Method and system for separating carbon dioxide

Abstract

A method (100) is proposed for separating carbon dioxide from one or more gas mixtures (1) containing carbon dioxide. The method comprises providing a first carbon dioxide-containing feed stream (2) and a second carbon dioxide-containing feed stream (3) using the gas mixture or gas mixtures (1), providing a first separating device (10), which is designed to adsorptively separate carbon dioxide, and a second separating device (20), which is designed to absorptively separate carbon dioxide, and adsorptively separating carbon dioxide from the first feed stream (2) in the first separating device (10) and absorptively separating carbon dioxide from the second feed stream (3) in the second separating device (20). The first separating device (10) and the second separating device (20) are operated in parallel with one another. In the first separating device (10), compression is carried out using a compressor arrangement (11) in and / or downstream of which compression heat is dissipated. Furthermore, an absorption agent is regenerated in the second separating device (20) using regeneration heat, wherein the compression heat, or a part thereof, dissipated in and / or downstream of the compressor arrangement (11) is used in the provision of the regeneration heat. A corresponding system is also proposed.

Description

[0001] P40362-EP

[0002] October 2, 2024 - Fischer

[0003] 1

[0004] Description

[0005] Process and plant for the separation of carbon dioxide

[0006] Area

[0007] The present disclosure relates to a process and a plant for separating carbon dioxide from one or more gas mixtures containing carbon dioxide.

[0008] background

[0009] Concerns about global warming and climate change are intensifying worldwide efforts to reduce the release of greenhouse gases such as carbon dioxide into the atmosphere. Carbon capture and storage (CCS) technologies play a strategic role in achieving today's carbon emission reduction targets.

[0010] The focus is increasingly shifting to the need to remove carbon dioxide from process exhaust gases and flue gases released during various processes such as hydrogen production, process heat generation, power generation, chemical manufacturing, and cement and steel production. As a first step, it makes sense to consider processes with relatively easy-to-process carbon dioxide sources. These are sources where carbon dioxide is present in high concentrations and / or partial pressures. The captured carbon dioxide can be safely stored or used for other purposes, such as in the food industry or for the production of chemicals like methanol.

[0011] There remains a need for improved approaches to separating carbon dioxide from gas mixtures. P40362-EP

[0012] October 2, 2024 - Fischer

[0013] 2

[0014] Overview

[0015] Against this background, a method and a system with the features of the independent patent claims are proposed. Embodiments are the subject of the dependent patent claims and the following description.

[0016] The proposed method serves to separate carbon dioxide from one or more gas mixtures containing carbon dioxide. The method comprises providing a first feed stream containing carbon dioxide and a second feed stream containing carbon dioxide using the gas mixture(s), providing a first separation unit configured for the adsorptive separation of carbon dioxide and a second separation unit configured for the absorptive separation of carbon dioxide, and adsorbing carbon dioxide from the first feed stream in the first separation unit and absorptively separating carbon dioxide from the second feed stream in the second separation unit.

[0017] The first and second isolating devices are operated in parallel, meaning that the first operating current is supplied to the first isolating device without having passed through the second isolating device, nor any precursor current of the first operating current, and the second operating current is supplied to the second isolating device without having passed through the first isolating device, nor any precursor current of the second operating current. The term "parallel" here refers specifically to temporal parallelism.

[0018] In the first separation device, the first feed stream is compressed using a compressor arrangement, and the compression heat is dissipated into and / or downstream of the unit.

[0019] It is understood that when "one" compression stage and "one" compressor arrangement are mentioned here, this does not preclude the use of multiple compression stages and compressor arrangements. In the case of multiple compression stages and compressor arrangements, which can also be sub-stages or compression levels in a multi-stage compressor arrangement, each P40362-EP downstream can be used.

[0020] October 2, 2024 - Fischer

[0021] 3

[0022] In each compression step, each compressor arrangement or each compressor stage, heat is removed according to the designs proposed here.

[0023] The compression heat, or a portion thereof, discharged into and / or downstream of the compressor assembly is used in the proposed method to provide regeneration heat for the regeneration of an absorbent in the second separation device.

[0024] For example, the regeneration of the absorbent can be carried out using a regeneration column with a bottom evaporator. The compression heat dissipated in and / or downstream of the compressor assembly, or a portion thereof, can be used to heat the bottom evaporator of the regeneration column. Other configurations include additional or alternative heating tasks during the regeneration of the absorbent, such as preheating it before feeding it into a regeneration column.

[0025] The first and second separation devices can be spatially separated and positioned at a certain distance from each other, provided that means are available for heat transfer. This means can be, in particular, a connecting line that carries a heat transfer medium from the first to the second separation device. For example, the heat transfer medium could be steam carried in a steam line. After the supply of heat for compression and corresponding cooling, certain configurations may include the return of condensate from the second to the first separation device. In this way, a cycle can be created. However, the configurations proposed here involve carrying out the heat transfer without a temperature increase using a heat engine such as a heat pump.

[0026] For the large-scale direct separation of carbon dioxide from gas mixtures containing carbon dioxide, which are generated, for example, in conventional hydrogen, cement or steel production or in power plants as flue or process gases, there are currently predominantly two approaches: adsorptive removal by pressure swing adsorption and subsequent partial condensation P40362-EP

[0027] October 2, 2024 - Fischer

[0028] 4. The process also includes absorptive removal by washing, i.e., by isorptive separation using an absorbent or washing agent. Both processes are known per se and are employed in the first and second separation units of the proposed method. The method proposed here and its embodiments combine both processes in a particularly advantageous manner.

[0029] The adsorptive process, also known by the applicant under the trademark HISORP® CC, and carried out in the first separation unit, primarily requires energy for compressing gases in compressor units. This typically amounts to 150 to 600 kWh per ton of carbon dioxide at a purity of more than 95 mol% and a pressure of 30 bar. Due to the process design, cooling the gases heated during compression, i.e., removing the heat of compression, is both necessary and desirable. To minimize the compressor workload, the lowest possible temperature at the inlet of a compressor stage is desirable. For this purpose, the compressors are equipped with intermediate and final coolers through which heat is dissipated during and after compression. The proposed configurations can utilize heat dissipated at any point.

[0030] Any number of compression stages can be provided, and coolers can be located before and after all or some of the compression stages. It is understood that in not all embodiments proposed here is the heat of compression dissipated in all intercoolers and the final cooler utilized in the manner proposed. In other words, the process can also be carried out in embodiments with only one or some of the intercoolers and with or without a final cooler. Furthermore, in embodiments of the process, only a portion of the dissipated heat of compression can be utilized in the second separation unit.

[0031] The compression or waste heat generated in the first separation unit is of the same order of magnitude as the energy used for compression. It is typically generated at a low temperature level of below 100°C.

[0032] The chemisorptive or absorptive process using carbon dioxide scrubbing with an absorbent, which in turn is used in the second separation unit P40362-EP

[0033] October 2, 2024 - Fischer

[0034] The process carried out in step 5 requires primarily thermal energy for the regeneration of the carbon dioxide-laden adsorbent. Typical specific thermal energies range from 200 to 900 kWh per ton of carbon dioxide, but at a higher temperature level of over 100°C.

[0035] The problem in industry is that the waste heat from the adsorptive process is currently not utilized. One possibility would be to use a heat pump to raise the temperature level, but this would require additional equipment and thus incur investment costs. Therefore, such an application is not included in the proposed designs. The thermal energy for the chemisorptive process is currently typically supplied by burning fossil fuels, which, however, leads to additional secondary carbon dioxide emissions. Renewable energy at the required temperature level is not available on an industrial scale. Therefore, depending on the location and application, a new infrastructure (pipeline) for the supply of, for example, natural gas as a fossil fuel may also be necessary.

[0036] The proposed method and its embodiments address these issues and eliminate the aforementioned problems. The proposed method and its embodiments initially involve utilizing the compression heat generated in the compressor assembly of the first separation unit in the second separation unit. Embodiments of the method include a particularly advantageous increase in the temperature level at which the compression heat is supplied to the second separation unit.

[0037] Such configurations include the dissipation of at least a portion of the compression heat generated in and / or downstream of the compressor assembly of the first separation unit at a temperature level of more than 100°C or more than 130°C and up to 150°C or up to 200°C. Thus, in corresponding configurations, the compression carried out in the first separation unit in connection with the adsorptive process is adapted to provide waste heat at a higher temperature level for large-scale use in the second separation unit. This allows the waste heat generated to be used for steam generation to regenerate the absorption fluid in P40362-EP.

[0038] October 2, 2024 - Fischer

[0039] 6. The parallel chemisorptive or absorptive process can be used. The overall process becomes more efficient because the specific energy requirement can be reduced.

[0040] The adsorptive separation of carbon dioxide, as carried out in the first separation unit, generally has a high power consumption. Raising the temperature level of the cooling stages to dissipate the heat of compression increases the specific compressor power by at least 10%, i.e., from 150 to 600 kWh per ton of carbon dioxide to approximately 165 to 660 kWh per ton of carbon dioxide. A qualified professional would therefore not consider such a temperature increase, but would instead consider a heat pump (or other additional equipment) to raise the temperature level of the waste heat from the compressor assembly from 40 to 80°C to more than 100°C, preferably more than 130°C.

[0041] While the proposed direct increase in the temperature level of the waste heat generated during intermediate and / or final cooling does lead to an increase in compressor workload due to less efficient cooling, it offers a significant advantage over existing concepts. This allows for large-scale utilization of the waste heat generated during adsorptive separation, yielding between 165 and 660 kWh per ton of carbon dioxide. This corresponds to a coefficient of performance (COP) of 4 to 8, significantly exceeding the typical COP for a heat pump performing the same task. Furthermore, the proposed method requires no additional equipment.

[0042] In embodiments of the proposed process, the compression heat discharged into and / or downstream of the compressor assembly can be used to generate steam, which is then used for the aforementioned purposes, for example, to heat the bottom evaporator of the regeneration column or to heat the absorbent in the second separation unit. Thus, steam can be used as a heating medium or heat transfer medium, which is also used in conventional absorptive carbon dioxide separation systems.

[0043] By combining the adsorptive process and the absorptive process, the specific operating costs for carbon dioxide separation from P40362-EP can be reduced.

[0044] October 2, 2024 - Fischer

[0045] 7

[0046] Gas mixtures can be significantly reduced by 10 to 30% compared to the state of the art. A large portion of the carbon dioxide is separated, primarily using the adsorptive process, while a smaller portion is removed absorptively, utilizing the waste heat generated in this process. Furthermore, the integrated concept eliminates the need for fossil fuels for steam generation and the associated additional operating costs. The overall process remains based on electrical energy consumption.

[0047] In embodiments of the proposed method, a carbon dioxide stream containing water, or a portion thereof, generated in the second separation unit can be fed to the first separation unit, particularly on the suction side of a (further) compressor unit. This eliminates the need for separate drying of the water-containing carbon dioxide stream. The invention is not limited with respect to the combination of material streams, especially a water-containing carbon dioxide stream. Rather, product or carbon dioxide streams from one of the separation units can be fed into the other separation unit at any suitable point. A division to different positions is also possible.

[0048] In the embodiments proposed here, the flow rate of the first and second feed streams can be adjusted such that the compression heat discharged into and / or downstream of the compressor assembly of the first separation unit covers the heat requirement for heating the bottom evaporator of the regeneration column of the second separation unit, thus eliminating the need for additional heat sources. In embodiments of the present invention, the proposed measures can also provide steam for export to other consumers.

[0049] In certain embodiments proposed here, it may be possible to use two or more gas mixtures containing carbon dioxide from different sources, in particular those with different carbon dioxide contents. The first feed stream may be provided exclusively, predominantly, or partially using one of the gas mixtures, and the second feed stream exclusively, predominantly, or partially using another of the gas mixtures. For example, a gas mixture with a higher P40362-EP

[0050] October 2, 2024 - Fischer

[0051] 8

[0052] Carbon dioxide content is predominantly or exclusively fed to the first separation unit, and a gas mixture with a lower carbon dioxide content is predominantly or exclusively fed to the second separation unit. Adjustment of the carbon dioxide content by means of a suitable mixture is also possible. The gas mixtures could, for example, be exhaust gas from a gas turbine or flue gas from a fired furnace.

[0053] In summary, the above explanations may include the following: one or more gas mixtures may be flue gas and / or process gas, and / or be formed from these; adsorptive separation in the first separation unit may be carried out using an adsorption unit, and / or carbon dioxide separated in the first separation unit may be partially condensed, and / or absorptive separation in the second separation unit may be carried out using an amine-containing absorbent.

[0054] The proposed system for separating carbon dioxide from one or more gas mixtures containing carbon dioxide comprises a first separation unit configured for the adsorptive separation of carbon dioxide and a second separation unit configured for the absorptive separation of carbon dioxide, as well as a connecting line between the first and second separation units. The system is designed to provide a first feed stream containing carbon dioxide and a second feed stream containing carbon dioxide using the one or more gas mixtures, and to adsorb carbon dioxide from the first feed stream in the first separation unit and adsorb carbon dioxide from the second feed stream in the second separation unit. For this purpose, an adsorption unit and an absorption unit are provided.

[0055] The system is designed to perform compression in the first separation unit using a compressor assembly and to dissipate the compression heat in and / or downstream of the same. The system is further designed to perform the regeneration of an absorbent in the second separation unit using regeneration heat, and the system is designed to dissipate the compression heat dissipated in and / or downstream of the compressor assembly, or a portion thereof, via a [missing element] in the connecting line P40362-EP.

[0056] October 2, 2024 - Fischer

[0057] 9. To use a guided heat transfer medium to provide regeneration heat. The heat transfer medium, in particular steam, can be guided in the manner described above.

[0058] In particular, the proposed system is designed to guide the heat transfer medium between the first separation device and the second separation device without increasing the temperature by means of a heat engine, resulting in the advantages already explained above.

[0059] Further advantages and features described regarding the proposed process and its configurations also apply to the proposed plant, and vice versa. These are therefore described only once; reference is made to the respective explanations.

[0060] The terms used in this disclosure have the meanings generally accepted in the field. Adsorptive and absorptive methods for removing carbon dioxide are generally known and described in the literature. For example, see Chapters 6 and 7, "Absorption capture systems" and "Adsorption capture systems," in Steve A. Rackley, "Carbon Capture and Storage," 2nd edition, Butterworth-Heinemann, 2017. In the present disclosure, pressure swing adsorption is used as the adsorptive method, which may be followed by partial condensation of carbon dioxide. In particular, the method designated by the applicant as "HISORP® CC," which is described in various publications, can be used. An amine-containing solution, for example, can be used as the absorbent in an absorptive method, as is also extensively described.

[0061] Drawings

[0062] Aspects proposed within the scope of this disclosure are explained in more detail with reference to the accompanying drawing. This drawing shows

[0063] Figure 1 schematically shows an embodiment of a proposed method. P40362-EP

[0064] October 2, 2024 - Fischer

[0065] 10

[0066] Figure 1 illustrates a process according to a proposed embodiment in the form of a highly simplified flowchart, denoted by 100. It is understood that the process illustrated in Figure 1 may comprise 100 further process steps, or that additional apparatus may be installed in a corresponding plant, which have been omitted from the illustration for the sake of clarity.

[0067] In process 100, a gas mixture 1 containing carbon dioxide is provided, which in the illustrated example serves to form two partial streams as feed streams 2 and 3 for a first separation device 10 and a second separation device 20. Other embodiments may also include the provision of several gas mixtures instead of the gas mixture 1, which can be used separately or together to provide the feed streams 2 and 3.

[0068] The first separation unit 1 is configured for the adsorptive separation of carbon dioxide, as illustrated in Figure 1 with a highly simplified adsorption unit 12, for example, a pressure swing adsorption unit. For the separation of carbon dioxide using this adsorption unit 12, the first feed stream 2, or a subsequent stream formed using at least a portion of the first feed stream 2, must be compressed.

[0069] For compression, a compression unit 11 is provided, which in the illustrated example has three compressor stages 111, 112, and 113. In other embodiments, any other number of compressor stages 111, 112, and 113 can be provided. In the illustrated example, intermediate coolers 114 and 115 are connected downstream of compressor stages 111 and 112, respectively, and a final cooler is provided downstream of compressor stage 116. Any pretreatment steps, for example, for drying, temperature control, and separation of unwanted components, can be connected upstream of the compression unit 11.

[0070] It should be emphasized that the compression unit 11, whose compression heat is utilized according to the embodiments proposed here, can also be a compression unit at another point in the adsorptive process 12. In corresponding adsorptive processes 12, in order to achieve a carbon dioxide purity of 90% or over 95%, a second compression downstream of the pressure swing adsorption in the form of P40362-EP is required.

[0071] October 2, 2024 - Fischer

[0072] 11 of a so-called raw carbon dioxide compressor is required. If carbon dioxide is to be provided for pipeline transport, another, so-called carbon dioxide product compressor can be used.

[0073] Further steps or components may also be interposed between the compression unit 11 and the adsorption unit 12. Downstream of the adsorption unit 12, which may have any number of adsorber containers 121 and 122 instead of the two shown, a carbon dioxide stream generated here is subjected, for example, to cryogenic treatment and thereby partially condensed. Further process steps or equipment for membrane separation, recirculation, temperature control, compression, expansion, and the like, as well as circuits, valves, control and regulating devices, are omitted for the sake of clarity.

[0074] As previously mentioned, the operation of the first separation unit 10, designed for the adsorptive separation of carbon dioxide, differs from that of known separation units 10 of a similar type, in particular in that the intermediate and final coolers 114, 115 and 116, or a part thereof, are operated at a higher temperature level than usual. As also mentioned, this increases the required compressor power of the compression unit 11, but in this way heat 30 is available which can be used in the absorptively operating second separation unit 20.

[0075] The second separation device 20 comprises an absorption arrangement 21, which can be constructed and operated in a manner known per se. Further process steps or... can also be added to this absorption arrangement 21.

[0076] System components can be located upstream and downstream.

[0077] It comprises an absorption column 211, which is illustrated without internals for clarity only, and a regeneration column 212, for which the same applies. Further coolers, pumps, compressors, separators, valves, control and regulating devices, as well as feed lines for absorbent, are again omitted for clarity only. P40362-EP

[0078] October 2, 2024 - Fischer

[0079] 12

[0080] An unspecified absorbent stream is fed into the top of absorption column 211. Also at the top of the absorption column...

[0081] 211 A product stream depleted of carbon dioxide is taken from the absorption column. Carbon dioxide-laden absorbent is drawn off from the bottom of the absorption column, heated in a countercurrent heat exchanger 213, and fed into the regeneration column 212. The regeneration column 212 is operated with a top condenser 214 and a bottom evaporator 215.

[0082] In the head condenser 214, in particular, head gas from the regeneration column is supplied.

[0083] The liquid from regeneration column 212 condenses and is returned to the regeneration column 212. Uncondensed overhead gas is essentially formed by carbon dioxide, which can be removed from the second separation unit 20. In the bottom evaporator 215, the bottom liquid from regeneration column 212 is evaporated, with the majority of the carbon dioxide passing into the gas phase and rising in regeneration column 212. Unevaporated bottom liquid, i.e., regenerated absorbent, is cooled in the countercurrent heat exchanger 213 and fed back into the absorption column 211.

[0084] In the embodiment illustrated here, the heat 30 removed in the intermediate and final coolers 114, 115 and 116 of the compressor unit 11 of the first separation unit 10 is used, directly or via any heat transfer media, to heat the sump evaporator 215 of the regeneration column 212 of the absorption arrangement 21 of the second separation unit 20.

[0085] In total, product streams 4 and 5, each depleted of carbon dioxide, are extracted from the first separation unit 10 and the second separation unit 20. These can optionally be combined into a single stream 6 and used further. Additionally, carbon dioxide streams 7 and 8 are extracted from the first separation unit 10 and the second separation unit 20. These can also optionally be combined into a single stream 9 and used or stored. Particularly in the first separation unit 10, due to partial condensation taking place there, carbon dioxide streams in different states of matter can also be extracted. This is not illustrated separately for the sake of clarity. As mentioned previously, it is also P40362-EP

[0086] October 2, 2024 - Fischer

[0087] 13. It is possible at any time to direct one of the product streams 4 and 5 and / or one of the carbon dioxide streams 7 and 8 from one of the separation devices 10, 20 into the other, for example, to separate water from a water-containing carbon dioxide stream. This can be done at any suitable position.

Claims

P40362-EP October 2, 2024 - Fischer 14 Patent claims 1. Method (100) for separating carbon dioxide from one or more gas mixtures containing carbon dioxide (1), comprising: Providing a first carbon dioxide-containing feed stream (2) and a second carbon dioxide-containing feed stream (3) using one or more gas mixtures (1); Providing a first separation unit (10) configured for the adsorptive separation of carbon dioxide and a second separation unit (20) configured for the absorptive separation of carbon dioxide; adsorptive separation of carbon dioxide from the first feed stream (2) in the first separation unit (10);and absorptive separation of carbon dioxide from the second feed stream (3) in the second separation device (20), wherein the first separation device (10) and the second separation device (20) are operated in parallel to each other, wherein compression is carried out in the first separation device (10) using a compressor arrangement (11), and the heat of compression is dissipated in and / or downstream, and wherein regeneration of an absorbent is carried out in the second separation device (20) using regeneration heat, and wherein the heat of compression dissipated in and / or downstream of the compressor arrangement (11), or a part thereof, is used in the provision of the regeneration heat.

2. Method (100) according to claim 1, wherein the regeneration of the absorbent is carried out using a regeneration column (212), wherein the regeneration column (212) is operated using a bottom evaporator (214) and the regeneration heat is used to operate the bottom evaporator (214), and / or wherein an absorbent supplied to the regeneration column (212) is subjected to preheating and the regeneration heat is used for preheating the absorbent. P40362-EP October 2, 2024 - Fischer 15 3. Method (100) according to claim 1 or 2, wherein the compression heat discharged into and / or downstream of the compressor arrangement (11) is discharged at least in part at a temperature level of more than 100°C or more than 130°C and up to 150°C or up to 200°C.

4. Method (100) according to one of the preceding claims, wherein the compression heat discharged into and / or downstream of the compressor arrangement (11) is used to generate steam which is used to heat the sump evaporator (214) of the regeneration column (212).

5. Method (100) according to one of the preceding claims, wherein a water-containing carbon dioxide stream is withdrawn from the regeneration column (212) of the second separation device (20), wherein the water-containing carbon dioxide stream, or a part thereof, is supplied to the first separation device (10).

6. Method (100) according to one of the preceding claims, wherein a quantity flow of the first input stream (2) and the second input stream (3) is adjusted such that the compression heat discharged into and / or downstream of the compressor arrangement (11) covers a heat requirement for heating the sump evaporator (214) of the regeneration column (212).

7. Method (100) according to one of the preceding claims, wherein the one or more gas mixtures (1) is or are flue gas and / or process gas and / or are formed therefrom.

8. Method (100) according to one of the preceding claims, wherein two or more of the gas mixtures (1) are used, wherein the first input stream (2) is provided exclusively, predominantly or partially using one of the gas mixtures (1) and / or wherein the second input stream (3) is provided exclusively, predominantly or partially using another of the gas mixtures (1).

9. Method (100) according to one of the preceding claims, wherein the adsorptive separation in the first separation device (10) is carried out using a P40362-EP October 2, 2024 - Fischer 16 Adsorption unit (12) is carried out and / or carbon dioxide separated in the first separation unit (10) is partially condensed.

10. Method (100) according to one of the preceding claims, wherein the absorptive separation in the second separation device (20) is carried out using an amine-containing absorbent.

11. Plant for separating carbon dioxide from one or more gas mixtures containing carbon dioxide (1), comprising a first separation device (10) configured for the adsorptive separation of carbon dioxide and a second separation device (20) configured for the absorptive separation of carbon dioxide, and a connecting line from the first separation device (10) to the second separation device (20), wherein the plant is configured to carry out the following steps: Providing a first carbon dioxide-containing feed stream (2) and a second carbon dioxide-containing feed stream (3) using one or more gas mixtures (1);adsorptive separation of carbon dioxide from the first feed stream (2) in the first separation device (10) and absorptive separation of carbon dioxide from the second feed stream (3) in the second separation device (20), wherein the system is configured to carry out compression in the first separation device (10) using a compressor arrangement (11) and to dissipate compression heat in and / or downstream of the same, wherein the system is configured to regenerate an absorbent in the second separation device (20) using regeneration heat, and wherein the system is configured to use the compression heat dissipated in and / or downstream of the compressor arrangement (11), or a part thereof, via a heat transfer medium carried in the connecting line to provide the regeneration heat.

12. System according to claim 11, wherein the system is configured to guide the heat transfer medium between the first separation device (10) and the second separation device (20) without increasing the temperature by means of a heat engine. P40362-EP October 2, 2024 - Fischer 17 13. Plant according to claim 11 or 12, wherein the plant is configured to carry out a method (100) according to any one of claims 1 to 10.

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