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

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

Experimental investigation of the CO2 sealing efficiency of caprocks

Using a combination of experimental (petrophysical and mineralogical) methods, the effects of high-pressure CO₂ exposure on fluid transport properties and mineralogical composition of two pelitic caprocks, a limestone and a clay-rich marl lithotype have been studied. Single and multiphase permeability tests, gas breakthrough and diffusion experiments were conducted under in situ p/T conditions on cylindrical plugs (28.5 mm diameter, 10–20 mm thickness).The capillary CO₂ sealing efficiency of the initially water-saturated sample plugs was found to decrease in repetitive gas breakthrough experiments on the same sample from 0.74 to 0.41 MPa for the limestone and from 0.64 to 0.43 MPa for the marl. Helium breakthrough experiments before and after the CO₂ tests showed a decrease in capillary threshold (snap-off) pressure from 1.81 to 0.62 MPa for the limestone.Repetitive CO₂ diffusion experiments on the marlstone revealed an increase in the effective diffusion coefficient from 7.8 × 10^?11 to 1.2 × 10^?10 m².Single-phase (water) permeability coefficients derived from steady-state permeability tests ranged between 7 and 56 nano-Darcy and showed a consistent increase after each CO₂ test cycle. Effective gas permeabilities were generally one order of magnitude lower than water permeabilities and exhibit the same trend. XRD measurements performed before and after exposure to CO₂ did not reveal any distinct change in the mineral composition for both samples. Similarly, no significant changes were observed in specific surface areas (determined by BET) and pore-size distributions (determined by mercury injection porosimetry). High-pressure CO₂ sorption experiments on powdered samples revealed significant CO₂ sorption capacities of 0.27 and 0.14 mmol/g for the marlstone and the limestone, respectively.The changes in transport parameters in the absence of detectable mineral alterations may be explained by carbonate dissolution and further precipitation along a pH profile across the sample plug which would not be subject to quantitative mineral alteration.     

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.     

3D geomechanical modelling for CO2 geologic storage in the Dogger carbonates of the Paris Basin

CO₂ injection into a depleted hydrocarbon field or aquifer may give rise to a variety of coupled physical and chemical processes. During CO₂ injection, the increase in pore pressure can induce reservoir expansion. As a result the in situ stress field may change in and around the reservoir. The geomechanical behaviour induced by oil production followed by CO₂ injections into an oil field reservoir in the Paris Basin has been numerically modelled. This paper deals with an evaluation of the induced deformations and in situ stress changes, and their potential effects on faults, using a 3D geomechanical model. The geomechanical analysis of the reservoir–caprock system was carried out as a feasibility study using pressure information in a “one way” coupling, where pressures issued from reservoir simulations were integrated as input for a geomechanical model. The results show that under specific assumptions the mechanical effects of CO₂ injection do not affect the mechanical stability of the reservoir–caprock system. The ground vertical movement at the surface ranges from ?2 mm during oil production to +2.5 mm during CO₂ injection. Furthermore, the changes in in situ stresses predicted under specific assumptions by geomechanical modelling are not significant enough to jeopardize the mechanical stability of the reservoir and caprock. The stress changes issued from the 3D geomechanical modelling are also combined with a Mohr–Coulomb analysis to determine the fault slip tendency. By integrating the stress changes issued from the geomechanical modelling into the fault stability analysis, the critical pore pressure for fault reactivation is higher than calculated for the fault stability analysis considering constant horizontal stresses.     

Geoelectrical methods for monitoring geological CO2 storage: First results from cross-hole and surface–downhole measurements from the CO2SINK test site at Ketzin (Germany)

The feasibility of monitoring CO₂ migration in a saline aquifer at a depth of about 650 m with cross-hole and surface–downhole electrical resistivity tomography (ERT) is investigated at the CO₂SINK test site close to Ketzin (Germany). The permanent vertical electrical resistivity array (VERA) consists of 45 electrodes (15 in the injection well Ktzi201 and 15 in each of the two observation wells Ktzi200 and Ktzi202), successfully placed on the electrically insulated casings, in the depth range of about 590–740 m with a spacing of about 10 m. The three Ketzin wells are arranged as perpendicular triangle with distances of 50 and 100 m.First synthetic modelling studies indicate an increase of the electrical resistivity of about 200% caused by CO₂ injection, corresponding to a bulk CO₂ saturation of 50%, which is in good agreement with laboratory studies. Finite difference inversion of field data delivers three-dimensional resistivity distributions between the wells which are consistent with the reservoir modelling studies.To increase the limited observation area provided by the cross-hole measurements, additional surface–downhole measurements were deployed. A main CO₂ migration in SE–NW direction is deduced from surface to downhole resistivity experiments.The first cross-hole time-lapse results show that the resolution and the coverage of the electrode array in the Ketzin setting are sufficient to resolve the expected resistivity changes on the characteristic length scale of the electrode array. Significant resistivity changes could be measured, however, detailed information on the CO₂ plume could not be resolved yet by VERA under the existing geological circumstances.     

Carbon dioxide storage capacity in uneconomic coal beds in Alberta,Canada: Methodology,potential and site identification

Methodology is presented for a first-order regional-scale estimation of CO₂ storage capacity in coals under sub-critical conditions, which is subsequently applied to Cretaceous-Tertiary coal beds in Alberta, Canada. Regions suitable for CO₂ storage have been defined on the basis of groundwater depth and CO₂ phase at in situ conditions. The theoretical CO₂ storage capacity was estimated on the basis of CO₂ adsorption isotherms measured on coal samples, and it varies between ∼20 kt CO₂/km² and 1260 kt CO₂/km², for a total of approximately 20 Gt CO₂. This represents the theoretical storage capacity limit that would be attained if there would be no other gases present in the coals or they would be 100% replaced by CO₂, and if all the coals will be accessed by CO₂. A recovery factor of less than 100% and a completion factor less than 50% reduce the theoretical storage capacity to an effective storage capacity of only 6.4 Gt CO₂. Not all the effective CO₂ storage capacity will be utilized because it is uneconomic to build the necessary infrastructure for areas with low storage capacity per unit surface. Assuming that the economic threshold to develop the necessary infrastructure is 200 kt CO₂/km², then the CO₂ storage capacity in coal beds in Alberta is greatly reduced further to a practical capacity of only ∼800 Mt CO₂.     

CO2 capture from power plants: Part II. A parametric study of the economical performance based on mono-ethanolamine

While the demand for reduction in CO₂ emission is increasing, the cost of the CO₂ capture processes remains a limiting factor for large-scale application. Reducing the cost of the capture system by improving the process and the solvent used must have a priority in order to apply this technology in the future. In this paper, a definition of the economic baseline for post-combustion CO₂ capture from 600 MW_e bituminous coal-fired power plant is described. The baseline capture process is based on 30% (by weight) aqueous solution of monoethanolamine (MEA). A process model has been developed previously using the Aspen Plus simulation programme where the baseline CO₂-removal has been chosen to be 90%. The results from the process modelling have provided the required input data to the economic modelling. Depending on the baseline technical and economical results, an economical parameter study for a CO₂ capture process based on absorption/desorption with MEA solutions was performed.Major capture cost reductions can be realized by optimizing the lean solvent loading, the amine solvent concentration, as well as the stripper operating pressure. A minimum CO₂ avoided cost of € 33 tonne⁻¹ CO₂ was found for a lean solvent loading of 0.3 mol CO₂/mol MEA, using a 40 wt.% MEA solution and a stripper operating pressure of 210 kPa. At these conditions 3.0 GJ/tonne CO₂ of thermal energy was used for the solvent regeneration. This translates to a € 22 MWh⁻¹ increase in the cost of electricity, compared to € 31.4 MWh⁻¹ for the power plant without capture.     

1D and 2D absorption-rate/kinetic modeling and simulation of carbon dioxide absorption into mixed aqueous solutions of MDEA and PZ in a laminar jet apparatus

The kinetics of the reaction between carbon dioxide (CO₂) and mixed solutions of methyldiethanolamine (MDEA) and piperazine (PZ) was investigated experimentally in a laminar jet apparatus. The experimental kinetic data were obtained under no interfacial turbulence and over a temperature range from 313 to 333 K, MDEA/PZ wt% concentration ratios of 27/3, 24/6 and 21/9, and CO₂ loadings from 0.0095 to 0.33 mol CO₂/mol amine. In addition, a new absorption-rate/kinetics model for the kinetics of the mixed of solvents was developed, which takes into account the coupling between chemical equilibrium, mass transfer, and all possible chemical reactions involved in the CO₂ reaction with MDEA/PZ solvent. The partial differential equations of this model were solved by the finite element numerical method (FEM) based on COMSOL software. The obtained experimental kinetics data were used to obtain the kinetic parameters of CO₂ absorption into MDEA/PZ solutions. The reaction-rate constant obtained for PZ blended with MDEA was kPZ = 2.572 × 10¹² exp(?5211/T). The 2D model for the blended amines MDEA/PZ has revealed the concentration profiles of all the species in both the radial and axial directions of the laminar jet which has enabled a better understanding of the correct sequence in which the reaction steps involved in the reactive absorption of CO₂ in aqueous mixed MDEA/PZ solution occur. It also revealed that PZ may be depleted by the time the solvent blend of MDEA/PZ with a loading greater than 0.015 mol/mol amine is exposed to CO₂ from the top of the laminar jet absorber.     

The potential for increased atmospheric CO2 emissions and accelerated consumption of deep geologic CO2 storage resources resulting from the large-scale deployment of a CCS-enabled unconventional fossil fuels industry in the U.S.

Desires to enhance the energy security of the United States have spurred renewed interest in the development of abundant domestic heavy hydrocarbon resources including oil shale and coal to produce unconventional liquid fuels to supplement conventional oil supplies. However, the production processes for these unconventional fossil fuels create large quantities of carbon dioxide (CO₂) and this remains one of the key arguments against such development. Carbon dioxide capture and storage (CCS) technologies could reduce these emissions and preliminary analysis of regional CO₂ storage capacity in locations where such facilities might be sited within the U.S. indicates that there appears to be sufficient storage capacity, primarily in deep saline formations, to accommodate the CO₂ from these industries. Nevertheless, even assuming wide-scale availability of cost-effective CO₂ capture and geologic storage resources, the emergence of a domestic U.S. oil shale or coal-to-liquids (CTL) industry would be responsible for significant increases in CO₂ emissions to the atmosphere. The authors present modeling results of two future hypothetical climate policy scenarios that indicate that the oil shale production facilities required to produce 3 MMB/d from the Eocene Green River Formation of the western U.S. using an in situ retorting process would result in net emissions to the atmosphere of between 3000 and 7000 MtCO₂, in addition to storing potentially 900–5000 MtCO₂ in regional deep geologic formations via CCS in the period up to 2050. A similarly sized, but geographically more dispersed domestic CTL industry could result in 4000–5000 MtCO₂ emitted to the atmosphere in addition to potentially 21,000–22,000 MtCO₂ stored in regional deep geologic formations over the same period. While this analysis shows that there is likely adequate CO₂ storage capacity in the regions where these technologies are likely to deploy, the reliance by these industries on large-scale CCS could result in an accelerated rate of utilization of the nation's CO₂ storage resource, leaving less high-quality storage capacity for other carbon-producing industries including electric power generation.     

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.     

Experimental assessment of brine and/or CO2 leakage through well cements at reservoir conditions

Two sets of experiments on typical Class G well cement were carried out in the laboratory to understand better the potential processes involved in well leakage in the presence of CO₂. In the first set, good-quality cement samples of permeability in the order of 0.1 μD (10^?19 m²) were subjected to 90 days of flow through with CO₂-saturated brine at conditions of pressure, temperature and water salinity characteristic of a typical geological sequestration zone. Cement permeability dropped rapidly at the beginning of the experiment and remained almost constant thereafter, most likely mainly as a result of CO₂ exsolution from the saturated brine due to the pressure drop along the flow path which led to multi-phase flow, relative-permeability effects and the observed reduction in permeability. These processes are identical to those which would occur in the field as well if the cement sheath in the wellbore annulus is of good quality. The second set of experiments, carried out also at in situ conditions and using ethane rather than CO₂ to eliminate any possible geochemical effects, assessed the effect of annular spaces between wellbore casing and cement, and of radial cracks in cement on the effective permeability of the casing-cement assemblage. The results show that, if both the cement and the bond are of good quality, the effective permeability of the assemblage is extremely low (in the order of 1 nD, or 10^?21 m²). The presence of an annular gap and/or cracks in the order of 0.01–0.3 mm in aperture leads to a significant increase in effective permeability, which reaches values in the range of 0.1–1 mD (10^?15 m²). The results of both sets of experiments suggest that good cement and good bonding with casing and the surrounding rock will likely constitute a good and reliable barrier to the upward flow of CO₂ and/or CO₂-saturated brine. The presence of mechanical defects such as gaps in bonding between the casing or the formation, or cracks in the cement annulus itself, leads to flow paths with significant effective permeability. This indicates that the external and internal interfaces of cements in wells would most probably constitute the main flow pathways for fluids leakage in wellbores, including both gaseous/supercritical phase CO₂ and CO₂-saturated brine.     

Coastal spreading of olivine to control atmospheric CO2 concentrations: A critical analysis of viability

Qualitative proposals to control atmospheric CO₂ concentrations by spreading crushed olivine rock along the Earth's coastlines, thereby accelerating weathering reactions, are presently attracting considerable attention. This paper provides a critical evaluation of the concept, demonstrating quantitatively whether or not it can contribute significantly to CO₂ sequestration. The feasibility of the concept depends on the rate of olivine dissolution, the sequestration capacity of the dominant reaction, and its CO₂ footprint. Kinetics calculations show that offsetting 30% of worldwide 1990 CO₂ emissions by beach weathering means distributing of 5.0 Gt of olivine per year. For mean seawater temperatures of 15–25 °C, olivine sand (300 μm grain size) takes 700–2100 years to reach the necessary steady state sequestration rate and is therefore of little practical value. To obtain useful, steady state CO₂ uptake rates within 15–20 years requires grain sizes <10 μm. However, the preparation and movement of the required material poses major economic, infrastructural and public health questions. We conclude that coastal spreading of olivine is not a viable method of CO₂ sequestration on the scale needed. The method certainly cannot replace CCS technologies as a means of controlling atmospheric CO₂ concentrations.     

Modeling the impacts of climate policy on the deployment of carbon dioxide capture and geologic storage across electric power regions in the United States

This paper summarizes the results of a first-of-its-kind holistic, integrated economic analysis of the potential role of carbon dioxide (CO₂) capture and storage (CCS) technologies across the regional segments of the United States (U.S.) electric power sector, over the time frame 2005–2045, in response to two hypothetical emissions control policies analyzed against two potential energy supply futures that include updated and substantially higher projected prices for natural gas. This paper's detailed analysis is made possible by combining two specialized models developed at Battelle: the Battelle CO₂-GIS to determine the regional capacity and cost of CO₂ transport and geologic storage; and the Battelle Carbon Management Electricity Model, an electric system optimal capacity expansion and dispatch model, to examine the investment and operation of electric power technologies with CCS against the background of other options. A key feature of this paper's analysis is an attempt to explicitly model the inherent heterogeneities that exist in both the nation's current and future electricity generation infrastructure and in its candidate deep geologic CO₂ storage formations. Overall, between 180 and 580 gigawatts (GW) of coal-fired integrated gasification combined cycle with CCS (IGCC + CCS) capacity is built by 2045 in these four scenarios, requiring between 12 and 41 gigatonnes of CO₂ (GtCO₂) storage in regional deep geologic reservoirs across the U.S. Nearly all of this CO₂ is from new IGCC + CCS systems, which start to deploy after 2025. Relatively little IGCC + CCS capacity is built before that time, primarily under unique niche opportunities. For the most part, CO₂ emissions prices will likely need to be sustained at over $20/tonne CO₂ before CCS begins to deploy on a large scale within the electric power sector. Within these broad national trends, a highly nuanced picture of CCS deployment across the U.S. emerges. Across the four scenarios studied here, power plant builders and operators within some North American Electric Reliability Council (NERC) regions do not employ any CCS while other regions build more than 100 GW of CCS-enabled generation capacity. One region sees as much as 50% of its geologic CO₂ storage reservoirs’ total theoretical capacity consumed by 2045, while most of the regions still have more than 90% of their potential storage capacity available to meet storage needs in the second half of the century and beyond. A detailed presentation of the results for power plant builds and operation in two key regions: ECAR in the Midwest and ERCOT in Texas, provides further insight into the diverse set of economic decisions that generate the national and aggregate regional results.     

Pulverized coal stream ignition delay under conventional and oxy-fuel combustion conditions

The coal stream ignition process is critical to the performance of modern pulverized coal burners, particularly when operating under novel conditions such as experienced in oxy-fuel combustion. However, experimental studies of coal stream ignition are lacking, and recent modeling efforts have had to rely on comparisons with a single set of experiments in vitiated air. To begin to address this shortfall, we have conducted experiments on the ignition properties of two U.S. and two Chinese coals in a laminar entrained flow reactor. Most of the measurements focused on varying the coal feed rate for furnace temperatures of 1230–1320 K and for 12–20 vol.% O₂ in nitrogen. The influence of coal feed rate on ignition with a carbon dioxide diluent was also measured for 20 vol.% O₂ at 1280 K. A second set of measurements was performed for ignition of a fixed coal feed rate in N₂ and CO₂ environments at identical furnace temperatures of 1200 K, 1340 K, and 1670 K. A scientific CCD camera equipped with a 431 nm imaging filter was used to interrogate the ignition process. Under most conditions, the ignition delay decreased with increasing coal feed rate until a minimum was reached at a feed rate corresponding to a particle number density of approximately 4 × 10⁹ m^?3 in the coal feed pipe. This ignition minimum corresponds to a cold flow group number, G, of ～0.3. At higher coal feed rates the ignition delay increased. The ignition delay time was shown to be very sensitive to (a) the temperature of the hot coflow into which the coal stream is introduced, and (b) the coal particle size. The three high volatile bituminous coals showed nearly identical ignition delay as a function of coal feed rate, whereas the subbituminous coal showed slightly greater apparent ignition delay. Bath gas CO₂ content was found to have a minor impact on ignition delay.     

Pathways towards large-scale implementation of CO2 capture and storage: A case study for the Netherlands

We sketch four possible pathways how carbon dioxide capture and storage (CCS) (r)evolution may occur in the Netherlands, after which the implications in terms of CO₂ stored and avoided, costs and infrastructural requirements are quantified. CCS may play a significant role in decarbonising the Dutch energy and industrial sector, which currently emits nearly 100 Mt CO₂/year. We found that 15 Mt CO₂ could be avoided annually by 2020, provided some of the larger gas fields that become available the coming decade could be used for CO₂ storage. Halfway this century, the mitigation potential of CCS in the power sector, industry and transport fuel production is estimated at maximally 80–110 Mt CO₂/year, of which 60–80 Mt CO₂/year may be avoided at costs between 15 and 40 €/t CO₂, including transport and storage. Avoiding 30–60 Mt CO₂/year by means of CCS is considered realistic given the storage potential represented by Dutch gas fields, although it requires planning to assure that domestic storage capacity could be used for CO₂ storage. In an aggressive climate policy, avoiding another 50 Mt CO₂/year may be possible provided that nearly all capture opportunities that occur are taken. Storing such large amounts of CO₂ would only be possible if the Groningen gas field or large reservoirs in the British or Norwegian part of the North Sea will become available.     

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.     

Analytical solution for Joule–Thomson cooling during CO2 geo-sequestration in depleted oil and gas reservoirs

Mathematical tools are needed to screen out sites where Joule–Thomson cooling is a prohibitive factor for CO₂ geo-sequestration and to design approaches to mitigate the effect. In this paper, a simple analytical solution is developed by invoking steady-state flow and constant thermophysical properties. The analytical solution allows fast evaluation of spatiotemporal temperature fields, resulting from constant-rate CO₂ injection. The applicability of the analytical solution is demonstrated by comparison with non-isothermal simulation results from the reservoir simulator TOUGH2. Analysis confirms that for an injection rate of 3 kg s^?1 (0.1 MT yr^?1) into moderately warm (>40 °C) and permeable formations (>10^?14 m² (10 mD)), JTC is unlikely to be a problem for initial reservoir pressures as low as 2 MPa (290 psi).     

Techno-economic evaluation of biogas upgrading process using CO2 facilitated transport membrane

The biogas upgrading by membrane separation process using a highly efficient CO₂-selective polyvinylamine/polyvinylalcohol (PVAm/PVA) blend membrane was investigated by experimental study and simulation with respect to process design, operation optimization and economic evaluation. This blend membrane takes advantages of the unique CO₂ facilitated transport from PVAm and the robust mechanical properties from PVA, exhibits both high CO₂/CH₄ separation efficiency and very good stability. CO₂ transports through the water swollen membrane matrix in the form of bicarbonate. CO₂/CH₄ selectivity up to 40 and CO₂ permeance up to 0.55 m³(STP)/m² h bar at 2 bar were documented in lab with synthesized biogas (35% CO₂ and 65% CH₄). Membrane performances at varying feed pressures were recorded and used as the simulation basis in this work. The process simulation of an on-farm scale biogas upgrading plant (1000 Nm³/h) was conducted. Processes with four different membrane module configurations with or without recycle were evaluated technically and economically, and the 2-stage in cascade with recycle configuration was proven optimal among the four processes. The sensitivity of the process to various operation parameters was analyzed and the operation conditions were optimized.     

CCS scenarios optimization by spatial multi-criteria analysis: Application to multiple source sink matching in Hebei province

A method, based on spatial analysis of the different criteria to be taken into consideration for building scenarios of CO₂ capture and storage (CCS), has been developed and applied to real case studies in the Hebei province. Totally 88 point sources (42 from power sector, 9 from iron and steel, 18 from cement, 16 from ammonia, and 3 from oil refinery) are estimated and their total emission amounts to 231.7 MtCO₂/year with power, iron and steel, cement, ammonia and oil refinery sharing 59.13%, 25.03%, 11.44%, 3.5%, and 0.91%, respectively. Storage opportunities can be found in Hebei province, characterised by a strong tectonic subsidence during the Tertiary, with several kilometres of accumulated clastic sediments. Carbon storage potential for 25 hydrocarbon fields selected from the Huabei complex is estimated as 215 MtCO₂ with optimistic assumption that all recovered hydrocarbon could be replaced by an equivalent volume of CO₂ at reservoir conditions. Storage potential for aquifers in the Miocene Guantao formation is estimated as 747 MtCO₂ if closed aquifer assumed or 371 MtCO₂ if open aquifer and single highly permeable horizon assumed. Due to poor knowledge on deep hydrogeology and to pressure increase in aquifer, injecting very high rates requested by the major CO₂ sources (>10 MtCO₂/year) is the main challenge, therefore piezometry and discharge must be carefully controlled. A source sink matching model using ArcGIS software is designed to find the least-cost pathway and to estimate transport route and cost accounting for the additional costs of pipeline construction due to landform and land use. Source sink matching results show that only 15–25% of the emissions estimated for the 88 sources can be sequestrated into the hydrocarbon fields and the aquifers if assuming sinks should be able to accommodate at least 15 years of the emissions of a given source.     

Heat of absorption of CO2 in aqueous ammonia and ammonium carbonate/carbamate solutions

A reaction calorimeter was used to determine the enthalpies of absorption of CO₂ in aqueous ammonia and in aqueous solutions of ammonium carbonate at temperatures of 35–80 °C. The heat of absorption of CO₂ with 2.5 wt% aqueous ammonia solution was found to be about 70 kJ/mol CO₂, which is lower than that with MEA (around 85 kJ/mol) at 35 and 40 °C. The value decreases with increased loading, but not to as low a value as expected by the carbonate–bicarbonate reaction (26.88 kJ/mol). The enthalpy of absorption of CO₂ in aqueous ammonia at 60 and 80 °C decreases with loadings at first, then increases between 0.2 mol CO₂/mol NH₃ and 0.6 mol CO₂/mol NH₃, and then decreases again. The behavior of the heat of absorption of CO₂ in 10 wt% ammonium carbonate solution was found to be the same as that of aqueous ammonia at loadings above 0.6 mol CO₂/mol NH₃. The heat of absorption increases with increasing temperature. The heats of absorption are directly related to the extent of the various reactions with CO₂ and can be assessed from the species variation in the liquid phase.