Hydrate composite particles for ocean carbon sequestration: field verification

This paper reports on the formation and dissolution of CO2/seawater/CO2 hydrate composite particles produced during field experiments in Monterey Bay, CA using a CO2 injector system previously developed in the laboratory. The injector consisted of a coflow reactor wherein water was introduced as a jet into liquid CO2, causing vigorous mixing of the two immiscible fluids to promote the formation of CO2 hydrate that is stable at ambient pressures and temperatures typical of ocean depths greater than approximately 500 m. Using flow rate ratios of water and CO2 of 1:1 and 5:1, particulate composites of CO2 hydrate/liquid CO2/seawater phases were produced in seawater at depths between 1100 and 1300 m. The resultant composite particles were tracked by a remotely operated vehicle system as they freely traveled in an imaging box that had no bottom or top walls. Results from the field experiments were consistent with laboratory experiments, which were conducted in a 70 L high-pressure vessel to simulate the conditions in the ocean at intermediate depths. The particle velocity and volume histories were monitored and used to calculate the conversion of CO2 into hydrate and its subsequent dissolution rate after release into the ocean. The dissolution rate of the composite particles was found to be higher than that reported for pure CO2 droplets. However, when the rate was corrected to correspond to pure CO2, the difference was very small. Results indicate that a higher conversion of liquid CO2 to CO2 hydrate is needed to form negatively buoyant particles in seawater when compared to freshwater, due primarily to the increased density of the liquid phase but also due to processes involving brine rejection during hydrate formation.     

Limestone-particle-stabilized macroemulsion of liquid and supercritical carbon dioxide in water for ocean sequestration

When liquid or supercritical CO2 is mixed with an aqueous slurry of finely pulverized (1-20 microm) limestone (CaCO3) in a high-pressure reactor, a macroemulsion is formed consisting of droplets of CO2 coated with a sheath of CaCO3 particles dispersed in water. The coated droplets are called globules. Depending on the globule diameter and the CaCO3 sheath thickness, the globules sink to the bottom of the water column, are neutrally buoyant, or float on top of the water. The CaCO3 particles are lodged at the CO2/ H2O interface, preventing the coalescence of the CO2 droplets, and thus stabilizing the CO2-in-water emulsion. We describe the expected behavior of a CO2/H2O/CaCO3 emulsion plume released in the deep ocean for sequestration of CO2 in the ocean to ameliorate global warming. Depending on the amount of CO2 injected, the dense plume will descend a few hundred meters while entraining ambient seawater until it acquires neutral buoyancy in the stratified ocean. After equilibration, the globules will rain out from the plume toward the ocean bottom. This mode of CO2 release will prevent acidification of the seawater around the release point, which is a major environmental drawback of ocean sequestration of liquid, unemulsified CO2.     

Field studies on the formation of sinking CO2 particles for ocean carbon sequestration: effects of injector geometry on particle density and dissolution rate and model simulation of plume behavior

We have carried out the second phase of field studies to determine the effectiveness of a coflow injector which mixes liquid CO2 and ambient seawater to produce a hydrate slurry as a possible CO2 delivery method for ocean carbon sequestration. The experiments were carried out at ocean depths of 1000-1300 m in Monterey Bay, CA, using a larger injector than that initially employed under remotely operated vehicle control and imaging of the product. Solidlike composite particles comprised of water, solid CO2 hydrate, and liquid CO2 were produced in both studies. In the recent injections, the particles consistently sank at rates of approximately 5 cm s(-1). The density of the sinking particles suggested that approximately 40% of the injected CO2 was converted to hydrate, while image analysis of the particle shrinking rate indicated a CO2 dissolution rate of 0.76-1.29 micromol cm(-2) s(-1). Plume modeling of the hydrate composite particles suggests that while discrete particles may sink 10-70 m, injections with CO2 mass fluxes of 1-1000 kg s(-1) would result in sinking plumes 120-1000 m belowthe injection point.     

Fate of rising CO2 droplets in seawater

The sequestration of fossil fuel CO2 in the deep ocean has been discussed by a number of workers, and direct ocean experiments have been carried out to investigate the fate of rising CO2 droplets in seawater. However, no applicable theoretical models have been developed to calculate the dissolution rate of rising CO2 droplets with or without hydrate shells. Such models are important for the evaluation of the fate of CO2 injected into oceans. Here, I adapt a convective dissolution model to investigate the dynamics and kinetics of a single rising CO2 droplet (or noninteracting CO2 droplets) in seawater. The model has no free parameters; all of the required parameters are independently available from literature. The input parameters include: the initial depth, the initial size of the droplet, the temperature as a function of depth, density of CO2 liquid, the solubility of CO2 liquid or hydrate, the diffusivity of CO2, and viscosity of seawater. The effect of convection in enhancing mass transfer is treated using relations among dimensionless numbers. The calculated dissolution rate for CO2 droplets with a hydrate shell agrees with data in the literature. The theory can be used to explore the fate of CO2 injected into oceans under various temperature and pressure conditions.     

Experimental investigation of the rising behavior of CO2 droplets in seawater under hydrate-forming conditions

In a laboratory-based test series, seven experiments along a simulated Pacific hydrotherm at 152 degrees W, 40 degrees N were carried out to measure the rise velocities of liquefied CO2 droplets under (clathrate) hydrate forming conditions. The impact of a hydrate skin on the rising behavior was investigated by comparing the results with those from outside the field of hydrate stability at matching buoyancy. A thermostatted high-pressure tank was used to establish conditions along the natural oceanic hydrotherm. Under P-/T-conditions allowing hydrate formation, the majority of the droplets quickly developed a skin of CO2 hydrate upon contact with seawater. Rise rates of these droplets support the parametrization by Chen et al. (Tellus 2003, 55B, 723-730), which is based on empirical equations developed to match momentum of hydrate covered, deformed droplets. Our data do not support other parametrizations recently suggested in the literature. In the experiments from 5.7 MPa, 4.8 oC to 11.9 MPa, 2.8 degrees C positive and negative deviations from predicted rise rates occurred, which we propose were caused by lacking hydrate formation and reflect intact droplet surface mobility and droplet shape oscillations, respectively. This interpretation is supported by rise rates measured at P-/T-conditions outside the hydrate stability field atthe same liquid CO2-seawater density difference (delta rho) matching the rise rates of the deviating data within the stability field. The results also show that droplets without a hydrate skin ascend up to 50% faster than equally buoyant droplets with a hydrate skin. This feature has a significant impact on the vertical pattern of dissolution of liquid CO2 released into the ocean. The experiments and data presented considerably reduce the uncertainty of the parametrization of CO2 droplet rise velocity, which in the past emerged partly from their scarcity and contradictions in constraints of earlier experiments.     

Ocean sequestration of carbon dioxide: modeling the deep ocean release of a dense emulsion of liquid Co2-in-water stabilized by pulverized limestone particles

The release into the deep ocean of an emulsion of liquid carbon dioxide-in-seawater stabilized by fine particles of pulverized limestone (CaCO3) is modeled. The emulsion is denser than seawater, hence, it will sink deeper from the injection point, increasing the sequestration period. Also, the presence of CaCO3 will partially buffer the carbonic acid that results when the emulsion eventually disintegrates. The distance that the plume sinks depends on the density stratification of the ocean, the amount of the released emulsion, and the entrainment factor. When released into the open ocean, a plume containing the CO2 output of a 1000 MW(el) coal-fired power plant will typically sink hundreds of meters below the injection point. When released from a pipe into a valley on the continental shelf, the plume will sink about twice as far because of the limited entrainment of ambient seawater when the plume flows along the valley. A practical system is described involving a static mixer for the in situ creation of the CO2/seawater/pulverized limestone emulsion. The creation of the emulsion requires significant amounts of pulverized limestone, on the order of 0.5 tons per ton of liquid CO2. That increases the cost of ocean sequestration by about $13/ ton of CO2 sequestered. However, the additional cost may be compensated by the savings in transportation costs to greater depth, and because the release of an emulsion will not acidify the seawater around the release point.     

Experimental determination of the fate of rising CO2 droplets in seawater

Direct oceanic disposal of fossil fuel CO2 is being considered as a possible means to moderate the growth rate of CO2 in the atmosphere. We have measured the rise rate and dissolution rate of freely released CO2 droplets in the open ocean to provide fundamental data for carbon sequestration options. A small amount of liquid CO2 was released at 800 m, at 4.4 degrees C, and the rising droplet stream was imaged with a HDTV camera carried on a remotely operated vehicle. The initial rise rate for 0.9-cm diameter droplets was 10 cm/s at 800 m, and the dissolution rate was 3.0 micromol cm(-2) s(-1). While visual contact was maintained for 1 h and over a 400 m ascent, 90% of the mass loss occurred within 30 min over a 200 m ascent above the release point. Images of droplets crossing the liquid-gas-phase boundary showed formation of a gas head, pinching off of a liquid tail, and rapid gas bubble separation and dissolution.     

Efficient recovery of CO2 from flue gas by clathrate hydrate formation in porous silica gels

Thermodynamic measurements and NMR spectroscopic analysis were used to show that it is possible to recover CO2 from flue gas by forming a mixed hydrate that removes CO2 preferentially from CO2/N2 gas mixtures using water dispersed in the pores of silica gel. Kinetic studies with 1H NMR microimaging showed that the dispersed water in the silica gel pore system reacts readily with the gas, thus obviating the need for a stirred reactor and excess water. Hydrate phase equilibria for the ternary CO2-N2-water system in silica gel pores were measured, which show that the three-phase hydrate-water-rich liquid-vapor equilibrium curves were shifted to higher pressures at a specific temperature when the concentration of CO2 in the vapor phase decreased. 13C cross-polarization NMR spectral analysis and direct measurement of the CO2 content in the hydrate phase suggested that the mixed hydrate is structure I at gas compositions of more than 10 mol % CO2, and that the CO2 molecules occupy mainly the more abundant 5(12)6(2) cages. This makes it possible to achieve concentrations of more than 96 mol % CO2 gas in the product after three cycles of hydrate formation and dissociation. 1H NMR microimaging showed that hydrate yields of better than 85%, based on the amount of water, could be obtained in 1 h when a steady state was reached, although approximately 90% of this yield was achieved after approximately 20 min of reaction time.     

Production of CO2 clathrate hydrate frozen desserts by flash freezing

CO₂ clathrate hydrate is a crystalline water–carbon dioxide structure that can enable novel, strongly carbonated frozen desserts. A CO₂ flash-freezing process has been developed to form CO₂ hydrates during freezing of a dessert mixture. In the process, liquid CO₂ and liquid dessert mixture are emulsified and then sprayed into a chamber in which the CO₂ flashes to a vapor causing the dessert mixture to freeze into a low-density powder. To ensure CO₂ hydrate formation it is important to avoid ice formation because ice to CO₂ hydrate conversion proceeds too slowly to occur during flash freezing. To avoid ice formation it is important to flash the emulsion to a pressure greater than 4.7 bars and disperse the mixture in fine droplets. In this work the key parameters of the process are described, which will enable development of commercial dispensers.     

Formation of carbon dioxide hydrate in soil and soil mineral suspensions with electrolytes

We have identified the effects of solid surface (soil, bentonite, kaolinite, nontronite, and pyrite) and electrolyte (NaCl, KCl, CaCl2, and MgCl2) types on the formation and dissociation of CO2 hydrate in this study. The hydrate formation experiments were conducted by injecting CO2 gas into the soil suspensions with and without electrolytes in a 50 mL pressurized vessel. The formation of CO2 hydrate in deionized water was faster than that in aqueous electrolyte solutions. The addition of soil suspensions accelerated the formation of CO2 hydrate in the electrolyte solutions. The hydrate formation times in the solid suspensions without electrolytes were very similar to that in the deionized water. We did not observe any significant differences between the hydrate dissociation in the solid suspension and that in the deionized water. The pHs of clay mineral suspensions decreased significantly after CO2 hydrate formation and dissociation experiments, while the pH of the soil suspension slightly decreased by less than pH 1 and that of pyrite slightly increased due to the dissolution of CO2 forming carbonic acid. The results obtained from this research could be indirectly applied to the fate of CO2 sequestered into geological formations as well as its storage as a form of CO2 hydrate.     

Effect of organic matters on CO2 hydrate formation in Ulleung Basin sediment suspensions

Marine sediment core samples collected from a gas hydrate deposit site (Ulleung Basin (UB), East Sea, Korea) were explored to identify the role of sediment organic matters (SOMs) on the formation of CO(2) hydrate. Two distinct CO(2) hydrate formation regimes (favorable (≤40 min) and unfavorable (>250 min)) were observed from the hydrate formation tests. CO(2) hydrate induction time in UB sediment suspensions was approximately seven times faster than that in UB sediment suspensions without SOMs (baked UB), showing a direct influence of SOMs. Spectrometric and spectroscopic analyses confirmed the existence of different types of SOMs including nonhumic and humic substances in UB sediment samples. We found SOMs with aromatic ring structures in all sediment extracts and SOMs with amine and amide groups and lignin in alkaline extracts. SOMs were extracted from UB sediment core samples (1 g each). Measured CO(2) hydrate induction times were different in baked UB sediment suspensions with different extracts of UB sediments. The experimental results demonstrated that SOMs can play a significant role to accelerate the formation of CO(2) hydrate in UB sediment suspensions, suggesting that the gas hydrate deposit site at UB may be a proper place for CO(2) sequestration as a form of CO(2) hydrate.     

Potential restrictions for CO2 sequestration sites due to shale and tight gas production

Carbon capture and geological sequestration is the only available technology that both allows continued use of fossil fuels in the power sector and reduces significantly the associated CO(2) emissions. Geological sequestration requires a deep permeable geological formation into which captured CO(2)can be injected, and an overlying impermeable formation, called a caprock, that keeps the buoyant CO(2) within the injection formation. Shale formations typically have very low permeability and are considered to be good caprock formations. Production of natural gas from shale and other tight formations involves fracturing the shale with the explicit objective to greatly increase the permeability of the shale. As such, shale gas production is in direct conflict with the use of shale formations as a caprock barrier to CO(2) migration. We have examined the locations in the United States where deep saline aquifers, suitable for CO(2) sequestration, exist, as well as the locations of gas production from shale and other tight formations. While estimated sequestration capacity for CO(2) sequestration in deep saline aquifers is large, up to 80% of that capacity has areal overlap with potential shale-gas production regions and, therefore, could be adversely affected by shale and tight gas production. Analysis of stationary sources of CO(2) shows a similar effect: about two-thirds of the total emissions from these sources are located within 20 miles of a deep saline aquifer, but shale and tight gas production could affect up to 85% of these sources. These analyses indicate that colocation of deep saline aquifers with shale and tight gas production could significantly affect the sequestration capacity for CCS operations. This suggests that a more comprehensive management strategy for subsurface resource utilization should be developed.     

Modeling and measurement of electrostatic spray behavior in a rectangular throat of Pease-Anthony venturi scrubber

This paper presents the simulation and experimental results of the distribution of droplets produced by electrostatic nozzles inside a venturi scrubber. The simulation model takes into account initial liquid momentum, hydrodynamic, gravitational and electric forces, and eddy diffusion. The velocity and concentration profile of charged droplets injected from an electrostatic nozzle in the scrubber under the combined influence of hydrodynamic and electric fields were simulated. The effects of operating parameters, such as gas velocity, diameter of the scrubbing droplets, charge-to-mass ratio, and liquid-to-gas ratio on the distribution of the water droplets within the scrubber, were also investigated. The flux distribution of scrubbing liquid in the presence of electric field is improved considerably over a conventional venturi scrubber, and the effect increases with the increase in charge-to-mass ratio. Improved flux distribution using charged droplets increases the calculated overall collection efficiency of the submicron particles. However, the effect of an electric field on the droplet distribution pattern for small drop sizes in strong hydrodynamic field conditions is negligible. Simulated results are in good agreement with the experimental data obtained in the laboratory.     

Chemical looping combustion in a rotating bed reactor--finding optimal process conditions for prototype reactor

A lab-scale rotating bed reactor for chemical looping combustion has been designed, constructed, and tested using a CuO/Al(2)O(3) oxygen carrier and methane as fuel. Process parameters such as bed rotating frequency, gas flows, and reactor temperature have been varied to find optimal performance of the prototype reactor. Around 90% CH(4) conversion and >90% CO(2) capture efficiency based on converted methane have been obtained. Stable operation has been accomplished over several hours, and also--stable operation can be regained after intentionally running into unstable conditions. Relatively high gas velocities are used to avoid fully reduced oxygen carrier in part of the bed. Potential CO(2) purity obtained is in the range 30 to 65%--mostly due to air slippage from the air sector--which seems to be the major drawback of the prototype reactor design. Considering the prototype nature of the first version of the rotating reactor setup, it is believed that significant improvements can be made to further avoid gas mixing in future modified and up-scaled reactor versions.     

Environmental controls of cadmium desorption during CO₂ leakage

Geologic carbon sequestration represents a promising option for carbon mitigation. Injected CO(2), however, can potentially leak into water systems, increase water acidity, and mobilize metals. This study used column experiments to quantify the effects of environmental controls on cadmium desorption during CO(2) leakage in subsurface systems without ambient flow. Results show that fast leakage rates are responsible for earlier and larger amounts of Cd desorption. Long weathering time of Cd laden clay leads to low Cd desorption. Calcite content as low as 10% can mitigate the effect of pH reduction and result in zero Cd desorption. Increasing the salinity of the leaking fluid has a relatively minor effect, primarily due to the offsetting impacts of an increased extent of ion exchange and the decrease in CO(2) solubility (and therefore acidity). This work systematically quantifies, for the first time, the effects of environmental controls on Cd desorption and points to key parameters for risk assessment associated with metal mobilization during CO(2) leakage.     

Visual observations and Raman spectroscopic studies of supercritical water oxidation of chlorobenzene in an anticorrosive fused-silica capillary reactor

Supercritical water oxidation of chlorobenzene (CB) was studied using an anticorrosive fused-silica capillary reactor (FSCR) combined with a polarization microscope recorder system for visual observations and a Raman spectroscopic system for qualitative and quantitative analyses of the gaseous products. The effects of operating parameters, including the stoichiometric amount of oxidizer, temperature, and reaction time, on oxidation behavior were investigated. Our results show that a 100% conversion yield of CB and 100% CO(2) yield were achieved with a 150% stoichiometric amount of H(2)O(2) at 450 °C within 8 and 10 min, respectively. The conversion yield and the CO(2) yield both depend strongly on temperature, and the CO(2) yield is always less than the CB conversion yield under the same experimental conditions, suggesting that some carbon exists in intermediate products of incomplete oxidation, as confirmed by gas chromatography-mass spectrometry. Global kinetics analysis based on the complete conversion of CB to CO(2) showed that the reaction was first order. CB phase-changes in sub- and supercritical H(2)O-H(2)O(2) system in the FSCR were observed and recorded; CB eventually dissolved completely to form a homogeneous liquid solution above 326.1 °C. This method has great potential for use in the theoretical study of fluids and chemical reactions under elevated pressure-temperature conditions.     

Carbon dioxide capture from atmospheric air using sodium hydroxide spray

In contrast to conventional carbon capture systems for power plants and other large point sources, the system described in this paper captures CO2 directly from ambient air. This has the advantages that emissions from diffuse sources and past emissions may be captured. The objective of this research is to determine the feasibility of a NaOH spray-based contactor for use in an air capture system by estimating the cost and energy requirements per unit CO2 captured. A prototype system is constructed and tested to measure CO2 absorption, energy use, and evaporative water loss and compared with theoretical predictions. A numerical model of drop collision and coalescence is used to estimate operating parameters for a full-scale system, and the cost of operating the system per unit CO2 captured is estimated. The analysis indicates that CO2 capture from air for climate change mitigation is technically feasible using off-the-shelf technology. Drop coalescence significantly decreases the CO2 absorption efficiency; however, fan and pump energy requirements are manageable. Water loss is significant (20 mol H2O/mol CO2 at 15 degrees C and 65% RH) but can be lowered by appropriately designing and operating the system. The cost of CO2 capture using NaOH spray (excluding solution recovery and CO2 sequestration, which may be comparable) in the full-scale system is 96 $/ton-CO2 in the base case, and ranges from 53 to 127 $/ton-CO2 under alternate operating parameters and assumptions regarding capital costs and mass transfer rate. The low end of the cost range is reached by a spray with 50 microm mean drop diameter, which is achievable with commercially available spray nozzles.     

Process for recycling waste aluminum with generation of high-pressure hydrogen

An innovative environmently friendly hydrolysis process for recycling waste aluminum with the generation of high-pressure hydrogen has been proposed and experimentally validated. The effect of the concentration of sodium hydroxide solution on hydrogen generation rate was the main focus of the study. In the experiments, distilled water and aluminum powder were placed in the pressure-resistance reactor made of Hastelloy, and was compressed to a desired constant water pressure using a liquid pump. The sodium hydroxide solution was supplied by liquid pump with different concentrations (from 1.0 to 5.0 mol/dm3) at a constant flow rate into the reactor by replacing the distilled water, and the rate of hydrogen generated was measured simultaneously. The liquid temperature in the reactor increased due to the exothermic reaction given by Al + OH(-) + 3H2O = 1.5H2 + Al(OH)4(-) + 415.6 kJ. Therefore, a high-pressure hydrogen was generated at room temperature by mixing waste aluminum and sodium hydroxide solution. As the hydrogen compressor used in this process consumes less energy than the conventional one, the generation of hydrogen having a pressure of almost 30 MPa was experimentally validated together with Al(OH)3, a useful byproduct.     

Reducing risk in basin scale CO2 sequestration: a framework for integrated monitoring design

Injection of CO(2) into geological structures is a key technology for sequestering CO(2) emissions captured from the combustion of fossil fuels. Current projects inject volumes on the order of megatonnes per year. However, injection volumes must be increased by several orders of magnitude for material reductions in ambient concentrations. A number of questions surrounding safety and security of injection have been raised about the large scale deployment of geological CO(2) sequestration. They are site specific and require an effective monitoring strategy to mitigate risks of concern to stakeholders. This paper presents a model-based framework for monitoring design that can provide a quantitative understanding of the trade-offs between operational decisions of cost, footprint size, and uncertainty in monitoring strategies. Potential risks and challenges of monitoring large scale CO(2) injection are discussed, and research areas needed to address uncertainties are identified. Lack of clear guidance surrounding monitoring has contributed to hampering the development of policies to promote the deployment of large scale sequestration projects. Modeling provides an understanding of site specific processes and allows insights into the complexity of these systems, facilitating the calibration of an appropriate plan to manage risk. An integrated policy for risk-based monitoring design, prior to large scale deployment of sequestration will ensure safe and secure storage through an understanding of the real risks associated with large scale injection.     

Application of amine-tethered solid sorbents for direct CO2 capture from the ambient air

While current carbon capture and sequestration (CCS) technologies for large point sources can help address the impact of CO(2) buildup on global climate change, these technologies can at best slow the rate of increase of the atmospheric CO(2) concentration. In contrast, the direct CO(2) capture from ambient air offers the potential to be a truly carbon negative technology. We propose here that amine-based solid adsorbents have significant promise as key components of a hypothetical air capture process. Specifically, the CO(2) capture characteristics of hyperbranched aminosilica (HAS) materials are evaluated here using CO(2) mixtures that simulate ambient atmospheric concentrations (400 ppm CO(2) = "air capture") as well as more traditional conditions simulating flue gas (10% CO(2)). The air capture experiments demonstrate that the adsorption capacity of HAS adsorbents are only marginally influenced even with a significant dilution of the CO(2) concentration by a factor of 250, while capturing CO(2) reversibly without significant degradation of performance in multicyclic operation. These results suggest that solid amine-based air capture processes have the potential to be an effective approach to extracting CO(2) from the ambient air.