using polymeric membrane for separation of carbon dioxide from CO₂/N₂ streams have been discussed. A novel composition for fabrication of a blend membrane prepared from acrylonitrile-butadiene-styrene (ABS) terpolymer and polyethylene glycol (PEG) has been suggested. The influence of PEG molecular weight (in the range of 400 to 20000) on membrane characteristics and gas separation performance, the effect of PEG content (0–30 wt%) on gas transport properties, and the effect of feed side pressure (ranging from 1 to 8 bar) on CO₂ permeability have been studied. The results show that CO₂ permeability increases from 5.22 Barrer for neat ABS to 9.76 Barrer for ABS/PEG20000 (10 wt%) while the corresponding CO₂/N₂ selectivity increases from 25.97 to 44.36. Furthermore, it is concluded that this novel membrane composition has the potential to be considered as a commercial membrane.     

Gas hydrates: A cleaner source of energy and opportunity for innovative technologies

The global energy system is characterized by a gradual de-carbonization and move to cleaner burning technologies: from wood to coal to oil and to natural gas. A final destination characterized by the term“hydrogen economy” is desired. Gas hydrate found in the earth’s crust is considered a source of natural gas that is essentially 100% methane (CH₄) gas. Natural gas hydrate estimates worldwide range from 10,000 to 40,000 trillion cubic meters (TCM). Efforts are underway to exploit this resource. These methane hydrates in the earth’s crust also have the potential to be a significant factor in global climate change. Moreover, gas hydrates offer opportunities for the development of innovative technologies (separation of CO₂ from CO₂/N₂ and CO₂/H₂ mixtures, CO₂ sequestration, natural gas transportation and storage and H₂ storage). In this work we assess the progress towards exploitation of gas hydrates as a resource for methane (cleaner energy) and summarize the state of the art with respect to the role of gas hydrates in the development of innovative technologies.     

Ca-based sorbent looping combustion for CO2 capture in pilot-scale dual fluidized beds

To demonstrate process feasibility of in situ CO₂ capture from combustion of fossil fuels using Ca-based sorbent looping technology, a flexible atmospheric dual fluidized bed combustion system has been constructed. Both reactors have an ID of 100 mm and can be operated at up to 1000 °C at atmospheric pressure. This paper presents preliminary results for a variety of operating conditions, including sorbent looping rate, flue gas stream volume, CaO/CO₂ ratio and combustion mode for supplying heat to the sorbent regenerator, including oxy-fuel combustion of biomass and coal with flue gas recirculation to achieve high-concentration CO₂ in the off-gas. It is the authors' belief that this study is the first demonstration of this technology using a pilot-scale dual fluidized bed system, with continuous sorbent looping for in situ CO₂ capture, albeit at atmospheric pressure. A multi-cycle test was conducted and a high CO₂ capture efficiency (> 90%) was achieved for the first several cycles, which decreased to a still acceptable level (> 75%) even after more than 25 cycles. The cyclic sorbent was sampled on-line and showed general agreement with the features observed using a lab-scale thermogravimetric analysis (TGA) apparatus. CO₂ capture efficiency decreased with increasing number of sorbent looping cycles as expected, and sorbent attrition was found to be another significant factor to be limiting sorbent performance.     

Pilot plant study of post-combustion carbon dioxide capture by reactive absorption: Methodology, comparison of different structured packings, and comprehensive results for monoethanolamine

Post-combustion carbon capture (PCC) from fossil fuel power plants by reactive absorption can substantially contribute to reduce emissions of the greenhouse gas CO₂. To test new solvents for this purpose small pilot plants are used. The present paper describes results of comprehensive studies of the standard PCC solvent MEA (0.3 g/g monoethanolamine in water) in a pilot plant in which the closed cycle of absorption/desorption process is continuously operated (column diameters: 0.125 m, absorber/desorber packing height: 4.25/2.55 m, packing type: Sulzer BX 500, flue gas flow: 30-110 kg/h, CO₂ partial pressure: 35-135 mbar). The data establish a base line for comparisons with new solvents tested in the pilot plant and can be used for a validation of models of the PCC process with MEA. The ratio of the solvent to the flue gas mass flow is systematically varied at constant CO₂ removal rate, and CO₂ partial pressure in the flue gas. Optimal operating points are determined. In the present study the structured packing Sulzer BX 500 is used. The experiments with the removal rate variation are carried out so that the results can directly be compared to those from a previous study in the same plant that was carried out using Sulzer Mellapak 250.Y. A strategy for identifying the influence of absorption kinetics on the results is proposed, which is based on a variation of the gas load at a constant L/G ratio and provides valuable insight on the transferability of pilot plant results.