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Thermodynamic Properties of CO2 Mixtures and Their Applications in Advanced Power Cycles with CO2 Capture Processes
KTH, School of Chemical Science and Engineering (CHE), Chemical Engineering and Technology, Energy Processes.
2008 (English)Doctoral thesis, comprehensive summary (Other scientific)
Abstract [en]

The thermodynamic properties of CO2-mixtures are essential for the design and operation of CO2 Capture and Storage (CCS) systems. A better understanding of the thermodynamic properties of CO2 mixtures could provide a scientific basis to define a proper guideline of CO2 purity and impure components for the CCS processes according to technical, safety and environmental requirements. However the available accurate experimental data cannot cover the whole operation conditions of CCS processes. In order to overcome the shortage of experimental data, theoretical estimation and modelling are used as a supplemental approach.

 

In this thesis, the available experimental data on the thermodynamic properties of CO2 mixtures were first collected, and their applicability and gaps for theoretical model verification and calibration were also determined according to the required thermodynamic properties and operation conditions of CCS. Then in order to provide recommendations concerning calculation methods for engineering design of CCS, totally eight equations of state (EOS) were evaluated for the calculations about vapour liquid equilibrium (VLE) and density of CO2-mixtures, including N2, O2, SO2, Ar, H2S and CH4.

 

With the identified equations of state, the preliminary assessment of impurity impacts was further conducted regarding the thermodynamic properties of CO2-mixtures and different processes involved in CCS system. Results show that the increment of the mole fraction of non-condensable gases would make purification, compression and condensation more difficult. Comparatively N2 can be separated more easily from the CO2-mixtures than O2 and Ar. And a lower CO2 recovery rate is expected for the physical separation of CO2/N2 under the same separation conditions. In addition, the evaluations about the acceptable concentration of non-condensable impurities show that the transport conditions in vessels are more sensitive to the non-condensable impurities and it requires very low concentration of non-condensable impurities in order to avoid two-phase problems.

 

Meanwhile, the performances of evaporative gas turbine integrated with different CO2 capture technologies were investigated from both technical and economical aspects. It is concluded that the evaporative gas turbine (EvGT) cycle with chemical absorption capture has a smaller penalty on electrical efficiency, while a lower CO2 capture ratio than the EvGT cycle with O2/CO2 recycle combustion capture. Therefore, although EvGT + chemical absorption has a higher annual cost, it has a lower cost of electricity because of its higher efficiency. However considering its lower CO2 capture ratio, EvGT + chemical absorption has a higher cost to avoid 1 ton CO2. In addition the efficiency of EvGT + chemical absorption can be increased by optimizing Water/Air ratio, increasing the operating pressure of stripper and adding a flue gas condenser condensing out the excessive water.

Place, publisher, year, edition, pages
Stockholm: KTH , 2008. , xii, 63 p.
Series
Trita-CHE-Report, ISSN 1654-1081 ; 2008:58
Keyword [en]
Thermodynamic property, vapour liquid equilibrium, density, equation of state, interaction parameter, CO2 mixtures, evaporative gas turbine, chemical absorption, oxy-fuel combustion, cost evaluation, CO2 capture and storage
National Category
Chemical Engineering
Identifiers
URN: urn:nbn:se:kth:diva-9109ISBN: 978-91-7415-091-9 (print)OAI: oai:DiVA.org:kth-9109DiVA: diva2:15031
Public defence
2008-10-10, FA32, Roslagstullsbacken 21, Stockholm, 10:00 (English)
Opponent
Supervisors
Note
QC 20100819Available from: 2008-09-26 Created: 2008-09-19 Last updated: 2010-08-19Bibliographically approved
List of papers
1. A new modification on RK EOS for gaseous CO2 and gaseous mixtures of CO2 and H2O
Open this publication in new window or tab >>A new modification on RK EOS for gaseous CO2 and gaseous mixtures of CO2 and H2O
2006 (English)In: International journal of energy research (Print), ISSN 0363-907X, E-ISSN 1099-114X, Vol. 30, no 3, 135-148 p.Article in journal (Refereed) Published
Abstract [en]

To develop an equation of state with simple structure and reasonable accuracy for engineering application, Redlich-Kwong equation of state was modified for gaseous CO2 and CO2-H2O mixtures. In the new modification, parameter 'a' of gaseous CO2 was regressed as a function of temperature and pressure from recent reliable experimental data in the range: 220-750 K and 0.1-400 MPa. Moreover, a new mixing rule was proposed for gaseous CO2-H2O mixtures. To verify the accuracy of the new modification, densities were calculated and compared with experimental data. The average error is 1.68% for gaseous CO2 and 0.93% for gaseous mixtures of CO2 and H2O, Other thermodynamic properties, such as enthalpy and heat capacities of CO2 and excess enthalpy of gaseous CO2-H2O mixtures, were also calculated; results fit experimental data well, except for the critical region.

Keyword
CO2; H2O; mixtures; equation of state; mixing rule; thermodynamic properties
National Category
Chemical Engineering
Identifiers
urn:nbn:se:kth:diva-9107 (URN)10.1002/er.1129 (DOI)000235413200001 ()2-s2.0-32544461118 (Scopus ID)
Note
QC 20100819Available from: 2009-11-12 Created: 2008-09-19 Last updated: 2010-08-19Bibliographically approved
2. Impacts of impurities in CO2-fluids on CO2 transport process
Open this publication in new window or tab >>Impacts of impurities in CO2-fluids on CO2 transport process
2006 (English)In: 2006 ASME 51st Turbo Expo: Barcelona: 6 May 2006 through 11 May 2006, 2006, 367-375 p.Conference paper, Published paper (Refereed)
Abstract [en]

There are four possible transportation means that could be used to deliver CO2: motor carriers, railway carriers, water carriers, and pipeline. The impurities in CO2-fluids have significant impacts on the thermodynamic properties that will further affect the design, operation and cost of CO2 transport. This paper focuses on how impurities in CO-fluids affect thermodynamic properties, and how the changes of properties affect CO2 transport process. Vapor-liquid equilibrium (VLE), critical point and densities are essential thermodynamic properties for designing a CO2 transport process. Studies on these properties will be carried out for CO2-mixtures based on the combinations of the common impurities such as SO2, H2S, CH4, Ar, O-2 and N-2. Moreover with a real case of pipeline for CO transport, the impact of impurities on transport process will be demonstrated in more details.

Keyword
thermodynamic properties, CO2 transportation, mixtures, PR EOS
National Category
Chemical Engineering
Identifiers
urn:nbn:se:kth:diva-24166 (URN)000243378600036 ()2-s2.0-33750851933 (Scopus ID)0-7918-4239-8 (ISBN)
Note
QC 20100819Available from: 2010-08-19 Created: 2010-08-19 Last updated: 2010-08-19Bibliographically approved
3. Preliminary study on CO2 processing in CO2 capture from oxy-fuel combustion
Open this publication in new window or tab >>Preliminary study on CO2 processing in CO2 capture from oxy-fuel combustion
2007 (English)In: Proceedings of the ASME Turbo Expo, vol. 3: Montreal, Que.: 14 May 2007 through 17 May 2007, 2007, 353-361 p.Conference paper, Published paper (Refereed)
Abstract [en]

Oxy-fuel combustion is one of promising technologies for CO2 capture, which uses simple flue gas processing normally including compression, dehydration and purification/liquefaction (non-condensable gas separation). However relatively high levels of impurities in the flu gas present more challenges for the gas processing procedure. This paper studied the sensitivity of operating parameters to inlet composition, the effects of impurities on energy consumption, and the relationship between energy consumption and operating parameters. Results show that comparatively the total compression work is more sensitive to the composition of SO2 if the total mass flow is constant; while the operating temperature of purification is more sensitive to N-2. To pursue the minimum energy consumption, from the viewpoint of impurity, the content Of O-2, N-2, Ar and H2O should be lowered as much as possible, which means the amount of air leakage into the system and excess oxygen should be controlled at a low level in the combustion; as to SO2, if it is possible to co-deposit with CO2, its existence may be helpful to decrease compression work. From the viewpoint of operating parameters, low intermediate pressure, high intercooling temperature and high outlet pressure are favorable to achieve high energy utilization, if heat recovery is considered.

Keyword
oxy-fuel combustion, CO2 processing, impurity, operating parameters, energy consumption, sensitivity analysis
National Category
Chemical Engineering
Identifiers
urn:nbn:se:kth:diva-24167 (URN)000252771900036 ()2-s2.0-34548779734 (Scopus ID)978-0-7918-4792-3 (ISBN)
Note
QC 20100819Available from: 2010-08-19 Created: 2010-08-19 Last updated: 2010-08-19Bibliographically approved
4. Impurity impacts on the purification process in oxy-fuel combustion based CO2 capture and storage system
Open this publication in new window or tab >>Impurity impacts on the purification process in oxy-fuel combustion based CO2 capture and storage system
2009 (English)In: Applied Energy, ISSN 0306-2619, E-ISSN 1872-9118, Vol. 86, no 2, 202-213 p.Article in journal (Refereed) Published
Abstract [en]

Based on the requirements of CO2 transportation and storage, non-condensable gases, such as O-2, N-2 and At should be removed from the CO2-stream captured from an oxy-fuel combustion process. For a purification process, impurities have great impacts on the design, operation and optimization through their impacts on the thermodynamic properties of CO2-streams. Study results show that the increments of impurities will make the energy consumption of purification increase: and make CO2 purity of separation product and CO2 recovery rate decrease, In addition, under the same operating conditions, energy consumptions have different sensitivities to the variation of the impurity mole fraction of feed fluids. The isothermal compression work is more sensitive to the variation of SO2: while the isentropic compression work is more sensitive to the variation of Ar. In the flash system, the energy consumption of condensation in is more sensitive to the variation of Ar; but in the distillation system, the energy consumption of condensation is more sensitive to the variation of SO2, and CO2 purity of separation is more sensitive to the variation of SO2.

Keyword
Thermodynamic properties, Impurity impacts, Purification, Oxy-fuel, combustion, CO2 capture and storage
National Category
Chemical Engineering
Identifiers
urn:nbn:se:kth:diva-17907 (URN)10.1016/j.apenergy.2008.05.006 (DOI)000260269000011 ()2-s2.0-52149108934 (Scopus ID)
Note
QC 20100525Available from: 2010-08-05 Created: 2010-08-05 Last updated: 2017-12-12Bibliographically approved
5. Evaluating cubic equations of state for calculation of vapor-liquid equilibrium of CO2 and CO2-mixtures for CO2 capture and storage processes
Open this publication in new window or tab >>Evaluating cubic equations of state for calculation of vapor-liquid equilibrium of CO2 and CO2-mixtures for CO2 capture and storage processes
2009 (English)In: Applied Energy, ISSN 0306-2619, E-ISSN 1872-9118, Vol. 86, no 6, 826-836 p.Article in journal (Refereed) Published
Abstract [en]

Proper solution of vapor liquid equilibrium (VLE) is essential to the design and operation of CO2 capture and storage system (CCS). According to the requirements of engineering applications, cubic equations of state (EOS) are preferable to predict VLE properties. This paper evaluates the reliabilities of five cubic EOSs, including PR, PT, RK, SRK and 3P1T for predicting VLE Of CO2 and binary CO2-mixtures containing CH4, H2S, SO2, Ar, N-2 or O-2, based on the comparisons with the collected experimental data. Results show that SRK is superior in the calculations about the saturated pressure of pure CO2; while for the VLE properties of binary CO2-mixtures, PR, PIT and SRK are generally superior to RK and 3P1T. The impacts of binary interaction parameter k(ij) were also analyzed. k(ij) has very clear effects on the calculating accuracy of an EOS in the property calculations Of CO2-mixtures. In order to improve the calculation accuracy, the binary interaction parameter was calibrated for all of the studied EOSs regarding every binary CO2-mixture.

Keyword
CO2 capture and storage, Vapor liquid equilibria, Cubic equation of, state, Binary interaction parameter, CO2 binary CO2-mixtures, carbon dioxide system, thermodynamic properties, co2-h2o-nacl systems, temperature relation, gaseous-mixtures, phase-equilibria, degrees c, pressures, methane, region
National Category
Chemical Engineering
Identifiers
urn:nbn:se:kth:diva-18302 (URN)10.1016/j.apenergy.2008.05.018 (DOI)000264657300005 ()2-s2.0-60549097049 (Scopus ID)
Note
QC 20100525Available from: 2010-08-05 Created: 2010-08-05 Last updated: 2017-12-12Bibliographically approved
6. Performance comparison on the evaporative gas turbine cycles combined with different Co2-capture options
Open this publication in new window or tab >>Performance comparison on the evaporative gas turbine cycles combined with different Co2-capture options
2009 (English)In: International Journal of Green Energy, ISSN 1543-5075, E-ISSN 1543-5083, Vol. 6, no 5, 512-526 p.Article in journal (Refereed) Published
Abstract [en]

This article studied the integration of CO2 capture with evaporative gas turbine (EvGT) cycles. Two CO2 capture technologies are involved: MEA-based (monoethanolamine-based) chemical-absorption capture and O-2/CO2 recycle combustion capture. Based on them, three system configurations were analyzed: (1) EvGT cycle without CO2 capture, (2) EvGT cycle with chemical-absorption capture, and (3) EvGT cycle with O-2/CO2 recycle combustion capture. Simulation results show that the EvGT cycle with chemical-absorption capture has a higher electrical efficiency (39.73%) than the EvGT cycle with O-2/CO2 recycle combustion capture (37.45%). Compared with the EvGT cycle without CO2 capture, the penalty on electrical efficiency caused by CO2 capture is 11.91% if EvGT is combined with chemical-absorption capture, and 14.19% if EvGT is combined with O-2/CO2 recycle combustion capture. Moreover compared with combined cycles, EvGT cycles have a smaller gross electricity generation and a lower electrical efficiency no matter if they are combined with CO2 capture or not. Based on the analysis results of this article, several suggestions are also proposed to improve the net electrical efficiency of EvGT cycles with CO2 capture.

Keyword
Evaporative gas turbines, Humid air turbines, CO2 capture, Chemical absorption, O-2/CO2 recycle combustion, Oxy-fuel combustion, Performance analysis
National Category
Chemical Engineering
Identifiers
urn:nbn:se:kth:diva-24168 (URN)10.1080/15435070903231369 (DOI)000273991400010 ()
Note
QC 20100819Available from: 2010-08-19 Created: 2010-08-19 Last updated: 2017-12-12Bibliographically approved
7. Integrating Evaporative Gas Turbine with Chemical Absorptionfor Carbon Dioxide Capture
Open this publication in new window or tab >>Integrating Evaporative Gas Turbine with Chemical Absorptionfor Carbon Dioxide Capture
2008 (English)In: International Green Energy Conference IV: Beijing, China 2008, 2008Conference paper, Published paper (Refereed)
Keyword
evaporative gas turbines; humid air turbines; Co2 capture; chemical absorption; electrical efficiency
National Category
Chemical Engineering
Identifiers
urn:nbn:se:kth:diva-24169 (URN)
Note
QC 20100819Available from: 2010-08-19 Created: 2010-08-19 Last updated: 2010-08-19Bibliographically approved
8. Impacts of equations of state (EOS) and impurities on the volume calculation of CO2 mixtures in the applications of CO2 capture and storage (CCS) processes
Open this publication in new window or tab >>Impacts of equations of state (EOS) and impurities on the volume calculation of CO2 mixtures in the applications of CO2 capture and storage (CCS) processes
2009 (English)In: Applied Energy, ISSN 0306-2619, E-ISSN 1872-9118, Vol. 86, no 12, 2760-2770 p.Article in journal (Refereed) Published
Abstract [en]

Volume property is the necessary thermodynamic property in the design and operation of the CO2 Capture and storage system (CCS). Because of their simple structures, cubic equations of state (EOS) are preferable to be applied in predicting volumes for engineering applications. This paper evaluates the reliabilities of seven cubic EOS, including PR, PT, RK, SRK, MPR, MSRK and ISRK for predicting volumes of binary CO2 mixtures containing CH4, H2S, SO2, At and N-2, based on the comparisons with the collected experimental data. Results show that for calculations on the volume properties of binary CO2 mixtures, PR and PT are generally superior to others for all of the studied mixtures. In addition, it was found that the binary interaction parameter has clear effects on the calculating accuracy of an EOS in the volume calculations Of CO2 mixtures. In order to improve the accuracy, k(ij) was calibrated for all of the EOS regarding the gas and liquid phases of all the studied binary CO2 mixtures, respectively.

Keyword
CO2 capture and storage, Volume, Cubic equation of state, Binary, interaction parameter, Impurity, CO2 mixtures, vapor-liquid-equilibrium, gaseous-mixtures, cubic equations, systems, behavior
National Category
Chemical Engineering
Identifiers
urn:nbn:se:kth:diva-18790 (URN)10.1016/j.apenergy.2009.04.013 (DOI)000270120000025 ()2-s2.0-68849105338 (Scopus ID)
Note
QC 20100525Available from: 2010-08-05 Created: 2010-08-05 Last updated: 2017-12-12Bibliographically approved

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