Patent Application
20140178276
This application claims priority to PCT/IB2012/001649 filed Aug. 28, 2012, which in turn claims priority to European application 11179402.0 filed Aug. 30, 2011, the contents of which are both incorporated in their entireties.
The present invention relates to a method of capturing CO2 from a flue gas stream in a CO2-absorber.
The present invention further relates to system for capturing CO2 from a flue gas stream.
In the combustion of a fuel, such as coal, oil, peat, waste, natural gas, etc., in a combustion plant, such as a power plant, a hot process gas is generated, such process gas containing, among other components, carbon dioxide, CO2. The negative environmental effects of releasing carbon dioxide to the atmosphere have been widely recognized, and have resulted in the development of processes adapted for capturing carbon dioxide from the hot process gas generated in the combustion of the above mentioned fuels. One such system and process has previously been disclosed and is directed to a Chilled Ammonia based system and method for capture of CO2 from a post-combustion flue gas stream using an ammoniated solution and/or slurry for capturing CO2 from a flue gas stream. WO 2009/055419 discloses a process and system using three absorbers to improve efficiency of the CO2 capture process. The system disclosed in WO 2009/055419 is, however, complicated from a technical point of view, and has a high operating cost.
The above drawbacks and deficiencies of the prior art are overcome or alleviated by means of a method of capturing CO2 from a flue gas stream in a CO2-absorber, the method comprising:
An advantage of this method is that carbon dioxide can be efficiently captured, without an undue slip of ammonia, with lower operating cost and capital costs compared to the prior art.
According to one embodiment the method further comprises forwarding the recirculated CO2-enriched ammoniated solution first through the second absorption stage, and then through the first absorption stage. An advantage of this embodiment is that the recirculated CO2-enriched ammoniated solution acts as a barrier to gaseous ammonia and serves to collect not only carbon dioxide, but also ammonia from the flue gas, before the flue gas is forwarded from the second stage to a water wash vessel or an ammonia polishing stage, as the case may be.
According to one embodiment the method further comprises forwarding the CO2-lean ammoniated solution through the first absorption stage without forwarding the CO2-lean ammoniated solution through the second absorption stage. An advantage of this embodiment is an improved mass transfer of CO2 from the gas phase to the liquid phase by achieving a concentration profile with regard to CO2 in the ammoniated solution which varies in an optimum manner along the CO2-absorber.
According to one embodiment the recirculated CO2-enriched ammoniated solution and the CO2-lean ammoniated solution are kept at a temperature, while passing through the first and second absorption stages, which is above a temperature at which ammonium bicarbonate particles may start to precipitate from the respective ammoniated solution. An advantage of this embodiment is that the absorber operates entirely in solution mode, with no, or almost no, formation of solid carbonate particles. This reduces risks of clogging in the absorber and makes absorber operation more robust. It is also possible to reduce the liquid to gas ratio, L/G, in the absorber since operating with solid formation in accordance with the prior art requires high liquid to gas ratios to reduce risks of solids accumulating in unwanted locations inside the absorber.
According to one embodiment the partly cleaned flue gas stream is passed vertically upwards from the first absorption stage to the second absorption stage, and wherein the recirculated CO2-enriched ammoniated solution is passed vertically downwards from the second absorption stage to the first absorption stage. An advantage of this embodiment is that gas distribution of the partly cleaned flue gas stream entering vertically upwards into the second absorption stage becomes very even and efficient, and so does the liquid distribution of the recirculated CO2-enriched ammoniated solution entering vertically downwards into the first absorption stage.
According to one embodiment the method further comprises contacting, in a third absorption stage, being an ammonia polishing stage, of the CO2-absorber, the cleaned flue gas stream coming from the second absorption stage with a polishing portion of the recirculated CO2-enriched ammoniated solution to form a further cleaned flue gas stream, the polishing portion of the recirculated CO2-enriched ammoniated solution being cooled, prior to being supplied to the third stage, to a polishing temperature which is lower than an absorbing temperature of the absorbing portion of the recirculated CO2-enriched ammoniated solution supplied to the second stage. An advantage of this embodiment is that a very low equilibrium pressure of ammonia, beneficial for low slip of ammonia, is achieved in the third absorption stage. Still further, only a small amount of the recirculated CO2-enriched ammoniated solution needs to be cooled to the low temperature for ammonia capture in the third absorption stage, which reduces the need for installed cooling power, and in particular the need for installed refrigeration unit capacity.
According to one embodiment the method further comprises mixing the polishing portion of the recirculated CO2-enriched ammoniated solution, after having passed through the third absorption stage, with the absorbing portion of the recirculated CO2-enriched ammoniated solution to form the recirculated CO2-enriched ammoniated solution passing through the second absorption stage. An advantage of this embodiment is that the polishing portion of the recirculated CO2-enriched ammoniated solution is utilized in an efficient manner for absorbing ammonia in both the third and second absorption stages in a counter-current mode in relation to the flue gas flow.
According to one embodiment the R-value, being the molar concentration of NH3 divided by the molar concentration of CO2, of the recirculated CO2-enriched ammoniated solution supplied to the second absorption stage is within the range of 1.75 to 2.00. An advantage of this embodiment is that efficient capture of carbon dioxide is achieved, still at a low slip of ammonia, and with little, or no, formation of solid ammonium bicarbonate. More preferably, the R-value of the recirculated CO2-enriched ammoniated solution supplied to the second absorption stage may be within the range of 1.81 to 1.96.
According to one embodiment, the temperature of the recirculated CO2-enriched ammoniated solution supplied to the second absorption stage is controlled to be within the range of 8-30° C., more preferably 20-25° C. An advantage of this temperature range is that efficient capture of carbon dioxide, low slip of ammonia, and little, or no, formation of solid ammonium bicarbonate is achieved.
According to one embodiment, the R-value of the ammoniated solution is within the range of 1.70 to 2.80 throughout the entire first absorption stage. An advantage of this embodiment is that very efficient capture of carbon dioxide is achieved, still with no, or only little, formation of solid ammonium bicarbonate.
According to one embodiment, the R-value of the recirculated CO2-enriched ammoniated solution entering to the second absorption stage is lower than the R-value of the mixture of recirculated CO2-enriched ammoniated solution and the CO2-lean ammoniated solution entering the first absorption stage. An advantage of this embodiment is that efficient capture of carbon dioxide is achieved in the first absorption stage, and a very low slip of ammonia is achieved from the second absorption stage.
According to one embodiment, the temperature of the mixture of recirculated CO2-enriched ammoniated solution and CO2-lean ammoniated solution entering the first absorption stage is higher than the temperature of the recirculated CO2-enriched ammoniated solution entering the second absorption stage. An advantage of this embodiment is that kinetics beneficial for efficient absorption of CO2 are improved in the mass transfer device of the first stage, which significantly reduces the need for height of the mass transfer device packing of the first absorption stage.
According to one embodiment, the liquid to gas ratio, L/G, on a mass basis is 5 to 16, more preferably 7 to 12, and most preferably 8 to 10 kg solution/kg flue gas in the first absorption stage. The L/G is 3 to 10, and more preferably 4 to 8, kg solution/kg flue gas in the second absorption stage. Such liquid to gas ratios have been found to result in efficient capture of carbon dioxide, with low energy consumption. Additionally, the relatively low L/G increases the temperature inside the absorber, in particular in the first absorption stage, since the exothermic absorption of CO2 has to heat a smaller amount of solution. An increased temperature in the absorber is beneficial for the kinetics of the capture of CO2. Furthermore, the relatively low L/G reduces back-mixing, i.e., occasional entrainment upwards of solution, which further increases the CO2 capture due to a more stable counter-current flow between solution and gas.
According to one embodiment the first portion of the collected CO2-enriched ammoniated solution comprises 30 to 70% by weight of the collected CO2-enriched ammoniated solution, and wherein the second portion of the collected CO2-enriched ammoniated solution comprises 70 to 30% by weight of the collected CO2-enriched ammoniated solution. An advantage of this embodiment is that efficient balance between recirculation and regeneration of the collected CO2-enriched ammoniated solution is achieved, resulting in efficient operation of the first and second absorption stages, and low total liquid to gas ratio.
According to one embodiment 4-30% of the total flow of the CO2-lean ammoniated solution forwarded to the CO2-absorber is forwarded to the second absorption stage for contacting the partly cleaned flue gas stream. An advantage of this embodiment is that an enhanced removal of CO2 in the second absorption stage may be achieved.
The above mentioned drawbacks and deficiencies of the prior art are also overcome or alleviated by means of a system for capturing CO2 from a flue gas stream which comprises:
An advantage of this system is that it is robust and has lower operating and capital costs compared to the prior art systems.
According to one embodiment, the system comprises a heat exchanger arranged on the recirculation pipe for cooling the recirculated CO2-enriched ammoniated solution prior to being supplied to the second absorption stage. An advantage of this embodiment is that cooling to a suitable temperature for the second absorption stage can be achieved efficiently. Often a relatively simple water cooled heat exchanger is sufficient. At the relatively high temperature level of the second absorption stage much of the heat that needs to be cooled away can be rejected using cooling water, for example from a cooling tower, thus reducing the heat load on a refrigeration unit involving, for example, compression stages and organic cooling media. If cooling water is available at low temperatures, such as 5-10° C., the need for refrigeration can be eliminated so that the capacity of the refrigeration unit is significantly reduced.
According to one embodiment, the absorber comprises a single tower housing the first and the second contacting means, with the second contacting means being located vertically above the first contacting means inside the tower. An advantage of this embodiment using a single tower which is common to the first and second contacting means is that a simple absorber design can be utilized. Furthermore, the transfer of partly cleaned flue gas and recirculated CO2-enriched ammoniated solution between the first and second absorption stages can be made efficient, in a “plug flow” manner and in a way which ensures good distribution of flue gas and solution within packing material of the respective stage. Optionally, when a third absorption stage is included in the absorber for polishing ammonia, a third contacting means of the third absorption stage may be arranged within the single tower housing together with the first and the second contacting means. In such case the third contacting means would be located vertically above the second contacting means.
Further objects and features of the present invention will be apparent from the following detailed description and claims.
The invention is described in more detail below with reference to the appended drawings in which:
The conventional air pollution control system 6 could comprise further devices, such as a selective catalytic reduction reactor, e.g., of the type described in U.S. Pat. No. 5,555,849, for capturing nitrogen oxides from the flue gas stream, such further devices not being illustrated in
The flue gas stream, which comprises very small amounts of most pollutants, but still most of the original concentration of carbon dioxide, oxygen and nitrogen, leaves the conventional air pollution control system 6 via a duct 14. The duct 14 is operative for forwarding the flue gas stream to a carbon dioxide capture system 16. The carbon dioxide capture system 16 comprises a CO2-absorber 18 in which the flue gas stream is brought into contact with an ammoniated solution. The ammoniated solution may also include a promoter to enhance the chemical reaction kinetics involved in the capture of CO2 by the ammoniated solution. For example, the promoter may include an amine (e.g. piperazine) or an enzyme (e.g., carbonic anhydrase or its analogs), which may be in the form of a solution or immobilized on a solid or semi-solid surface.
A CO2-enriched solution pipe 20 is operative for forwarding, by means of a high pressure pump, not illustrated in
A duct 36 is operative for forwarding a cleaned flue gas stream, having a low concentration of carbon dioxide, from the CO2-absorber 18 to a water wash vessel 38, which is optional and which is operative for capturing ammonia, NH3, from the flue gas stream that has been treated in the CO2-absorber 18. A stream of cold water containing low concentration of ammoniated solution is supplied via pipe 40, is cooled in a heat exchanger 42 and is supplied to the water wash vessel 38. A duct 44 is operative for forwarding a flue gas stream that has been further cleaned in the water wash vessel 38, to a stack 46 which releases the further cleaned flue gas stream to the atmosphere. Optionally, a portion of the cold water circulating in water wash vessel 38 and having captured ammonia may be transported, via pipe 47, to the CO2-absorber 18.
As is illustrated in
A collecting device in the form of a tank 66 is arranged at the bottom of the tower 48 for collecting CO2-enriched ammoniated solution to form a collected CO2-enriched ammoniated solution. A pipe 68 is connected to the tank 66 for transporting a stream of CO2-enriched solution from the tank 66 to a splitting point 70. At the splitting point 70 the flow of collected CO2-enriched solution is split into a first portion being a first CO2-enriched solution stream which is forwarded, via CO2-enriched solution pipe 20 and a high-pressure pump 72, to the regenerator 22 illustrated in
A central portion 75 of the tower 48 forms a transfer device which allows the direct transfer of partly cleaned flue gas stream FG coming from the first absorption stage 54 to the second absorption stage 56, and allows transfer of recirculated CO2-enriched solution from the second absorption stage 56 to the first absorption stage 54. The recirculated CO2-enriched solution flows vertically downwards, by gravity, from the second absorption stage 56 to the first absorption stage 54. A pump is not needed for transferring the recirculated CO2-enriched solution from second stage 56 to first stage 54. Furthermore, it is not necessary to cool or heat the recirculated CO2-enriched solution when passing vertically downward from second stage 56 to first stage 54.
A recirculation pump 76 is arranged on the recirculation pipe 74 for transporting the second stream from the splitting point 70 to the second stage 56. A water cooler 78 is arranged on the recirculation pipe 74 for cooling the recirculated CO2-enriched solution before allowing the recirculated CO2-enriched solution to enter the liquid distributor 64 of the second stage 56.
As alternative to being connected to the splitting point 70, the pipe 20 and the recirculation pipe 74 could be fluidly connected directly to the tank 66.
Typically, the second stream of collected CO2-enriched solution forwarded, as a recirculated CO2-enriched solution, via recirculation pipe 74 to the second stage 56 would comprise 30-70% by weight of the total amount of collected CO2-enriched solution being transported from tank 66. The first stream of collected CO2-enriched solution forwarded via pipe 20 to the regenerator 22 illustrated in
CO2-lean solution is supplied from the regenerator 22 illustrated in
Optionally, the CO2-lean solution supplied via pipe 34 could be heat-exchanged in a heat exchanger 80 with the CO2-enriched solution of pipe 20 before entering liquid distributor 60. Furthermore, a further heat exchanger 82 could be arranged in the pipe 34 for further cooling the CO2-lean solution before the latter enters the liquid distributor 60. The cooling medium of the heat exchanger 82 is preferably water, for example from a cooling tower, since the cooling requirement for the CO2-lean solution is moderate.
Both in the first absorption stage 54 and in the second absorption stage 56, the contact between the flue gas stream and the respective solution occurs in a counter-current mode, with the flue gas stream FG flowing vertically upwards, and the respective solution flowing vertically downwards.
The amount of the first portion of the collected CO2-enriched ammoniated solution, forwarded to the regenerator 22 via pipe 20, in relation to the amount of the second portion of the collected CO2-enriched ammoniated solution, forwarded to the second absorption stage 56 via pipe 74 can be controlled. To this end, a first control valve 84 may be arranged in the pipe 20, and a second control valve 86 may be arranged in the pipe 74.
According to a further embodiment, the absorber 18 may be provided with a third, uppermost, absorption stage 90. The third stage 90 is an ammonia polishing stage having the purpose of further reducing the load of ammonia on the water wash vessel 38 illustrated in
A “polishing portion” of the recirculated CO2-enriched ammoniated solution supplied from pump 76 via recirculation pipe 74 may, in this further embodiment, be branched off to a polishing stage recirculation pipe 96. The remainder of the recirculated CO2-enriched ammoniated solution, which remainder may be referred to as a “CO2 absorbing portion” of the recirculated CO2-enriched ammoniated solution, is, in this further embodiment, transported via a further recirculation pipe 98, to the second stage 56 for being used in the absorption of CO2 and ammonia in the second absorption stage 56 in accordance with the principles described hereinbefore. To control the amount of the recirculated CO2-enriched ammoniated solution being transported to the respective second and third stages 56, 90, a valve 100 has been arranged on the polishing stage recirculation pipe 96, and a valve 102 has been arranged on the further recirculation pipe 98. By controlling the valves 100, 102 a suitable amount of recirculated CO2-enriched ammoniated solution can be supplied to each of the stages 56, 90. Typically, 50-90%, more preferably 70-80%, of the total amount of recirculated CO2-enriched ammoniated solution pumped by pump 76 is transported, as the CO2 absorbing portion, to the second stage 56 via pipe 98, and the remaining 10-50%, more preferably 20-30%, of the recirculated CO2-enriched ammoniated solution is transported, as polishing portion, to the third stage 90 via pipe 96.
To improve the polishing capacity of the optional third stage 90 a refrigerated cooler 104 may be arranged in the polishing stage recirculation pipe 96. The refrigerated cooler 104 may be connected to a refrigeration unit, not shown, which supplies a low temperature cooling medium, such as a water-glycol mixture, an organic cooling media, or ammonia, having a temperature of typically 0-8° C., to the refrigerated cooler 104. The refrigerated cooler 104 may typically be arranged for cooling the polishing portion of the recirculated CO2-enriched ammoniated solution transported in the polishing stage recirculation pipe 96 to a polishing temperature of about 0-10° C., preferably 3-7° C. The polishing temperature of about 0-10° C., i.e., the temperature of the polishing portion of the recirculated CO2-enriched ammoniated solution supplied to the third stage 90, is lower than the absorbing temperature of typically 20-25° C. of the CO2 absorbing portion of the recirculated CO2-enriched ammoniated solution supplied to the second stage 56. The low polishing temperature of the polishing portion of the recirculated CO2-enriched ammoniated solution supplied to the third stage 90 is very efficient for polishing the cleaned flue gas coming from the second stage 56 with respect to its concentration of ammonia. Hence, in this optional embodiment, a further cleaned flue gas with a very low concentration of ammonia leaves the absorber 18 via the outlet 52 and is forwarded, via duct 36, to optional water wash vessel 38.
According to an alternative embodiment a portion of the recirculated CO2-enriched ammoniated solution pumped in pipe 74 by pump 76 is directed, via a first by-pass pipe 106, to the CO2-lean ammoniated solution pipe 34 and further to the first absorption stage 54. An advantage of forwarding a portion of the recirculated CO2-enriched ammoniated solution to the first stage 54 is that, in some cases, it is desired to reduce a concentration of gaseous ammonia of the partially cleaned flue gas leaving the first stage 54. Typically, 0-50% of the total flow of recirculated CO2-enriched ammoniated solution pumped by pump 76 would be directed to the first stage 54 for the purpose of reducing the concentration of ammonia of the partially cleaned flue gas, and the remaining 50-100% would be pumped to the second stage 56, and third stage 90, if present.
According to a further alternative embodiment a portion of the CO2-lean ammoniated solution forwarded from the regenerator 22 via the pipe 34 may be forwarded, via a second by-pass pipe 108, to the recirculation pipe 74, 98 and further to the second absorption stage 56. An advantage of forwarding a portion of the CO2-lean ammoniated solution to the second stage 56 is that in some cases it is desired to increase the CO2 absorption capacity of the second absorption stage 56. Typically 4-30%, and more preferably 10-20%, of the total flow of CO2-lean ammoniated solution of the pipe 34 would, in this alternative embodiment, be directed to the second stage 56 for the purpose of increasing the absorption of CO2 in the second absorption stage 56, and the remaining amount of CO2-lean ammoniated solution would be forwarded, via the pipe 34, to the first stage 54.
According to a still further alternative embodiment a portion of the CO2-lean ammoniated solution forwarded from the regenerator 22 via the pipe 34 may be forwarded, via a third by-pass pipe 110, to the polishing stage recirculation pipe 96, optionally via the refrigerated cooler 104, and further to the third absorption stage 90. An advantage of forwarding a portion of the CO2-lean ammoniated solution to the third stage 90 is that in some cases it is desired to reduce the risk of solid precipitation of ammonium bicarbonate and/or carbonate particles of the third stage 90. Typically, 0-5% of the total flow of CO2-lean ammoniated solution of the pipe 34 would be forwarded to the third stage 90 for the purpose of reducing the risk of solid precipitation in the third stage 90, and the remaining amount of CO2-lean ammoniated solution would be forwarded to the first stage 54. According to one embodiment a portion, typically 2-10% of the total flow of CO2-lean ammoniated solution transported to the absorber 18 from the regenerator 22 via the pipe 34, would be transported, via third by-pass pipe 110, to the third stage 90 in an intermittent manner. For example, the CO2-lean ammoniated solution could be supplied to third stage 90, via third by-pass pipe 110, on regular intervals, for example during a period of 1-10 minutes every second hour, or when a formation of solid precipitation of ammonium bicarbonate particles in the third stage 90 has been detected, in order to dissolve formed ammonium bicarbonate particles.
The function of the absorber 18 will now be described in more detail with reference to
In
Location AA refers to a location where the CO2-enriched solution forwarded via recirculation pipe 74 enters the absorber 18 and where the flue gas stream FG from which CO2 has been captured leaves the absorber 18. Hence, location AA refers to conditions of “fresh recirculated CO2-enriched solution” entering second stage 56 of absorber 18, and “cleaned flue gas stream” leaving second stage 56 of absorber 18.
Location BB refers to a location where the recirculated CO2-enriched solution supplied via pipe 74 has passed through mass transfer device 62 of second stage 56 of absorber 18, and where partly cleaned flue gas stream FG is about to enter second stage 56. Hence, location BB refers to conditions of “partly spent recirculated CO2-enriched solution” leaving second stage 56 of absorber 18, and “partly cleaned flue gas stream” about to enter second stage 56 of absorber 18.
Location CC refers to a location where the recirculated CO2-enriched solution having passed through mass transfer device 62 of second stage 56 of absorber 18 has been mixed with fresh CO2-lean solution entering via pipe 34, just prior to entering first stage 54 of absorber 18. The properties of the partly cleaned flue gas stream FG is substantially the same in location CC as in location BB. Hence, location CC refers to conditions of “mixture of partly spent recirculated CO2-enriched solution and fresh CO2-lean solution” about to enter first stage 54 of absorber 18, and “partly cleaned flue gas stream” leaving first stage 54 of absorber 18.
Location DD refers to a location where the mixture of the recirculated CO2-enriched solution and the CO2-lean solution has passed through mass transfer device 58 of first stage 54 of absorber 18, and where CO2-rich flue gas stream FG is about to enter first stage 54. Hence, location DD refers to conditions of “mixture of spent CO2-enriched solution and spent CO2-lean solution” leaving first stage 54 of absorber 18, and “CO2-rich flue gas stream” about to enter first stage 54 of absorber 18. The conditions of the mixture of the spent CO2-enriched solution and spent CO2-lean solution in location DD is substantially the same as the conditions of the solution collected in tank 66, and forwarded via pipes 68, 20 and 74.
The relation between concentration of CO2 and NH3 in the solutions at the various locations can be given in various manners. In
It has been found that the following conditions apply; a high R-value is beneficial for the capture of CO2 from the flue gas stream. A high R-value also causes an increased vapour pressure of NH3, which potentially increases slip of ammonia from absorber. Furthermore, it has been found that a high temperature is beneficial for the kinetics of the capture of CO2. A high temperature also increases the vapour pressure of NH3.
As illustrated in
The liquid to gas ratio, i.e. the amount of recirculated CO2-enriched solution passing through mass transfer device 62 of the second stage 56 in relation to the amount of flue gas passing through mass transfer device 62 of the second stage 56, also referred to as L/G, is, in the simulation, about 6 kg of recirculated CO2-enriched ammoniated solution per kg of flue gas, as viewed in location AA. Typically, the L/G of the second stage 56, as viewed in location AA, is 3 to 10, and more preferably 4 to 8, kg solution/kg flue gas. It will be appreciated that the L/G is not absolutely constant through the mass transfer device 62 since capture of CO2 and NH3 in the solution causes a transfer of mass from the flue gas stream to the solution. Typically, the concentration of ammonia, NH3, of the CO2-lean ammoniated solution and of the recirculated CO2-enriched ammoniated solution would be in the range of 4-12 mole NH3 per litre of solution. The corresponding concentration of carbon dioxide, CO2, can be calculated from the respective R-value of the solution in question.
The CO2-lean solution supplied via pipe 34 has an R-value of about 3.0. Typically, the R-value of the CO2-lean solution in pipe 34 would be in the range of 2.5 to 4.50. In location CC the CO2-lean solution is mixed with the partly spent recirculated CO2-enriched solution having passed through second stage 56. As an effect of such mixing, the R-value, in location CC, becomes about 2.09 (CO2 loading =0.478). Typically, the R-value of the mixture in location CC would be in the range of 1.90 to 2.40. Such a high R-value means that a very efficient capture of CO2 in first stage 54 can be obtained. As an effect of CO2 being captured from the flue gas stream in the first stage 54 the R-value gradually decreases to about 1.88 (CO2 loading=0.53), which is the R-value in location DD. Typically, the R-value of the ammoniated solution is within the range 1.70 to 2.00 in location DD. Solution with an R-value of about 1.88 is, hence, collected in tank 66, and is partly returned to second stage 56, via pipe 74, and partly forwarded to the regenerator 22, illustrated in
The liquid to gas ratio, L/G, i.e. the amount of the mixture of the recirculated CO2-enriched solution and the CO2-lean solution passing through mass transfer device 58 of the first stage 54 in relation to the amount of flue gas passing through mass transfer device 58 of the first stage 54 is, in the simulation, about 12 kg of the mixture of recirculated CO2-enriched solution and CO2-lean solution per kg of flue gas, as viewed in location CC. Typically, the L/G of the first stage 54, as viewed in location CC, is 5 to 16, more preferably 7 to 12, and most preferably 8 to 10 kg solution/kg flue gas. It will be appreciated that the L/G is not absolutely constant through the mass transfer device 58 since capture of CO2 and NH3 in the solution causes a transfer of mass from the flue gas stream to the solution.
According to one embodiment, the L/G is controlled by controlling the valves 84, 86. For example, increasing the degree of opening of valve 84 and reducing the degree of opening of valve 86 reduces the L/G in the second absorption stage 56.
As illustrated in
In
The CO2-lean solution supplied via pipe 34 has a temperature, upon entering the first stage 54 of the absorber 18, i.e., downstream of the further heat exchanger 82, of about 30° C. Typically, the temperature of the CO2-lean solution entering absorber 18 would be in the range of 20-40° C. In location CC the CO2-lean solution is mixed with the partly spent recirculated CO2-enriched solution having passed through second stage 56. As an effect of such mixing, the temperature, in location CC, becomes about 25°. Typically, the temperature of the mixture of the CO2-lean solution and the partly spent recirculated CO2-enriched solution in location CC would be in the range of 20-30° C. Such a relatively high temperature has been found to be positive to the kinetics of the CO2 absorption, and means that a very efficient capture of CO2 in first stage 54 can be obtained. As an effect of CO2 being captured from the flue gas stream in the first stage 54 in an exothermic reaction, and the fact that the flue gas stream heats the CO2-enriched solution upon contact therewith in the mass transfer device 58 of the first stage 54, the temperature gradually increases to about 29° C., which is the temperature in location DD. Solution with temperature of about 29° C. is, hence, collected in tank 66.
Throughout the first stage 54 the temperature is well above the solidification temperature, dashed line “solidification” in
The CO2-rich flue gas stream FG entering absorber 18 via inlet 50 contains a large amount of CO2. Almost immediately upon entering into tower 48 ammonia, NH3, will evaporate from the ammoniated solution, due to the equilibrium conditions at the R-value and temperature demonstrated hereinabove, and mix with the flue gas stream, FG. Hence, in location DD, just before entering the first stage 54, the flue gas stream FG will contain CO2 in a molar fraction of about 0.15, and NH3 in a molar fraction of about 0.03.
While passing through the mass transfer device 58 of the first stage 54 the solution will efficiently capture CO2. Hence, in location CC, just after leaving the first stage 54, the partly cleaned flue gas stream FG will contain CO2 in a molar fraction of about 0.055, and NH3 in a molar fraction of about 0.035.
The lower temperature and lower R-value of the recirculated CO2-enriched ammoniated solution of the second stage 56 will shift the equilibrium conditions with regard to ammonia. Hence, in location BB, just before entering the second stage 54, the partly cleaned flue gas stream FG will contain CO2 in a molar fraction of about 0.055, and NH3 in a molar fraction of about 0.01.
While passing through the mass transfer device 62 of the second stage 56 the solution will capture CO2. Hence, in location AA, just after leaving the second stage 56, the flue gas stream FG will contain CO2 in a molar fraction of about 0.018, and NH3 in a molar fraction of about 0.01.
With the absorber 18 described hereinbefore, a low slip of ammonia, NH3, is achieved, thanks to the conditions of the second stage 56. Very efficient capture of carbon dioxide, CO2, is achieved in the first stage 54, and capture of carbon dioxide continues also in the second stage 56. The total L/G is about 12 kg solution/kg flue gas, which is typically in the range of 10-20% lower than the three absorber process illustrated in the prior art document WO 2009/055419. Correspondingly electrical power supply may be reduced by about 10%, since the amount of solution pumped in the absorber is reduced. Furthermore, the absorber 18 is significantly simpler as regards construction and ancillary equipment, causing savings in capital and maintenance costs of at least 10%. Furthermore, the relatively high temperature of the solutions and the high R-values increases CO2 capture efficiency and reduces the required volume of the mass transfer devices 58 and 62, thereby reducing the size and height of the tower 48. Still further, the amount of energy consumed in the refrigeration unit is reduced, since solutions circulating in the absorber 18 are typically cooled to, on average, an as high temperature as 20° C. If cooling water from a cooling tower is available, the energy consumption could be even further reduced.
It will be appreciated that numerous variants of the embodiments described above are possible within the scope of the appended claims.
Hereinbefore it has been described that the absorber 18 comprises a single tower 48. It will be appreciated that the absorber could also comprise more than one tower. For example, the second stage 56 could be arranged in a first tower which is separate from a second tower in which the first stage 54 is arranged, with flue gas stream and solution being transferred between the two towers.
Hereinbefore, it has been described that the mass transfer devices 58, 62 may comprise structured or random packing. It will be appreciated that other mass transfer devices that provide efficient contact between solution and flue gas stream could also be arranged inside the tower.
Hereinbefore, it has been described that the absorber 18 comprises a first absorption stage 54 and a second absorption stage 56. It will be appreciated that the absorber 18 may also comprise further absorption stages. However, an absorber 18 comprising solely a first and a second absorption stage 54 and 56 is often very efficient with regard to capture of CO2 and with regard to capital and operating costs.
Hereinbefore, it has been described that the L/G may, preferably, be 5 to 16 kg solution/kg flue gas in the first absorption stage 54, and 3 to 10 kg solution/kg flue gas in the second absorption stage 56. If the absorber 18 is provided with the optional third absorption stage 90, then the L/G of that third stage 90 would, preferably, be 0.5 to 2.5 kg solution/kg flue gas. The L/G of the second absorption stage 56 could remain unaffected, since in one embodiment the solution that has passed through the third stage 90, when present, would subsequently pass through the second stage 56 along with the solution supplied thereto.
To summarize, a system for capturing CO2 from a flue gas stream comprises:
While the invention has been described with reference to a number of preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the present invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiments disclosed as the best mode contemplated for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. Moreover, the use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.
| Number | Date | Country | Kind |
|---|---|---|---|
| 11179402.0 | Aug 2011 | EP | regional |
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/IB2012/001649 | Aug 2012 | US |
| Child | 14193052 | US |
