This document relates generally to a new and improved apparatus and method for capturing carbon dioxide (CO2) from an acid gas stream.
The cleaning of acid gases or sour gas, such as carbon dioxide in particular, from natural gas and in oil refining has been an extensively practiced technology. The industrial removal of carbon dioxide from natural gas dates back to the 1930's.
In the 21st century, due to the potential impact of anthropogenic carbon dioxide emissions on the climate, post-combustion carbon dioxide capture has gained tremendous attention. While several technologies exist for the removal of acid gases, one of the most commonly employed practices is the use of aqueous amines.
In this process, an aqueous amine solution is circulated between an absorber/absorption tower and a stripper. The flue gas or acid gas, containing carbon dioxide enters the bottom of the absorber while the aqueous amine absorbent enters the top of the absorber in counter-current flow to the acid gas. As the acid gas and the amine absorbent come into contact in the absorber, the absorbent removes the carbon dioxide from the gas stream. The amine solution, now rich in carbon dioxide, is discharged from the bottom of the absorber and passed through a heat exchanger to improve efficiency before entering the top of the stripper where the amine solution is heated to a higher temperature. The stripper removes the carbon dioxide as a gas from the amine solution. The carbon dioxide is then passed through a condenser and separated from water at a separator. The carbon dioxide is then subjected to downstream processing or storage while the water is returned to the stripper. The carbon dioxide lean amine solution exits the bottom of the stripper and is returned to the absorber by way of the heat exchanger and a chiller.
The absorber tower is the single biggest capital expenditure in a CO2 capture process. Estimates put the absorber itself as 30-50% of the entire CO2 capture capital cost. Therefore, maximizing the effectiveness of the absorber tower, such as achieving maximum liquid-gas interface as described in the prior art, and minimizing the height is an important part of reducing the cost of CO2 capture. Toward this end, two aspects are both important—controlling the temperature profile and minimizing the liquid-gas maldistribution inside column.
During carbon capture, an exothermic chemical absorption reaction occurs in the absorber tower. The reaction is strongest at the top, after the lean solvent enters the column and depends on the local solvent mass to gas mass within the column (L/G). As the reaction proceeds, the temperature increases. As the temperature increases the driving force for CO2 capture decreases and the reaction slows. Also, as the reaction proceeds the amount of gas (G) decreases, as CO2 is transferred from the gas phase to the liquid phase. Typically, a temperature bulge occurs in the top section (10-20%) of the column and the column height (30-40% of the column) below this bulge is relatively ineffective.
We have now found that changing the type of structured packing in the absorber tower allows for different liquid-gas interface areas to be applied at different heights of the column. This allows the temperature and therefore the reaction rate to be controlled and this, in turn, allows advantage to be taken of the entire column height, minimizing the ineffective zone below the temperature bulge. This maximizes the effectiveness of the absorber tower thereby allowing the use of a smaller absorber tower, saving both capital and operating cost.
Traditionally, liquid and gas is redistributed inside a column with specialized internals that require 5-10 feet of column height. We use a few inches of random packing applied between sections of structured packing as built-in redistributor to cause short sections of higher pressure drop (15-20% of pressure drop of the value produced by section of structure packing above) that work to redistribute the liquid and gas. This will save significant column height and allows for a smaller column to be applied, saving capital cost.
This document is related to a new and unique apparatus having a discretized packing arrangement, as well as to a related method, that are both adapted to modify this temperature profile, effectively moving the temperature bulge down the absorber thereby resulting in as much as a 5-11% increase in rich loading, depending upon solvent lean loading.
In accordance with the purposes and benefits set forth herein, a new and improved apparatus is provided. That apparatus comprises an absorber having a discretized packing arrangement including a first packing segment, a second packing segment and a third packing segment wherein the first packing segment includes a first structured packing having a first specific surface area SA1, the second packing segment includes a second structured packing having a second specific surface area SA2 and the third packing segment includes a third structured packing having a third specific surface area SA3 where SA1<SA2<SA3. One or two or more packing makes up a section separated by pre-installed mechanical gas and liquid distributors.
More specifically, the second structured packing segment is provided between the first structured packing segment and the third structured packing segment within the absorber. Still more specifically, the first packing segment is provided above the second packing segment and the second packing segment is provided above the third packing segment. Generally, the first and second packing segments will be combined into one section (the top packing section of absorber), and the third packing segment makes up the bottom section of packing. A set of mechanical gas and liquid distributor is installed between top and bottom packing section.
In one or more of the many possible embodiments of the absorber, at least one liquid/gas distributor is included in at least one of the first packing segment, the second packing segment and the third packing segment. In one or more of the many possible embodiments of the apparatus, the at least one liquid/gas distributor is a section of random packing.
For purposes of this document, the terminology “structured packing” refers to a uniform arrangement of packing material or elements. For purposes of this document, the terminology “random packing” refers to randomly fitting material or elements used to increase the surface area over which reactants can interact while minimizing the complexity of the column. For purposes of this document, the packing “segment” refers a group of packing materials with same specification. For purposes of this document, the packing “section” refers a set of packing materials with one or more packing segments.
Significantly, the random packing used in the absorber is characterized by a random packing unit pressure drop that is greater than any unit pressure drop characteristic of the first structured packing of the first packing segment, the second structured packing of the second packing segment and the third structured packing of the third packing segment.
In one or more of the many possible embodiments of the apparatus, the first specific surface area SA1 of the first structured packing is less than 34 ft2/ft3, the second specific surface area SA2 is between 34 ft2/ft3 and 129 ft2/ft3 and the third specific surface area SA3 is above 152 ft2/ft3.
In one or more of the many possible embodiments of the apparatus, the first packing segment includes multiple layers of the first structured packing separated by a first layer of the random packing. In one or more of the many possible embodiments, the multiple layers of the first structured packing have a first thickness T1 of 121.92-182.88 cm and the layer of random packing has a second thickness T2 of 7.62-15.24 cm.
In one or more of the many possible embodiments of the apparatus, the second packing segment includes multiple layers of the second structured packing having the first thickness T1 separated by a second layer of the random packing having the second thickness T2.
In one or more of the many possible embodiments of the apparatus, the third packing segment includes multiple layers of the third structured packing having the first thickness T1 separated by a third layer of the random packing having the second thickness T2.
In one or more of the many possible embodiments of the apparatus, the absorber is adapted to remove carbon dioxide from a flue gas stream using an amine solvent and the apparatus further includes a stripper adapted to remove carbon dioxide from the amine absorbent.
In one or more of the many possible embodiments of the apparatus, the apparatus may also include a secondary stripper downstream from the stripper. The stripper may include (a) an upper packing section including the third structured packing having the third specific surface area SA3 and (b) a lower packing section including the first and/or second structured packing having the first specific surface area SA1 and the second specific surface area SA2.
In one or more of the many possible embodiments of the apparatus, the upper packing section may include multiple layers of the third structured packing separated by a fourth layer of the random packing.
In one or more of the many possible embodiments of the apparatus, the lower packing section includes multiple layers of the first and/or second structured packing separated by a fifth layer of the random packing.
In one or more of the many possible embodiments of the apparatus, the secondary stripper includes (a) a top packing section including the second structured packing, having the second specific surface area SA2, and (b) a lower packing section including a third structured packing, having a third specific surface area SA3.
In accordance with an additional aspect, a new and improved method of capturing carbon dioxide from an acid gas stream comprises the steps of: (a) providing an absorber tower with a first packing segment, having a first specific surface area SA1, a second packing segment, having a second specific surface area SA2, and a third packing segment, having a third specific surface area SA3, where SA1<SA2<SA3 to control local liquid-to-gas mass ratios, CO2 absorption rates and temperatures in order to reduce a packing height required to achieve a desirable carbon loading, (b) subjecting the acid gas stream to a countercurrent flow of a carbon dioxide lean amine solvent in the absorber tower, (c) separately discharging treated acid gas and a carbon dioxide rich amine solvent from the absorber tower and (d) recovering the carbon dioxide from the carbon dioxide rich amine solvent in a stripper and returning carbon dioxide lean amine solvent to the absorber tower.
In one or more of the many possible embodiments of the method, the method may include positioning the second packing segment between the first packing segment and the third packing segment. In one or more of the many possible embodiments, the method may further include separating the first and second structured packing segments with a first layer of a higher pressure drop random packing and the second and third structured packing segments with a second layer of higher pressure drop random packing whereby the first and second layers of the higher pressure drop random packing act to redistribute the carbon dioxide lean and the carbon dioxide rich CO2 absorbent in the absorber tower. In at least one possible embodiment, the method includes the step of controlling an exothermic CO2 absorption reaction rate by controlling a local liquid-to-gas mass ratio inside the absorber tower.
In accordance with yet another aspect, a method of capturing carbon dioxide from an acid gas stream, comprises: (a) providing an absorber tower with a plurality of packing segments having different specific surface areas at different heights in the absorber tower to control local liquid-to-gas mass ratios, CO2 absorption rates and temperatures in order to reduce a packing height required to achieve a desirable carbon loading; (b) subjecting the acid gas stream to a countercurrent flow of a carbon dioxide lean CO2 absorbent in the absorber tower to produce a carbon dioxide rich CO2 absorbent; (c) separately discharging treated acid gas and the carbon dioxide rich CO2 absorbent from the absorber tower; and (d) recovering the carbon dioxide from the carbon dioxide rich CO2 absorbent in a stripper and returning the carbon dioxide lean CO2 absorbent to the absorber tower. In some embodiments, the method further includes the step of separating the plurality of structured packing segments with a higher pressure drop random packing which acts to redistribute the carbon dioxide lean and the carbon dioxide rich CO2 absorbent in the absorber tower.
In the following description, there are shown and described several embodiments of the apparatus and the related method. As it should be realized, the apparatus and method are capable of other, different embodiments and their several details are capable of modification is various, obvious aspects all without departing from the apparatus and method as set forth and described in the following claims. Accordingly, the drawings and descriptions should be regarded as illustrative in nature and not as restrictive.
The accompanying drawing figures incorporated herein and forming a part of the specification, illustrate several aspects of the apparatus and method and together with the description serve to explain certain principles thereof.
Reference will now be made in detail to the illustrated embodiments of the apparatus, examples of which are illustrated in the accompanying drawing figures.
Reference is now made to
Next, a blower 20 delivers the flue gas to the pretreatment column 18 where the flue gas is treated with an aqueous solution of soda ash (Na2CO3) or sodium hydroxide (NaOH) to remove sulfur dioxide (SO2). More particularly, the pump 22 circulates the caustic solution through a second cooling water supply heat exchanger 24 if needed and the pretreatment column 18. The removal of the sulfur dioxide serves to minimize thermal stable salt formation and degradation of the solvent in the CO2 capture block.
The flue gas is then passed through a membrane 26, of a type known in the art, to split the flue gas into two streams. Such a membrane is more fully described in U.S. Pat. No. 9,409,120 (owned by the assignee of the present invention), the full disclosure of which is incorporated herein by reference.
The first stream 28 is a CO2-enriched permeate stream comprising approximately 24% of the total flue gas and containing approximately 25% CO2 after removal of water vapor at 40° C. The second stream 30 is a CO2-lean reject stream (approximately 76% of the total flue gas flow rate) containing approximately 10% CO2 after water removal at 40° C.
More particularly, the two streams 28 and 30 are both delivered to the absorber tower or absorber 32. There the flue gas is subjected to a concurrent stream of an CO2 absorbent or amine solvent of a type known in the art to be suitable for CO2 capture. Such a CO2 absorbent includes primary, secondary and tertiary amines including, for example, 1-amino-2-propanol (A2P), 2-amino-2-methyl-1-propanol (AMP), piperidine (PZ), methyldiethanolamine (MDEA) and other compounds, including, for example, anti-oxidant.
Following CO2 removal, the treated flue gas is delivered from the top of the absorber 32 to the solvent recovery column 34 where CO2 absorbent entrained in the treated flue gas is recovered using a countercurrent flow of wash water and an amine nucleation agent circulated through a separator element 36, such as a screen or filter, by a pump 38. As shown, the wash water, amine nucleation agent and entrained amine solvent may be cooled by a cooling water supply in the heat exchanger 40. Wash water, including entrained amine solvent separated from the amine nucleation agent by the separator element 36 is returned to the absorber 32 by means of a return circuit not shown.
The solvent recovery column 34 and the method for recovering the amine solvent from the treated flue gas are more fully described in U.S. patent application Ser. No. 16/460,229 entitled APPARATUS AND METHOD FOR RECOVERING AN AMINE SOLVENT FROM AN ACID GAS STREAM and filed on Jul. 2, 2019, the full disclosure of which is incorporated herein by reference. As disclosed therein, the amine nucleation agent may comprise an activated carbon having a density of 997 kg/m3+/−600 kg/m3 and a diameter less than 1.0 millimeter. The treated flue gas may then be discharged.
The now carbon dioxide rich CO2-absorbent or amine solvent is discharged from the bottom of the absorber 32 and directed by the pump 42 through the heat exchanger 44 to the stripper 46 where carbon dioxide is stripped from the carbon rich CO2-absorbent or amine solvent. The carbon dioxide exits at the top of the stripper 46 and is routed through a primary heat recovery exchanger 48 before exiting as a CO2 product stream that may be stored or undergo other chemical processing (not shown). The reboiler 52 functions to recycle carbon dioxide rich CO2-absorbent or amine solvent through the stripper 46 to ensure more efficient processing.
Carbon dioxide semi-lean CO2-absorbent or amine solvent exits the bottom of the stripper 46 and is transferred by pump 54 through the heat exchanger 56 to the secondary stripper 50 where even more carbon dioxide is stripped from the carbon dioxide semi-lean CO2-absorbent or amine solvent. This additional carbon dioxide exits the top of the secondary stripper 50 and is routed through the secondary heat exchanger 44 before being recycled to the power plant boiler. The now carbon dioxide lean CO2-absorbent or amine solvent exits the bottom of the secondary stripper 50 and is returned by the pump 58 through the lean heat recovery exchanger and the solvent polishing exchanger 62 to the absorber 32 where it is used to capture carbon dioxide from the flue gas as previously described. The water evaporator 61 supplies makeup water to amine loop from energy recovered from the heat exchangers 60 and 48 by operation of the pump 63.
Reference is now made to
In one possible embodiment of the apparatus 10, the first structured packing has a first specific surface area SA1 of less than 34 ft2/ft3, the second structured packing has a second specific surface area SA2 of between 34 ft2/ft3 and 129 ft2/ft3 and the third structured packing has a third specific surface area SA3 of above 152 ft2/ft3.
In the illustrated embodiment, a first in-situ “random packing” liquid/gas distributor 70 is provided between the first packing segment 64 and the second packing segment 66. A second in-situ “random packing” liquid/gas distributor 72 is provided at an intermediate point of the second packing segment 66. Two additional in-situ “random packing” liquid/gas distributors 74, 76 are provided at spaced points in the third packing segment 68. Each of the in-situ liquid/gas distributors 70, 72, 74, 76 may comprise a layer of random packing. That random packing is characterized by a first pressure drop per height PD1 that is greater than any pressure drop per height PD2 of the first structured packing 65 in the first packing segment 64, the second structured packing 67 in the second packing segment 66 and the third structured packing 69 in the third segment 68.
In one possible embodiment of the apparatus 10, the first or upper segment 64 comprises the top 20-30% of the total height of the top packing 64, 66 and 68. The second segment 66 comprises the middle 30-50% of the total height of the packing 64, 66 and 68. The third segment 68 comprises the bottom 30-40% of the total height of the packing 64, 66 and 68.
In one possible embodiment of the apparatus 10, every 60.96 to 243.84 cm of structured packing is interrupted by 7.62-15.24 cm of in-situ liquid/gas distributor in the form of random packing. This includes the first structured packing 65 used to form the first packing segment 64, the second structured packing 67 used to form the second packing segment 66 and/or the third structured packing 69 used to form the third packing segment 68.
It has been found that due to the low CO2 absorption driving force in utility flue gas and the highly viscous nature of second generation advanced amine solvents, the low pressure drop structured packing used in the packing sections 64, 66 and 68 suffers from a lack of macro-mixing/turbulence between the bulk solvent and the gas-liquid interface. This results in localized channel flow and significantly reduces column effectiveness. The application of short sections 7.62-15.24 cm of high pressure drop random packing in the form of in-situ liquid/gas distributors 70, 72, 74 and 76 re-adjusts the pressure and redistributes the liquid within the structured packing 65, 67, 69. As a result, the efficiency of the absorber 32 is significantly enhanced.
In one possible embodiment of the absorber 32, the first packing segment 64 includes multiple layers of the first structured packing 65 separated by in-situ gas/liquid distributor of random packing. The multiple layers of the first structured packing 65 may have a first thickness T1 of 121.92-182.88 cm and the layer of random packing may have a second thickness T2 of 7.62-15.24 cm. The second packing segment 66 may include multiple layers of the second structured packing 67 having a first thickness T1 of 121.92-182.88 cm separated by the layer of random packing 72 having a thickness T2 of 7.62-15.24 cm. The third packing segment 68 may have multiple layers of the third structured packing 69 having a thickness T1 of 121.92-182.88 cm separated by the layer of random packing 74 or 76 having a thickness T2 of 7.62-15.24 cm.
Reference is now made to
Reference is now made to
The apparatus 10 described herein is useful in a method of capturing carbon dioxide from an acid gas stream. That method includes a number of step including providing an absorber tower with a plurality of packing segments having different specific surface areas at different heights in the absorber tower to control local liquid-to-gas mass ratios, CO2 absorption rates and temperatures in order to reduce a packing height required to achieve a desirable carbon loading. The method also includes the step of subjecting the acid gas stream to a countercurrent flow of a carbon dioxide lean CO2 absorbent in the absorber tower to produce a carbon dioxide rich CO2 absorbent. Still further, the method includes the steps of separately discharging treated acid gas and the carbon dioxide rich CO2 absorbent from the absorber tower and recovering the carbon dioxide from the carbon dioxide rich CO2 absorbent in a stripper and returning the carbon dioxide lean CO2 absorbent to the absorber tower. The method also includes the step of separating the plurality of structured packing segments with a higher pressure drop random packing which acts to redistribute the carbon dioxide lean and the carbon dioxide rich CO2 absorbent in the absorber tower.
Controlling the exothermic CO2 absorption reaction rate is accomplished by controlling the local liquid-to-gas mass ratio inside the absorber tower. The reaction is strongest at the top, after the lean solvent enters the tower. As the reaction proceeds, the temperature increases. As the temperature increases the driving force for CO2 capture decreases and the reaction slows. Also, as the reaction proceeds the amount of gas (G) decreases, as CO2 is transferred from the gas phase to the liquid phase. Typically, a temperature bulge occurs in the top section of the absorber tower and the tower height below this bulge is relatively ineffective, as illustrated in
Changing the type of structured packing allows for different liquid-gas interface areas to be applied at different heights of the absorber tower. This allows the temperature and therefore the reaction rate to be controlled, which, in turn, allows advantage to be taken of the entire tower height, minimizing the ineffective zone below the temperature bulge. The magnitude of the bulge can be reduced and the temperature profile can be optimized in the CO2 absorber tower, as illustrated in
Traditionally, liquid and gas is redistributed inside an absorber tower with specialized internals every 5-10 ft of structure packing height. Significantly, these specialized internals require several feet of additional column height greatly increasing the overall height of the absorber tower. Instead, we use a few inches of random packing applied between sections of structured packing to cause short sections of higher gas pressure drop that work to redistribute the liquid and gas. Keeping the CO2 absorber tower or column short saves both capital and operating costs.
The foregoing has been presented for purposes of illustration and description. It is not intended to be exhaustive or to limit the embodiments to the precise form disclosed. Obvious modifications and variations are possible in light of the above teachings. All such modifications and variations are within the scope of the appended claims when interpreted in accordance with the breadth to which they are fairly, legally and equitably entitled.
This application is a continuation-in-part of U.S. patent application Ser. No. 16/711,633, filed on Dec. 12, 2019, which claims priority to U.S. Provisional Patent Application Ser. No. 62/779,702 filed on Dec. 14, 2018, both of which are i hereby incorporated by reference in their entirety.
This invention was made with government support under Grant No. DE-FE-0007395 awarded by the Department of Energy. The government has certain rights in the invention.
Number | Date | Country | |
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62779702 | Dec 2018 | US |
Number | Date | Country | |
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Parent | 16711633 | Dec 2019 | US |
Child | 17883482 | US |