Separation and capture of CO2 from large stationary sources and sequestration in geological formations--coalbeds and deep saline aquifers

The topic of global warming as a result of increased atmospheric CO2 concentration is arguably the most important environmental issue that the world faces today. It is a global problem that will need to be solved on a global level. The link between anthropogenic emissions of CO2 with increased atmospheric CO2 levels and, in turn, with increased global temperatures has been well established and accepted by the world. International organizations such as the United Nations Framework Convention on Climate Change (UNFCCC) and the Intergovernmental Panel on Climate Change (IPCC) have been formed to address this issue. Three options are being explored to stabilize atmospheric levels of greenhouse gases (GHGs) and global temperatures without severely and negatively impacting standard of living: (1) increasing energy efficiency, (2) switching to less carbon-intensive sources of energy, and (3) carbon sequestration. To be successful, all three options must be used in concert. The third option is the subject of this review. Specifically, this review will cover the capture and geologic sequestration of CO2 generated from large point sources, namely fossil-fuel-fired power gasification plants. Sequestration of CO2 in geological formations is necessary to meet the President's Global Climate Change Initiative target of an 18% reduction in GHG intensity by 2012. Further, the best strategy to stabilize the atmospheric concentration of CO2 results from a multifaceted approach where sequestration of CO2 into geological formations is combined with increased efficiency in electric power generation and utilization, increased conservation, increased use of lower carbon-intensity fuels, and increased use of nuclear energy and renewables. This review covers the separation and capture of CO2 from both flue gas and fuel gas using wet scrubbing technologies, dry regenerable sorbents, membranes, cryogenics, pressure and temperature swing adsorption, and other advanced concepts. Existing commercial CO2 capture facilities at electric power-generating stations based on the use of monoethanolamine are described, as is the Rectisol process used by Dakota Gasification to separate and capture CO2 from a coal gasifier. Two technologies for storage of the captured CO2 are reviewed--sequestration in deep unmineable coalbeds with concomitant recovery of CH4 and sequestration in deep saline aquifers. Key issues for both of these techniques include estimating the potential storage capacity, the storage integrity, and the physical and chemical processes that are initiated by injecting CO2 underground. Recent studies using computer modeling as well as laboratory and field experimentation are presented here. In addition, several projects have been initiated in which CO2 is injected into a deep coal seam or saline aquifer. The current status of several such projects is discussed. Included is a commercial-scale project in which a million tons of CO2 are injected annually into an aquifer under the North Sea in Norway. The review makes the case that this can all be accomplished safely with off-the-shelf technologies. However, substantial research and development must be performed to reduce the cost, decrease the risks, and increase the safety of sequestration technologies. This review also includes discussion of possible problems related to deep injection of CO2. There are safety concerns that need to be addressed because of the possibilities of leakage to the surface and induced seismic activity. These issues are presented along with a case study of a similar incident in the past. It is clear that monitoring and verification of storage will be a crucial part of all geological sequestration practices so that such problems may be avoided. Available techniques include direct measurement of CO2 and CH4 surface soil fluxes, the use of chemical tracers, and underground 4-D seismic monitoring. Ten new hypotheses were formulated to describe what happens when CO2 is pumped into a coal seam. These hypotheses provide significant insight into the fundamental chemical, physical, and thermodynamic phenomena that occur during coal seam sequestration of CO2.     

Performance of amine-multilayered solid sorbents for CO2 removal: Effect of fabrication variables

The emission of fossil fuel carbon dioxide (CO₂) to the atmosphere is implicated as the predominant cause of global climate change; therefore, advanced CO₂ capture technologies are of the utmost importance. In this study, innovative amine-multilayered sorbents were fabricated using layer-by-layer (LbL) nanoassembly technology via alternate deposition of a CO₂-adsorbing amine polymer (e.g. polyethylenimine or PEI) and an oppositely-charged polymer (e.g. polystyrene sulfonate or PSS). We found that the developed sorbents could be used for CO₂ capture and that LbL nanoassembly allows us to engineer their CO₂ capture performance through the fabrication variables (e.g. deposition polymers, deposition media, and number of bilayers). PEI/PSS was found to be the best polymer combination for developing sorbents with relatively high CO₂ capture capacity. The amine-multilayered solid sorbents possessed fine microstructures and may have similar polymer deposition within and on the surface of solid sorbents. These amine-multilayered sorbents had much faster CO₂ desorption rates compared to sorbents prepared using the current PEI-impregnation approach. Such fast CO₂ desorption could make sorbents a good option for CO₂ removal from power plants and even the atmosphere.     

The Bechtel Confined Zone dispersion Process for FGD Retrofit Situations Proof-of-Concept Tests

The Bechtel Confined Zone Dispersion (CZD) process for FGD retrofit situations was tested at two sites: one at a level of 5 MWe; the other at 70 MWe. The CZD process involves injecting a finely atomized slurry of hydrated lime into a straight run of duct between a boiler's air heater and its electrostatic precipitator (ESP). The effect of process variables on SO₂ removal and ESP performance was investigated for dolomitic/calcitic lime. Removals of SO₂ in excess of 50 percent were achieved for either lime type at the 5 MWe site. A very short duct length limited injection rate at the 70 MWe site, limiting sulfur removals to a maximum of 30 percent. SO₂ removal data for both sites were successfully correlated on a common basis. ESP performance was not fully acceptable during lime injection at both sites, but it is felt that optimization of ESP operations should eliminate this problem. Additional testing is recommended to further explore ESP performance and to optimize lime injection parameters. The results obtained to date continue to indicate that the CZD process is an attractive and economical candidate for FGD retrofit situations.     

Modeling sorbent injection for mercury control in baghouse filters: I--model development and sensitivity analysis

A two-stage mathematical model for Hg removal using powdered activated carbon injection upstream of a baghouse filter was developed, with the first stage accounting for removal in the ductwork and the second stage accounting for additional removal caused by the retention of carbon particles on the filter. The model shows that removal in the ductwork is minimal, and the additional carbon detention time from the entrapment of the carbon particles in the fabric filter enhances the Hg removal from the gas phase. A sensitivity analysis on the model shows that Hg removal is dependent on the isotherm parameters, the carbon pore radius and tortuosity, the C/Hg ratio, and the carbon particle radius.     

The thief process for mercury removal from flue gas

The Thief Process is a cost-effective variation to activated carbon injection (ACI) for removal of mercury from flue gas. In this scheme, partially combusted coal from the furnace of a pulverized coal power generation plant is extracted by a lance and then re-injected into the ductwork downstream of the air preheater. Recent results on a 500-lb/h pilot-scale combustion facility show similar removals of mercury for both the Thief Process and ACI. The tests conducted to date at laboratory, bench, and pilot-scales demonstrate that the Thief sorbents exhibit capacities for mercury from flue gas streams that are comparable to those exhibited by commercially available activated carbons. A patent for the process was issued in February 2003. The Thief sorbents are cheaper than commercially-available activated carbons; exhibit excellent capacities for mercury; and the overall process holds great potential for reducing the cost of mercury removal from flue gas. The Thief Process was licensed to Mobotec USA, Inc. in May of 2005.     

The Role of Pressure Drop and Flow Redistribution on Modeling Mercury Control Using Sorbent Injection in Baghouse Filters

Abstract

A mathematical model based on simple cake filtration theory was coupled to a reviously developed two-stage mathematical model for mercury (Hg) removal using powdered activated carbon injection upstream of a bag-house filter. Values of the average permeability of the filter cake and the filter resistance extracted from the model were 4.4× 10^?13 m² and 2.5 ×10^?4 m^?1, respectively. The flow is redistributed during partial cleaning of the filter, with flows higher across the newly cleaned filter section. The calculated average Hg removal efficiency from the baghouse is lower because of the high mass flux of Hg exiting the filter in the newly cleaned section. The model shows that calculated average Hg removal is affected by permeability, filter resistance, fraction of the baghouse cleaned, and cleaning interval.     

Modeling sorbent injection for mercury control in baghouse filters: II--pilot-scale studies and model evaluation

Activated carbon injection for Hg control in a 500-lb/hr pilot-scale coal-fired furnace equipped with a fabric filter for particulate control was evaluated at different operating conditions. The pilot-scale tests showed that Hg removal was improved at lower temperatures and higher C/Hg ratios. The two-stage mathematical model developed to describe Hg removal using powdered activated carbon injection upstream of a baghouse filter was used to obtain Langmuir isotherm parameters as a function of temperature by fitting the model to a subset of experimental data. The predictive capability of the model was then tested by comparing model calculations with additional experimental data from this system obtained using different operating temperatures and sorbent to Hg ratios. Model predictions were in good agreement with experimentally measured Hg removal efficiency. Based on the model predictions, Hg removal in the duct appears to be limited and higher C/Hg ratio, lower operating temperature, and longer cleaning cycle of the baghouse filter should be utilized to achieve higher Hg removal in this system.     

Status of the DOE/GEESI In-Duct Scrubbing Pilot Study

The recent promulgation of stack height regulations and possible changes in the National Ambient Air Quality Standards for sulfur dioxide and the associated dispersion model methodologies, could require older power plants to develop new compliance strategies and upgrade emission control systems. In such situations, an inexpensive, moderate removal efficiency flue gas desulfurization technology could maintain the cost effectiveness of these plants. Such a technology was selected by the Department of Energy for demonstration in its Acid Rain Precursor Control Technology Initiative. The process applies the rotary atomizer techniques developed for lime slurry dry flue gas desulfurization spray absorbers, and utilizes existing ductwork and particulate collectors. This induct scrubbing technology is anticipated to result in a dry desulfurization process of moderate removal efficiency. The critical elements for successful application are (i) adequate mixing for efficient reactant contact, (ii) sufficient residence time to produce a non-wetting product, and (iii) appropriate ductwork cross sectional areas to prevent deposition of reaction products before drying. The ductwork in many older power plants, previously modified to meet 1970 Clean Air Act requirements for particulate control, usually meets these criteria. A pilot study of the process is now in design-construct phase. Testing will start in 1987 and determine conditions under which the technology would be a cost effective approach to meeting emission reduction design criteria     

Modeling Sorbent Injection for Mercury Control in Baghouse Filters: I—Model Development and Sensitivity Analysis

Abstract

A two-stage mathematical model for Hg removal using powdered activated carbon injection upstream of a bag-house filter was developed, with the first stage accounting for removal in the ductwork and the second stage accounting for additional removal caused by the retention of carbon particles on the filter. The model shows that removal in the ductwork is minimal, and the additional carbon detention time from the entrapment of the carbon particles in the fabric filter enhances the Hg removal from the gas phase. A sensitivity analysis on the model shows that Hg removal is dependent on the isotherm parameters, the carbon pore radius and tortuosity, the C/Hg ratio, and the carbon particle radius.