Near-surface monitoring for the ZERT shallow CO2 injection project

As part of a collaborative effort operated by the Zero Emission Research and Technology Center (ZERT), a series of two shallow releases of CO₂ was performed at a test site in Bozeman, MT. The purpose of the experiment was to simulate possible leakage scenarios from a carbon capture and storage operation in order to further develop and verify monitoring technologies used to characterize and quantify the release of CO₂. The project included collaboration with several research groups and organizations. Presented here are the results of soil–gas monitoring conducted by researchers from the National Energy Technology Laboratory, including CO₂ flux measurement, soil–gas analysis, perfluorocarbon tracer monitoring, and soil resistivity measurements. Together, these methods proved to be effective in detecting and characterizing leakage in the near-surface.     

ELEVATED ATMOSPHERIC CO2 INCREASES WATER AVAILABILITY IN A WATER-LIMITED GRASSLAND ECOSYSTEM1

ABSTRACT: Californian annual grassland on sandstone (moderately fertile) and serpentine (very infertile) soils at the Jasper Ridge Biological Preserve, Stanford, California, were exposed to ambient or elevated (ambient + 36 Pa CO₂) atmospheric CO₂ in open-top chambers since December 1991. We measured ecosystem evapotranspiration with open gas-exchange systems, and soil moisture with time-domain reflectometry (TDR) over 0–15 cm (serpentine) and 0–30 cm (sandstone) depths, at times of peak above ground physiological activity. Evapotranspiration decreased by 12 to 63 percent under elevated CO₂ in three consecutive years in the sandstone ecosystem (p = 0.053, p = 0.162, p = 0.082 in 1992, 1993, and 1994, respectively). In correspondence with decreased evapotranspiration, late-season soil moisture reserves in the sandstone were extended temporally by 10 ± 3 days in 1993 and by 28 ± 11 days in 1994. The effect of elevated CO₂ on soil moisture was greater in the drier spring of 1994 (419 mm annual rainfall) than in 1993 (905 mm annual rainfall). In the serpentine ecosystem, evapotranspiration and soil moisture reserves were not clearly affected by elevated CO₂. Soil water may be conserved in drought-affected ecosystems exposed to elevated CO₂, but the amount of conservation appears to depend on the relative importance of transpiration and soil evaporation in controlling water flux.     

CO2 removal using membrane gas absorption

The objective of this study is to investigate the potential process for the removal of carbon dioxide (CO₂) from flue gas using fundamental membrane contactor, which is a membrane gas absorption (MGA) system. The experiments consisted of microporous polyvinylidenefluoride (PVDF) flat sheet membrane with 0.1 μm (as module I) and 0.45 μm (as module II) pore size. 2-Amino-2-methyl-1-propanol (AMP) solution was employed as the liquid absorbent. The effect of AMP concentration was studied with variation in the range 1–5 M. In addition, the experiments were carried out with 10%, 20%, 30% and 40% gas ratio of CO₂ to N₂ and pure CO₂ as well. Through contact angle measurement, membranes for module I and module II were obtained with CA values of around 130.25° and 127.77°, respectively. The mass transfer coefficients for module II are lower than those of module I for 1–5 M of AMP. Furthermore, the increase in CO₂ concentration in the feed gas stream enhanced the CO₂ flux as the driving force of the system was increased in sequence from 1 M to 5 M of AMP. However, after the particular percentage (40%) of CO₂ inlet concentration, the CO₂ fluxes seem saturated. The combination of AMP as liquid absorbent and PVDF microporous membrane in MGA system has shown the potential to remove the CO₂ from flue gas. In addition, the higher AMP concentration gave higher mass transfer coefficient at low liquid flow rates.     

Development and Experimental Study of CO2 Expander in CO2 Supercritical Refrigeration Cycles

Abstract

As one of the natural working fluids for the refrigeration system, CO₂ has been attracting increasing attention over the last ten years. But CO₂ has to work at the supercritical region for the so-called “condensation” process regarding the conventional refrigerants and evaporate at the two-phase region, and therefore results in larger throttling loss for the practical refrigeration application. Consequently, new technologies must be developed to improve the performance efficiency of the CO₂ transcritical cycle, and make it to be equal or closer to that of the refrigeration system with the conventional refrigerants. In this study, an expander is employed in the CO₂ transcritical cycle to replace the throttling valve, and as a result the throttling loss can be decreased significantly. The paper presents the development of a rolling piston expander and the activity items in the expander design, including the seal technology, the contact friction control, the suction design, etc. The performance experiments for the expander are conducted in the present testing system for the CO₂ transcritical cycle. The results show that the recovery power of the expander is related to the revolution speed of the expander. The efficiency of the expander prototype is observed to be about 32%.     

Seismic detection of CO2 leakage along monitoring wellbores

A pilot carbon dioxide (CO₂) sequestration experiment was carried out in the Michigan Basin in which ～10,000 tonnes of supercritical CO₂ was injected into the Bass Island Dolomite (BILD) at 1050 m depth. A passive seismic monitoring (PSM) network was operated before, during and after the ～17-day injection period. The seismic monitoring network consisted of two arrays of eight, three-component sensors, deployed in two monitoring wells at only a few hundred meters from the injection point. 225 microseismic events were detected by the arrays. Of these, only one event was clearly an injection-induced microearthquake. It occurred during injection, approximately 100 m above the BILD formation. No events, down to the magnitude ?3 detection limit, occurred within the BILD formation during the injection. The observed seismic waveforms associated with the other 224 events were quite unusual in that they appear to contain dominantly compressional (P) but no (or extremely weak) shear (S) waves, indicating that they are not associated with shear slip on faults. The microseismic events were unusual in two other ways. First, almost all of the events occurred prior to the start of injection into the BILD formation. Second, hypocenters of the 94 locatable events cluster around the wells where the sensor arrays were deployed, not the injection well. While the temporal evolution of these events shows no correlation with the BILD injection, they do correlate with CO₂ injection for enhanced oil recovery (EOR) into the 1670 m deep Coral Reef formation that had been going on for ～2.5 years prior to the pilot injection experiment into the BILD formation. We conclude that the unusual microseismic events reflect degassing processes associated with leakage up and around the monitoring wells from the EOR-related CO₂ injection into the Coral Reef formation, ～700 m below the depth of the monitoring arrays. This conclusion is also supported by the observation that as soon as injection into the Coral Reef formation resumed at the conclusion of the BILD demonstration experiment, seismic events (essentially identical to the events associated with the Coral Reef injection prior to the BILD experiment) again started to occur close to a monitoring arrays. Taken together, these observations point to vertical migration around the casings of the monitoring wellbores. Detection of these unusual microseismic events was somewhat fortuitous in that the arrays were deployed at the depth where the CO₂ undergoes a strong volume increase during transition from a supercritical state to a gas. Given the large number of pre-existing wellbores that exist in depleted oil and gas reservoirs that might be considered for CO₂ sequestration projects, passive seismic monitoring systems could be deployed at appropriate depths to systematically detect and monitor leakage along them.     

Mercury measurement and control in a CO2-enriched flue gas

Oxycombustion is being considered as a promising solution to carbon capture and sequestration. Standard sampling and measurement methods may or may not be valid under oxycombustion conditions because the flue gas differs significantly from that of conventional air-blown coal combustion.Bench-scale tests were conducted to evaluate the measurement validity of continuous mercury monitors (CMMs), with and without a flue gas preconditioning unit, in a simulated oxycombustion flue gas with varied CO₂ concentrations. Tests also included mercury capture with activated carbon in typical oxyfuel combustion flue gas. Research data indicated that highly concentrated CO₂ streams affect the accuracy of the mass flow rate and the subsequent gaseous mercury measurement, although this is specific to the type of CMM. Concentrated CO₂ streams also induced solid precipitation in the wet-chemistry conversion unit and resulted in a biased measurement of the gas-phase mercury. Flue gas dilution appeared to provide accurate measurement of total gas-phase mercury and be applicable to mercury measurement in highly concentrated CO₂ streams, although mercury speciation appeared to be problematic and will require additional modification and validation. Mercury capture with activated carbon under CO₂-enriched conditions showed similar performance to typical high-acid coal combustion flue gas.     

CO2 recycling by reaction with renewably-generated hydrogen

A laboratory-scale reactor system was built and operated to demonstrate the feasibility of catalytically reacting carbon dioxide (CO₂) with renewably-generated hydrogen (H₂) to produce methane (CH₄) according to the Sabatier reaction: CO₂ + 4H₂ → CH₄ + 2H₂O. A cylindrical reaction vessel packed with a commercial methanation catalyst (Haldor Topsøe PK-7R) was used. Renewable H₂ produced by electrolysis of water (from solar- and wind-generated electricity) was fed into the reactor along with a custom blend of 2% CO₂ in N₂, meant to represent a synthetic exhaust mixture. Reaction conditions of temperature, flow rates, and gas mixing ratios were varied to determine optimum performance. The extent of reaction was monitored by real-time measurement of CO₂ and CH₄. Maximum conversion of CO₂ occurred at 300–350 °C. Approximately 60% conversion of CO₂ was realized at a space velocity of about 10,000 h^?1 with a molar ratio of H₂/CO₂ of 4/1. Somewhat higher total CO₂ conversion was possible by increasing the H₂/CO₂ ratio, but the most efficient use of available H₂ occurs at a lower H₂/CO₂ ratio.     

Purification of oxyfuel-derived CO2

Oxyfuel combustion in a pulverised fuel coal-fired power station produces a raw CO₂ product containing contaminants such as water vapour plus oxygen, nitrogen and argon derived from the excess oxygen for combustion, impurities in the oxygen used, and any air leakage into the system. There are also acid gases present, such as SO₃, SO₂, HCl and NO_x produced as byproducts of combustion. At GHGT8 (White and Allam, 2006) we presented reactions that gave a path-way for SO₂ to be removed as H₂SO₄ and NO and NO₂ to be removed as HNO₃. In this paper we present initial results from the OxyCoal-UK project in which these reactions are being studied experimentally to provide the important reaction kinetic information that is so far missing from the literature. This experimental work is being carried out at Imperial College London with synthetic flue gas and then using actual flue gas via a sidestream at Doosan Babcock's 160 kW coal-fired oxyfuel rig. The results produced support the theory that SO_x and NO_x components can be removed during compression of raw oxyfuel-derived CO₂ and therefore, for emissions control and CO₂ product purity, traditional FGD and deNO_x systems should not be required in an oxyfuel-fired coal power plant.     

CO2 capture for refineries,a practical approach

This paper evaluates the opportunities and associated costs for post-combustion capture at a world-scale complex refinery. It is concluded that it is technically feasible to apply post-combustion capture at such a refinery. The costs for capture and sequestration from a gasifier are calculated to be lowest at about 30 Euro per ton; this process currently already produces a concentrated CO₂ stream. Next, the CO₂ source most suited for capture appears to be a combined stack, but there are a number of other sources that may be targeted at comparable costs. In total these sources may form about 40% of the overall refinery emissions. Our evaluations show the costs of capture from such sources based on available amine technology will be in the range of 90–120 Euro per ton, which is about 3–4 times higher than the current carbon trading values. The capture of CO₂ from a large amount of smaller CO₂ sources will bring along even much higher costs. A high-level study of the CO₂ emissions profile of a number of Shell refineries shows that, typically, up to 50% of the emitted CO₂ may be captured at similar costs. About 10–20% of concentrated CO₂ associated with hydrogen manufacturing may be captured at lower costs. The remainder of emitted dilute CO₂ will bring along significantly higher costs. Based on this study, it is concluded for the justification of the implementation of post-combustion capture at refineries, either a significant increase in carbon trading values, mandatory regulations, or a major technological break-through is required.     

Parametric investigation of the calcium looping process for CO2 capture in a 10 kWth dual fluidized bed

Calcium looping (CaL) is a promising post-combustion CO₂ capture technology which is carried out in a dual fluidized bed (DFB) system with continuous looping of CaO, the CO₂ carrier, between two beds. The system consists of a carbonator, where flue gas CO₂ is adsorbed by CaO and a regenerator, where captured CO₂ is released. The CO₂-rich regenerator flue gas can be sequestered after gas processing and compression. A parametric study was conducted on the 10 kW_th DFB facility at the University of Stuttgart, which consists of a bubbling fluidized bed carbonator and a riser regenerator. The effect of the following parameters on CO₂ capture efficiency was investigated: carbonator space time, carbonator temperature and calcium looping ratio. The active space time in the carbonator, which is a function of the space time and the calcium looping ratio, was found to strongly correlate with the CO₂ capture efficiency. BET and BJH techniques provided surface area and pore volume distribution data, respectively, for collected sorbent samples. The rate of sorbent attrition was found to be 2 wt.%/h which is below the expected sorbent make-up rate required to maintain sufficient sorbent activity. Steady-state CO₂ capture efficiencies greater than 90% were achieved for different combinations of operational parameters. Moreover, the experimental results obtained were briefly compared with results derived from reactor modeling studies. Finally, the implications of the experimental results with respect to commercialization of the CaL process have been assessed.     

Numerical simulation on multi-scale diffusion of CO2 injected in the deep ocean in a practical scenario

The direct injection of CO₂ into the deep ocean is one of the ways for the mitigation of the global warming. There is, however, a concern about its environmental impact near the injection point. To minimize its biological impact, it is necessary to make CO₂ disperse as fast as possible and it is thought that injection with pipes towed by moving-ships is effective for this purpose. Because the injection ships are planned to move in the site, the order of magnitude of which is 10² km, a mesoscale model is required to predict CO₂ fate in seawater. At the same time, it is required to predict the concentration precisely near the injection points, which move with the ships in the mesoscale domain. In this study, a multi-scale ocean model was developed to analyze the dispersion of CO₂ in the deep ocean: the model consists of a fixed mesoscale domain and 5 small-scale domains nesting in the mesoscale domain. Each small-scale domain involves 6 pipes and moves along with the trajectories of the injection ships. From the results of the present numerical simulation, the developed technique demonstrated its applicability as a tool to optimise the system to dilute CO₂ below some criterion of biological impact.     

Conceptual design of a three fluidised beds combustion system capturing CO2 with CaO

In this work, the Aspen Hysys conceptual design of a new process for energy generation at large scale with implicit CO₂ capture is presented. This process makes use of the CaO capability for CO₂ capture at high temperature and the possibility of regenerating this sorbent working in interconnected fluidised bed reactors operating at different temperatures. The proposed process has the advantage of producing power with minimum CO₂ emissions and very low energy penalties compared with similar air-based combustion power plants. In this system, five main parts can be distinguished: the combustor where coal is burnt with air, the calciner where the fresh and the recycled CaCO₃ is calcined, the carbonator where the CO₂ produced in the combustor is captured, the supercritical steam cycle and the CO₂ compression system. In this arrangement, the three fluidised bed reactors are interconnected in such a way that it is possible to perform the CaCO₃ calcination at a temperature of 950 °C with the energy transported by a hot solid stream produced in the circulating fluidised bed combustor operating at 1030 °C. The stream rich in CaO produced in the calciner is split into three parts. One of them is transported to the carbonator operating at 650 °C where most of the CO₂ in the flue gas produced in the combustor is captured. The second one is sent to the combustor, where it is heated up and used as energy carrier. The third solid stream that leaves the calciner is a purge in order to maintain the capture system activity and to avoid inert material accumulation. Because of the high temperatures involved in all the system, it is possible to recover most of the energy in the fuel and to produce power in a supercritical steam cycle. A case study is presented and it is demonstrated that under these operating conditions, 90% CO₂ capture efficiency can be achieved with no energy penalty further than the one originated in the CO₂ compression system.     

Chilled ammonia process for CO2 capture

The chilled ammonia process absorbs the CO₂ at low temperature (2–10 °C). The heat of absorption of carbon dioxide by ammonia is significantly lower than for amines. In addition, degradation problems can be avoided and a high carbon dioxide capacity is achieved. Hence, this process shows good perspectives for decreasing the heat requirement. However, a scientific understanding of the processes is required. The thermodynamic properties of the NH₃–CO₂–H₂O system were described using the extended UNIQUAC electrolyte model developed by Thomsen and Rasmussen in a temperature range from 0 to 110 °C and pressure up to 100 bars. The results show that solid phases consisting of ammonium carbonate and bicarbonate are formed in the absorber. The heat requirements in the absorber and in the desorber have been studied. The enthalpy calculations show that a heat requirement for the desorber lower than 2 GJ/ton CO₂ can be reached.     

Experimental study on CO2 monitoring and quantification of stored CO2 in saline formations using resistivity measurements

This paper reports CO₂ saturation estimations based on resistivity data obtained from laboratory measurements and induction logging results at the Nagaoka pilot CO₂ injection site. The laboratory experiments put in evidence that the presence of clay content tends to reduce the increase of resistivity caused by the displacement of brine by less conductive CO₂. As a result, CO₂ saturations estimated from resistivity measurements without any correction for the clay effect are considerably lower than the actual saturations. The resistivity index (RI) provides better estimates of CO₂ saturations than the Archie's equation because it requires the determination or assumption of only one rock parameter: the saturation exponent. CO₂ saturations estimated from the induction logging data acquired at Nagaoka are considerably lower than the neutron porosity changes due to displacement between brine and CO₂ in the reservoir. Even in the case of considering the De Witte's equation and the Poupon's to account for the clay effect, it was still difficult to get a good agreement with the neutron logging results. New relations based on the resistivity index with correction factors for the clay effect are developed and implemented in this study. One of these relations has proved to be effective to estimate CO₂ saturations in saline formations with high clay content.     

Natural analogue of the rise and dissolution of liquid CO2 in the ocean

The behavior of natural carbon dioxide (CO₂) droplets (8–10 mm in diameter) were observed in a seafloor hydrothermal system at the Okinawa Trough. The natural CO₂ droplet contain 95–98% of CO₂, 2–3% of H₂S, and other gas species. The ascending CO₂ droplets were tracked by a remotely operated vehicle (ROV), and depth, temperature, salinity, pH and partial pressure of CO₂ (pCO₂) in seawater near the CO₂ droplets were measured during droplet ascent by a conductivity-temperature-depth sensor (CTD) and in situ pH/pCO₂ sensor. The visual images of the rising CO₂ droplets were recorded with a high definition television camera on the ROV. A mapping survey (400 m × 400 m; 4 horizontal layers) revealed a dominant distribution of low pH area over the natural CO₂ venting site. The size and rise rate of CO₂ droplets decreased during their ascent in the water column from depths of 1424 to 679 m (a tracking interval of 745 m). The CO₂ droplets dissolved gradually to become small flakes of CO₂ hydrate while rising, and these ascending flakes were found to disappear at 679 m depth. Although a pH as low as 5 was detected just above the liquid CO₂ venting site on the seafloor, no detectable pH depression in the water column ambient to the rising CO₂ droplets was observed. The results of the pH mapping survey showed only localized pH depression over the CO₂ venting site.     

Short-Term Opportunities for Decreasing CO2 Emissions from the Steel Industry

There is a strong political will to decrease CO₂ emissions. Although the steel industry only accounts for some 5% of worldwide CO₂ emissions (which totalled 1,200 million tonnes per annum in the late 1990s), it will be strongly affected by this. The EU, for example, is putting up strong economic incentives for reductions. This is taking place at a time when demand for steel products is greater than ever. To radically change existing processes and production routes to decrease the CO₂ emissions would be extremely expensive, even if it were possible. Nevertheless, many of the solutions which have been discussed seem to go in this direction. The other alternative discussed seems to be the creation of process solutions and alterations that lead to a focusing of CO₂ streams, i.e., much higher CO₂ concentrations in flue gases than today, for entrapment of the CO₂ so that it is not discharged into the atmosphere. These solutions are feasible, but expensive.

However, there exists today a number of solutions and technologies which, if fully implemented, could substantially decrease CO₂ emissions without seriously altering current methods of operation; they are short-term viable solutions. The present paper reviews and discusses such technologies, throughout the steel production paths. If these solutions are fully implemented, the combined impact on CO₂ emissions from the steel industry worldwide is estimated to be a reduction of 100–150 million tonnes of CO₂ per annum, i.e., current emissions can be reduced by some 8–10% within a relatively short time span.     

CO2 emissions from Polish cement industry

The cement industry is one of the most significant sources of anthropogenic emissions of CO₂. It is connected with the specific character of the production processes, during which great quantities of CO₂ are produced. Basic actions to reduce CO₂ emissions recommended by the European Union's, Reference Document on Best Available Techniques in the Cement and Lime Manufacturing Industries, include: reduction of fuel consumption, selection of raw materials with low content of organic compounds and fuels with low coal contribution to heating value. All actions connected with the improvement of energy conversion efficiency of the cement production process cause CO₂ emissions reduction. The use of at most acceptable by the valid standards amounts of waste as raw materials and additives for cement production, also brings about the reduction of significant part of CO₂ emissions. These measures have been and continue to be pursued by the cement factories in Poland. This article describes the evolution of the cement industry in Poland over the period 1998–2008 and the resulting changes in CO₂ emissions and explores the drivers for these changes. The sources of CO₂ emissions in cement industry have been presented in this article as well as a discussion of potential ways to reduce Polish cement industry emissions even further.     

Techno-economic study of CO2 capture from natural gas based hydrogen plants

Canadian oil sands are considered to be the second largest oil reserves in the world. However, the upgrading of bitumen from oil sands to synthetic crude oil (SCO) requires nearly ten times more hydrogen (H₂) than conventional crude oils. The current H₂ demand for oil sands operations is met mostly by steam reforming of natural gas (SMR). The future expansion of oil sands operations is likely to quadruple the demand of H₂ for oil sand operations in the next decade.This paper presents modified process schemes that capture CO₂ at minimum energy penalty in modern SMR plants. The approach is to simulate a base case H₂ plant without CO₂ capture and then look for the best operating conditions that minimize the energy penalty associated with CO₂ capture while maximizing H₂ production. The two CO₂ capture schemes evaluated in this study include a membrane separation process and the monoethanolamine (MEA) absorption process. A low energy penalty is observed when there is lower CO₂ production and higher steam production. The process simulation results show that the H₂ plant with CO₂ capture has to be operated at lower steam to carbon ratio (S/C), higher inlet temperature of the SMR and lower inlet temperatures for the water gas-shift (WGS) converters to attain lowest energy penalty. Also it is observed that both CO₂ capture processes, the membrane process and the MEA absorption process, are comparable in terms of energy penalty and CO₂ avoided when both are operated at conditions where lowest energy penalty exists.