BIOCATALYST-BASED CO2 STRIPPING TECHNIQUES AND RELATED SYSTEMS
20220118403 · 2022-04-21
Inventors
- Sylvie FRADETTE (San Donato Milanese (Milano), IT)
- Richard SURPRENANT (San Donato Milanese (Milano), IT)
- Eric MADORE (San Donato Milanese (Milano), IT)
- Hana BOUTELDJA (San Donato Milanese (Milano), IT)
- Sylvain LEFEBVRE (San Donato Milanese (Milano), IT)
- Ferrere J. CLERVEAUX (San Donato Milanese (Milano), IT)
Cpc classification
C10K1/12
CHEMISTRY; METALLURGY
B01D53/1493
PERFORMING OPERATIONS; TRANSPORTING
Y02P70/10
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
Y02P20/151
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
Y02A50/20
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
B01D53/18
PERFORMING OPERATIONS; TRANSPORTING
B01D2252/602
PERFORMING OPERATIONS; TRANSPORTING
Y02C20/40
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
B01D53/1425
PERFORMING OPERATIONS; TRANSPORTING
International classification
B01D53/18
PERFORMING OPERATIONS; TRANSPORTING
Abstract
A method for stripping CO.sub.2 from a biocatalyst-containing CO.sub.2-rich absorption solution to produce a biocatalyst-containing CO.sub.2-lean absorption solution and a CO.sub.2-rich gas is provided. The method includes generating a stripping gas from a portion of the biocatalyst-containing CO.sub.2-lean absorption solution in a stripping gas generation unit, and contacting the biocatalyst-containing CO.sub.2-rich absorption solution with the stripping gas in a gas-liquid contactor to produce the CO.sub.2-lean absorption solution and the CO.sub.2-rich gas.
Claims
1. A method for stripping CO.sub.2 from a biocatalyst-containing CO.sub.2-rich absorption solution to produce a biocatalyst-containing CO.sub.2-lean absorption solution and a CO.sub.2-rich gas, the method comprising: generating a stripping gas from a portion of the biocatalyst-containing CO.sub.2-lean absorption solution in a stripping gas generation unit, and contacting the biocatalyst-containing CO.sub.2-rich absorption solution with the stripping gas in a gas-liquid contactor to produce the CO.sub.2-lean absorption solution and the CO.sub.2-rich gas.
2. The method of claim 1, wherein the stripping gas generation unit is a falling film evaporator.
3. The method of claim 1, wherein the gas-liquid contactor is a gas-liquid direct contactor.
4. The method of claim 3, wherein the gas-liquid contactor is a packed column, a tray column, a spray reactor or a rotating packed bed.
5. A method for stripping CO.sub.2 from a biocatalyst-containing CO.sub.2-rich absorption solution to produce a biocatalyst-containing CO.sub.2-lean absorption solution and a CO.sub.2-rich gas, the method comprising: generating a stripping gas from the biocatalyst-containing CO.sub.2-rich absorption solution, and contacting the biocatalyst-containing CO.sub.2-rich absorption solution with the stripping gas in a gas-liquid contactor to produce the CO.sub.2-lean absorption solution and the CO.sub.2-rich gas.
6. The method of claim 5, wherein generating the stripping gas comprises heating the biocatalyst-containing CO.sub.2-rich absorption solution in the gas-liquid contactor, thereby simultaneously generating the stripping gas and stripping CO.sub.2 from the biocatalyst-containing CO.sub.2-rich absorption solution in the gas-liquid contactor.
7. The method of claim 5, wherein the gas-liquid contactor is a gas-liquid direct contactor, optionally a falling film evaporator.
8. The method of claim 1, wherein the biocatalyst-containing CO.sub.2-rich absorption solution is an aqueous solution, and the generated stripping gas includes steam.
9. A method for stripping CO.sub.2 from a biocatalyst-containing CO.sub.2-rich absorption solution to produce a biocatalyst-containing CO.sub.2-lean absorption solution and a CO.sub.2-rich gas, the method comprising: condensing at least a portion of the CO.sub.2-rich gas to produce a stripping liquid, generating a stripping gas from the stripping liquid, and contacting the biocatalyst-containing CO.sub.2-rich absorption solution with the stripping gas to produce the biocatalyst-containing CO.sub.2-lean absorption solution and the CO.sub.2-rich gas.
10. The method of claim 9, wherein generating the stripping gas from the stripping liquid is performed in a reboiler.
11. The method of claim 9, wherein contacting the biocatalyst-containing CO.sub.2-rich absorption solution with the stripping gas is performed in a gas-liquid direct contactor.
12. The method of claim 11, wherein the gas-liquid direct contactor is a packed column, a tray column, a spray reactor, or a rotating packed bed.
13. The method of claim 9, wherein the stripping liquid is a water-containing liquid being water or an aqueous solution and wherein the stripping liquid optionally contains water derived from the CO.sub.2-lean absorption solution.
14. The method of claim 13, wherein the aqueous solution is a salt solution comprising NaCl, KCl, K.sub.2CO.sub.3, Na.sub.2CO.sub.3 or a combination thereof.
15. The method of claim 9, wherein the stripping liquid is an organic liquid compound.
16. The method of claim 15, wherein the stripping liquid is immiscible with water and has a lower density than water.
17. The method of claim 15, wherein the stripping liquid is immiscible with water and has a higher density than water.
18. The method of claim 15, wherein the organic liquid compound is a hydrocarbon CxHy where x=5 or 6; or a halogenated hydrocarbon derivative including hexane, cyclohexane, cyclopentane, cis-1,2-dichloroethene, 2-methyl pentane, trichloroethylene, CHCl.sub.3, Perfluorohexane, Tetramethylsilane or a combination thereof.
19. A method for stripping CO.sub.2 from a biocatalyst-containing CO.sub.2-rich absorption solution to produce a biocatalyst-containing CO.sub.2-lean absorption solution and a CO.sub.2-rich gas, the method comprising: directly contacting the biocatalyst-containing CO.sub.2-rich absorption solution with a stripping gas to produce the biocatalyst-containing CO.sub.2-lean absorption solution and the CO.sub.2-rich gas, the stripping gas being a non-condensable gas.
20. The method of claim 19, wherein directly contacting the biocatalyst-containing CO.sub.2-rich absorption solution with the stripping gas is performed in a packed column, a tray column, a spray reactor or a rotating packed bed.
21. The method of claim 19, wherein the non-condensable gas is air or nitrogen.
22. The method of claim 1, wherein the stripping gas is fed to a plurality of spaced-apart locations, preferably distributed along a height of the gas-liquid contactor.
23. The method of claim 1, wherein the biocatalyst-containing CO.sub.2-rich absorption solution is withdrawn from different sections of the gas-liquid contactor to be heated and reinjected in the gas-liquid contactor via heating loops.
24. The method of claim 1, comprising minimizing or avoiding exposure of the biocatalyst-containing CO.sub.2-rich absorption solution and the biocatalyst-containing CO.sub.2-lean absorption solution to bubble-formation conditions at which new gas-liquid interfaces are created via bubble formation.
25. A method for stripping CO.sub.2 from a biocatalyst-containing CO.sub.2-rich absorption solution, the method comprising: contacting the biocatalyst-containing CO.sub.2-rich absorption solution with a stripping gas to create a driving force stripping CO.sub.2 from the biocatalyst-containing CO.sub.2-rich absorption solution, thereby producing a biocatalyst-containing CO.sub.2-lean absorption solution and a CO.sub.2-rich gas; and minimizing or avoiding exposure of the biocatalyst-containing CO.sub.2-rich absorption solution and the biocatalyst-containing CO.sub.2-lean absorption solution to bubble-formation conditions at which new gas-liquid interfaces are created via bubble formation.
26. The method of claim 25, further comprising generating the stripping gas from a portion of the biocatalyst-containing CO.sub.2-lean absorption solution in a stripping gas generation unit, the stripping gas generation unit being optionally a falling film evaporator.
27. The method of claim 25, further comprising generating a stripping gas from the biocatalyst-containing CO.sub.2-rich absorption solution in a gas-liquid direct contactor, the gas-liquid direct contactor being optionally a falling film evaporator.
28. The method of claim 25, further comprising condensing at least a portion of the CO.sub.2-rich gas to produce a stripping liquid, and generating the stripping gas from the stripping liquid in a stripping generation unit, the stripping generation unit being optionally a reboiler or an evaporator.
29. The method of claim 26, wherein contacting the biocatalyst-containing CO.sub.2-rich absorption solution with the stripping gas is performed in a packed column, a tray column, a spray reactor or a rotating packed bed.
30. A biocatalyst-based CO.sub.2 capture process comprising: contacting a CO.sub.2-containing gas with a biocatalyst-containing absorption solution to produce a biocatalyst-containing CO.sub.2-rich absorption solution, and using a CO.sub.2 stripping method as defined in claim 1 to desorb CO.sub.2 from the biocatalyst-containing CO.sub.2-rich absorption solution, thereby producing the CO.sub.2-lean absorption solution and the CO.sub.2-rich gas.
31. A process for desorbing CO.sub.2 from a biocatalyst-containing CO.sub.2-rich absorption solution in an evaporator, the process comprising: feeding the biocatalyst-containing CO.sub.2-rich absorption solution to the evaporator, and heating the biocatalyst-containing CO.sub.2-rich absorption solution to simultaneously generate a stripping gas and create a driving force to desorb CO.sub.2 from the biocatalyst-containing CO.sub.2-rich absorption solution.
32. The process of claim 31, wherein the evaporator is a falling-film evaporator.
33. A use of an evaporator to generate a stripping gas for stripping CO.sub.2 from a biocatalyst-containing CO.sub.2-rich absorption solution and produce a biocatalyst-containing CO.sub.2-lean absorption solution.
34. The use of claim 33, wherein the evaporator is used to generate the stripping gas from the biocatalyst-containing CO.sub.2-rich absorption solution.
35. The use of claim 33, wherein the evaporator is used to generate the stripping gas from the biocatalyst-containing CO.sub.2-lean absorption solution.
36. The use of claim 33, wherein the evaporator is a falling-film evaporator.
37. The method of claim 1, wherein the biocatalyst-containing CO.sub.2-rich absorption solution contains biocatalysts in a soluble form or in an immobilized form and are able to flow in the stripping gas generation unit and/or the gas-liquid contactor.
38. The method of claim 37, wherein the biocatalysts are fixed on particles or entrapped inside a porous matrix.
39. The method of claim 37, wherein the biocatalysts are carbonic anhydrase or analogs thereof.
40. The method of claim 5, wherein the biocatalyst-containing CO.sub.2-rich absorption solution is an aqueous solution, and the generated stripping gas includes steam.
41. The method of claim 5, wherein the stripping gas is fed to a plurality of spaced-apart locations, preferably distributed along a height of the gas-liquid contactor.
42. The method of claim 5, wherein the biocatalyst-containing CO.sub.2-rich absorption solution is withdrawn from different sections of the gas-liquid contactor to be heated and reinjected in the gas-liquid contactor via heating loops.
43. The method of claim 5, comprising minimizing or avoiding exposure of the biocatalyst-containing CO.sub.2-rich absorption solution and the biocatalyst-containing CO.sub.2-lean absorption solution to bubble-formation conditions at which new gas-liquid interfaces are created via bubble formation.
44. The method of claim 9, comprising minimizing or avoiding exposure of the biocatalyst-containing CO.sub.2-rich absorption solution and the biocatalyst-containing CO.sub.2-lean absorption solution to bubble-formation conditions at which new gas-liquid interfaces are created via bubble formation.
45. The method of claim 19, comprising minimizing or avoiding exposure of the biocatalyst-containing CO.sub.2-rich absorption solution and the biocatalyst-containing CO.sub.2-lean absorption solution to bubble-formation conditions at which new gas-liquid interfaces are created via bubble formation.
46. A biocatalyst-based CO.sub.2 capture process comprising: contacting a CO.sub.2-containing gas with a biocatalyst-containing absorption solution to produce a biocatalyst-containing CO.sub.2-rich absorption solution, and using a CO.sub.2 stripping method as defined in claim 5 to desorb CO.sub.2 from the biocatalyst-containing CO.sub.2-rich absorption solution, thereby producing the CO.sub.2-lean absorption solution and the CO.sub.2-rich gas.
47. A biocatalyst-based CO.sub.2 capture process comprising: contacting a CO.sub.2-containing gas with a biocatalyst-containing absorption solution to produce a biocatalyst-containing CO.sub.2-rich absorption solution, and using a CO.sub.2 stripping method as defined in claim 9 to desorb CO.sub.2 from the biocatalyst-containing CO.sub.2-rich absorption solution, thereby producing the CO.sub.2-lean absorption solution and the CO.sub.2-rich gas.
48. A biocatalyst-based CO.sub.2 capture process comprising: contacting a CO.sub.2-containing gas with a biocatalyst-containing absorption solution to produce a biocatalyst-containing CO.sub.2-rich absorption solution, and using a CO.sub.2 stripping method as defined in claim 19 to desorb CO.sub.2 from the biocatalyst-containing CO.sub.2-rich absorption solution, thereby producing the CO.sub.2-lean absorption solution and the CO.sub.2-rich gas.
49. A biocatalyst-based CO.sub.2 capture process comprising: contacting a CO.sub.2-containing gas with a biocatalyst-containing absorption solution to produce a biocatalyst-containing CO.sub.2-rich absorption solution, and using a CO.sub.2 stripping method as defined in claim 25 to desorb CO.sub.2 from the biocatalyst-containing CO.sub.2-rich absorption solution, thereby producing the CO.sub.2-lean absorption solution and the CO.sub.2-rich gas.
50. The method of claim 5, wherein the biocatalyst-containing CO.sub.2-rich absorption solution contains biocatalysts in a soluble form or in an immobilized form and are able to flow in the stripping gas generation unit and/or the gas-liquid contactor.
51. The method of claim 9, wherein the biocatalyst-containing CO.sub.2-rich absorption solution contains biocatalysts in a soluble form or in an immobilized form and are able to flow in the stripping gas generation unit and/or the gas-liquid contactor.
52. The method of claim 19, wherein the biocatalyst-containing CO.sub.2-rich absorption solution contains biocatalysts in a soluble form or in an immobilized form and are able to flow in the stripping gas generation unit and/or the gas-liquid contactor.
53. The method of claim 25, wherein the biocatalyst-containing CO.sub.2-rich absorption solution contains biocatalysts in a soluble form or in an immobilized form and are able to flow in the stripping gas generation unit and/or the gas-liquid contactor.
54. The method of claim 50, wherein the biocatalysts are fixed on particles or entrapped inside a porous matrix.
55. The method of claim 51, wherein the biocatalysts are fixed on particles or entrapped inside a porous matrix.
56. The method of claim 52, wherein the biocatalysts are fixed on particles or entrapped inside a porous matrix.
57. The method of claim 53, wherein the biocatalysts are fixed on particles or entrapped inside a porous matrix.
58. The method of claim 50, wherein the biocatalysts are carbonic anhydrase or analogs thereof.
59. The method of claim 51, wherein the biocatalysts are carbonic anhydrase or analogs thereof.
60. The method of claim 52, wherein the biocatalysts are carbonic anhydrase or analogs thereof.
61. The method of claim 53, wherein the biocatalysts are carbonic anhydrase or analogs thereof.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0031] Implementations of the biocatalyst-based CO.sub.2 capture process and related units are represented in and will be further understood in connection with the following figures.
[0032]
[0033]
[0034]
[0035]
[0036]
[0037]
[0038]
[0039]
[0040]
[0041]
[0042]
[0043]
[0044]
[0045]
[0046]
[0047]
[0048]
[0049] While the invention will be described in conjunction with example embodiments, it will be understood that it is not intended to limit the scope of the invention to these embodiments. On the contrary, it is intended to cover all alternatives, modifications and equivalents as may be included as defined by the appended claims.
DETAILED DESCRIPTION
[0050] Present techniques relate to the field of biocatalyst-based CO.sub.2 capture. The CO.sub.2-containing gas may be a post-combustion flue gas, a process gas, a biogas or a natural gas from different sources. Specifically, the invention is related to a carbonic anhydrase-based CO.sub.2 capture processes where the biocatalyst carbonic anhydrase is present in the absorption solution and flows with this solution through gas-liquid contactor. More specifically, this invention discloses methods/processes enabling increasing the biocatalyst process lifetime and decreasing the biocatalyst cost in the technology.
[0051] Recent investigations clearly demonstrated that, in addition to pH and temperature, a third parameter has a very important impact on the biocatalyst process stability: the generation rate of new gas-liquid interfaces. This phenomenon takes place in the absorption unit, the stripping unit and more importantly in the reboiler attached to the stripping unit which provides the stripping gas, usually steam, by boiling the absorption solution. It was clearly demonstrated that the rate of biocatalyst activity loss is directly related to the generated steam flow rate in the reboiler. In fact, it is the high boiling rate providing high gas-liquid interface generation rate that mainly causes the biocatalyst activity loss in the CO.sub.2 capture process.
[0052] In the following description, the term “about” means within an acceptable error range for the particular value as determined by one of ordinary skill in the art, which will depend in part on how the value is measured or determined, i.e. the limitations of the measurement system. It is commonly accepted that a 10% precision measure is acceptable and encompasses the term “about”.
[0053] In the above description, an embodiment is an example or implementation of the invention. The various appearances of “one embodiment,” “an embodiment”, “some embodiments” or “some implementations” do not necessarily all refer to the same embodiments. Although various features of the invention may be described in the context of a single embodiment, the features may also be provided separately or in any suitable combination. Conversely, although the invention may be described herein in the context of separate embodiments for clarity, the invention may also be implemented in a single embodiment.
[0054] It is worth mentioning that throughout the following description when the article “a” is used to introduce an element it does not have the meaning of “only one” it can rather mean of “one or more”. It is also to be understood that where the specification states that a component, feature, structure, or characteristic “may”, “might”, “can” or “could” be included, that particular component, feature, structure, or characteristic is not required to be included.
[0055] The presently described biocatalyst-based CO.sub.2 capture techniques includes controlling gas-liquid interface generation rate to impact the biocatalyst lifetime. More particularly, there are provided processes that minimize the generation of new gas-liquid interfaces and increase the biocatalyst lifetime in the process.
[0056] The present specification should be read in light of the following definitions:
[0057] Absorber or Absorption Unit
[0058] The absorber (also referred to herein as an absorption unit) is a gas-liquid contactor which can be a packed column, a tray column, or a rotating packed bed for example.
[0059] Stripper
[0060] The stripper (also referred to herein as a stripping unit or stripping column) is a gas-liquid contactor which can be a packed column, a tray column, a spray reactor, a rotating packed bed or a falling-film evaporator.
[0061] Absorption Solution
[0062] The absorption solution is an aqueous solution that may include at least one of the following compounds: K.sub.2CO.sub.3, KHCO.sub.3, Na.sub.2CO.sub.3, NaHCO.sub.3, tertiary amines, tertiary alkanolamines, tertiary amino acids. The absorption solution includes non-carbamate forming solutions.
[0063] CO.sub.2-Rich Gas
[0064] The CO.sub.2-rich gas is the gas phase leaving the stripper, prior to any subsequent treatments or process steps.
[0065] Biocatalyst
[0066] The biocatalysts that can be used in the present techniques are selected from the group consisting of enzymes, liposomes, micro-organisms, animal cells, plant cells and any combination thereof. The biocatalyst may be used in a soluble form or in the immobilized form i.e. fixed on a particle or entrapped inside a porous matrix. For both biocatalyst delivery forms, the biocatalyst is flowing with the absorption solution in the absorption and desorption units. It should be noted that the biocatalyst may preferably be an enzyme, such as carbonic anhydrase. The enzyme may be present in the absorption solution in an enzyme concentration of about 0-2 g/L, optionally about 0.05-1 g/L, further optionally about 0.1-0.3 g/L.
[0067] The enzyme carbonic anhydrase, which is of relatively low molecular weight, may be made to form part of a complex in order to increase its size. Different types of enzyme complexes may be formed. Among these are those using whole cells such as red blood cells. However, with red blood cells, the enzymes rapidly leak out and are lost. The carbonic anhydrase may be immobilized on a surface of the support material of the micro-particles, entrapped within the support material of the micro-particles, or a combination thereof. In another optional aspect, the carbonic anhydrase may also be provided as cross-linked enzyme aggregates (CLEAs) and the support material comprises a portion of the carbonic anhydrase and crosslinker. In still another optional aspect, the carbonic anhydrase is provided as cross-linked enzyme crystals (CLECs) and the support material comprises a portion of the carbonic anhydrase. The selected materials and methods must enable a stabilisation of the enzyme to make it more robust towards process conditions, enable the enzyme to remain immobilized i.e. fixed or entrapped to/in the support material when used in the process. In other words, materials and chemical bonds (if chemical method is used) must remain stable for a long period of time to provide an enzyme long term stability in the process.
[0068] The present invention provides processes to reduce the rate of biocatalyst activity loss in CO.sub.2 capture processes by proposing alternate process configurations where boiling is nearly absent and where the biocatalyst, in the absorption solution, is flowing through the absorption and desorption units. Three options are discussed here below.
[0069] In a first option, the steam is produced by sending the CO.sub.2-lean absorption solution to an evaporator instead of a reboiler. A reboiler is commonly used in CO.sub.2 capture processes to generate steam from the CO.sub.2-lean absorption solution. The steam is generated when the absorption solution is boiled i.e. when water vapor bubbles are formed in the solution. The generation of these steam bubbles lead to the generation new gas/liquid interfaces (steam bubbles from absorption solution) which were found to be detrimental to the biocatalyst. To minimize bubble formation, reboiler (12) (
[0070] In a second option, the stripping gas is not provided following evaporation or boiling of the absorption solution but from an external stripping gas loop where the stripping gas is condensable such as water. The absorption solution is not fed to a reboiler and thus is not exposed to any boiling conditions. The reboiler (12) (
[0071] In a third option, the reboiler (12) (
[0072] The operation conditions in the absorption unit may include an absorption temperature of about 10-60° C. and an absorption pressure of about 1-40 bars. The operation conditions in the stripping unit: may include a stripping temperature of about 50-80° C. and a stripping pressure of about 0.1-1 atm.
Option 1: Falling-Film Evaporator
[0073] In a first option, it is proposed to replace the reboiler by an evaporator. Evaporators are used in many industries such as food, chemical, pharmaceutical and dairy industries for concentrating solutions or slurries. In such applications, water has to be removed from these solutions or slurries to obtain a product of a desired quality. In these applications, the water vapor is rejected whereas the concentrated solution is the final product. For example, for the preparation of condensed milk over 45% of the water is evaporated from natural milk.
[0074] Different types of evaporators may be used, these are: forced circulation, natural circulation, wiped film, rising film tubular, falling film tubular, rising/falling film tubular, rising film plate evaporator, falling film plate evaporators and rising/falling film plate evaporators. Among these, falling-film evaporators (tubular or plate) are preferred because they provide a very short residence time within the equipment, good heat transfer coefficients and they can operate under vacuum conditions where water evaporation takes place at lower temperatures as compared to atmospheric pressure or higher pressure. It has gained wide acceptance for the concentration of heat sensitive products in food industry.
[0075] A schematic representation of a tubular falling-film evaporator is provided in
[0076] Based on the above advantages of the falling-film evaporator, the reboiler can be replaced by a falling-film evaporator. The corresponding process configuration is shown in
[0077] In an alternate configuration which is not illustrated, stream (22) could be fed to a separator wherein gas and liquid phases would be separated and collected separately. The liquid phase (concentrated solution) could be sent back in the reservoir at the bottom of the stripping unit (9) or mixed with stream (10) or (15) to be sent towards the absorption unit (2). The gas phase could then be sent back to the stripper (9). Contrarily to the food, dairy, pharmaceutical and chemical industries, the gas and liquid phases are both reinjected in a same process unit (the stripping unit (9)) whereas in food industry the concentrated solution and steam have different fates. Another difference with conventional use is that less than 20% (weight) of the solution needs to be evaporated.
Option 2: Stripping Gas Loop
[0078] In a second option, the reboiler is removed from the process and replaced by an external stripping gas loop (
[0079] It should also be noted that stream (27) may be heated, to have a temperature closer to the reboiler temperature, using a heat exchanger prior to its entrance in the reboiler (not illustrated in
[0080] In a first embodiment, the stripping vapor (28) might be injected at different heights (28a to 28g) along the stripping column as shown in
[0081] In another embodiment shown in
[0082] For both embodiments, the number of heating loops or injection ports depends on the column height, the energy needed to be injected and the process economics.
[0083] The two previous embodiments i.e. different injection locations and heating loops might also be applied to process configuration shown in
[0084] Regarding the nature of the stripping liquid, the key properties for an adequate stripping liquid are the following:
[0085] It has to be in a vapor or gas phase under the stripping operation conditions.
[0086] The vapor or gas phase has to be easily condensable at a temperature slightly lower than the stripping temperature.
[0087] Stripping liquids might be selected from water, aqueous solutions and liquid organic compound having adequate properties. The liquids or solutions may be separated in two classes: water miscible and water immiscible. Depending on the properties of the liquids or solutions, different process configurations are possible as described below.
[0088] Stripping Liquid: Water-Containing Liquid
[0089] In a first embodiment, the stripping liquid comprises water. It might be pure water or an aqueous solution such as a salt solution (NaCl, KCl, K.sub.2CO.sub.3, Na.sub.2CO.sub.3). Salt concentration may be adjusted to reach the desired boiling temperature. When an aqueous solution is used as the stripping liquid, its composition or the salt concentration is adjusted such that the boiling temperature of the solution is slightly higher than the operation temperature of the stripping unit.
[0090] The stripping vapor leaving the reboiler has a temperature equal to the stripping temperature or slightly higher to produce a superheated vapor. Preferably the temperature of the stripping vapor leaving the reboiler is at most 15° C. higher than the stripping temperature, more preferably at most 10° C. higher than stripping unit, and most preferably at most 5° C. higher than the stripping temperature. The process would be as described in
[0091] Referring to
[0092] A first process configuration is shown in
[0093] The purpose of the evaporation loop is removing the water added to the absorption solution in the stripping column and recovering the original absorption solution composition. The evaporation loop comprises a flash drum (48) operated at a pressure lower than the stripping unit pressure. Upon entering into the flash drum (48), a fraction of the water present in solution is vaporised. The liquid phase (58) leaving the flash drum (48) having a decreased water content is pumped (pump 59) and stream (60) is mixed with stream (15′). The steam generated in the flash drum (57) is sent to a compressor (49) and then to a cooling unit (50) where water is partially condensed. The gas/liquid mixture (51) is sent to a reservoir (52) where the gas and liquid phases are separated. The gas phase (53) is released to the atmosphere. Stream (53) comprises CO.sub.2 and water vapor. The liquid phase (54), mainly composed of water, is recovered, pumped (stream 56) and ultimately mixed with streams (45) and (40) in the stripping gas loop. Alternatively, stream (54) may be mixed with stream (15′).
[0094] In an alternate configuration, the flash drum can be replaced with a falling-film evaporator.
[0095] A second process configuration is shown in
[0096] A third process configuration is shown in
[0097] Stripping Liquid: Liquid Organic Compound
[0098] To be considered as a suitable stripping liquid, the liquid organic compound must fulfill the following criteria: [0099] Be in a vapor or gaseous state under the stripping unit operation conditions. [0100] Be in a liquid state at temperatures slightly below the operation temperature of the stripping column. [0101] Be non-miscible with aqueous solutions. This property will facilitate the separation of the organic compound from the aqueous solution and prevent the dissolution of the compound in the aqueous solution.
[0102] Based on the previous criteria, the organic compound might be: [0103] a hydrocarbon CxHy where x=5 or 6 [0104] a halogenated hydrocarbon derivative [0105] any other compound meeting the above criteria
[0106] Some candidate compounds are hexane, cyclohexane, cyclopentane, cis-1,2-dichloroethene, 2-methyl pentane, trichloroethylene, CHCl.sub.3, Perfluorohexane and Tetramethylsilane.
[0107] The implementation of this strategy is shown in
[0108] For both configurations, heat exchanger (8) (as shown in
Option 3: External Stripping Gas
[0109] In this third option, the reboiler (12) (
[0110] Referring to
Option 4: Falling-Film Evaporator as a Stripper (Gas-Liquid Contactor)
[0111] The gas-liquid contactor in the stripping unit may also be a falling-film evaporator having a plate or tubular configuration. The stripping unit may also consist in a few falling-film evaporators in series or in parallel. In this case the packed column, tray column or rotating packed bed would be removed. Corresponding process configurations are shown in
[0112] A first process configuration is provided in
[0113] The process configuration where the stripping unit consists in two falling-film evaporators operated in parallel is provided in
[0114] The process configuration where the stripping unit consists in two falling-film evaporators operated in series is provided in
[0115] An alternate configuration to that shown in
[0116] It should be understood that any one of the above-mentioned optional aspects of each processes, methods, systems and units may be combined with any other of the aspects thereof, unless two aspects clearly cannot be combined due to their mutually exclusivity.
EXPERIMENTAL RESULTS
[0117] The next examples aim at demonstrating the impact of boiling the absorption solution containing the carbonic anhydrase enzyme on the enzyme half-life in the process and how a process configuration change such as using air as the stripping gas impacts the enzyme half-life in the process. These examples describe experimental laboratory tests. The software Protreat® from Optimized Gas Treating Inc was used where process simulations were needed.
Example 1: Determination of 1T1 Carbonic Anhydrase Half-Life in a Lab Scale CO.SUB.2 .Capture Unit Comprising a Reboiler to Produce Steam from the CO.SUB.2 .Lean Absorption Solution Containing Enzyme 1T1 (Reference Process)
[0118] Tests were performed to determine the carbonic anhydrase half-life in a laboratory scale capture unit. The process configuration is as shown in
[0119] For the present process conditions, the steam generation rate was 4.5 kg/h and the half-life of enzyme 1T1 was evaluated as 12 hours.
Example 2: Impact of Operation Conditions at the Reboiler on the Steam Generation Rate and the Half-Life of Enzyme 1T1 Under Same Process Configuration as Example 1
[0120] To determine the impact of the steam generation rate on the half-life of enzyme 1T1, additional tests were conducted. The tests conditions were changed around the reboiler, other conditions were the same as described in Example 1. They are found in Table 1. For each condition, the steam generation flow rate is provided as the corresponding half-life of enzyme 1T1.
TABLE-US-00001 TABLE 1 Steam generation rate as a function of reboiler operation conditions Solution flow Pressure at Steam rate to the Hot water the outlet of Hot water generation 1T1 half- reboiler flow rate the reboiler temperature flow rate life (liter/min) (liters/min) (kPa) (° C.) (kg/h) (h) 0.8 5 30 80.0 4.5 12 0.8 5 30 75.0 1.6 62 2.0 3 30 80.0 3.6 33 0.8 5 30 77.5 4.1 17 2.0 5 30 77.5 3.3 32 2.0 5 30 75.0 1.2 96
[0121] As it can be observed in Table 1, the enzyme half-life is affected by the steam generation flow rate. The highest is the steam generation flow rate, the lowest is 1T1 half-life.
Example 3: 1T1 Half-Life in a Lab Scale CO.SUB.2 .Capture Unit where the Stripping Gas is Air
[0122] The unit is operated in a process configuration as shown in
[0123] Tests were performed to determine the carbonic anhydrase half-life in a laboratory scale capture unit where the stripping gas is air. The absorption solution is a 1.45 M K.sub.2CO.sub.3 solution with a CO.sub.2 loading of 0.7 mol C/mol K.sub.+. The carbonic anhydrase enzyme 1T1 is used at a concentration of 0.5 g/L. The schematic diagram of the unit is the same as shown in
[0124] Under these process conditions the 1T1 half-life is 13 days (312h). As compared to the base case presented in Example 1, this represents a 2 500% increase. As compared to the other cases presented in Example 2 (Table 1), this represents a 225 to 1 735% increase. This clearly demonstrates that minimizing the enzyme exposition to high gas/liquid interfaces is a key process parameter to increase the enzyme half-life in a CO.sub.2 capture process.
Example 4: Simulation of CO.SUB.2 .Stripping Unit Comprising a Stripping Gas Loop where the Stripping Liquid is Water and where the Generated Steam is Injected at Different Heights of the Stripping Packed Column—Impact of the Number of Injection Points (FIG. 3a)
[0125] A 1.45 M K.sub.2CO.sub.3 rich absorption solution comprising enzyme 1T1 at a concentration of 0.5 g/L is fed at flowrate of 6.46×10.sup.4 kg/h to a CO.sub.2 stripping unit consisting in a packed column. The packed column is 25 m height×1.11 m diameter. The stripping unit is operated at a temperature of 66° C. and a pressure of 30 kPa. The stripping gas is steam which is provided via a stripping gas loop. The temperature of the rich absorption solution fed to the stripping unit is 65° C. and the pressure is 150 kPa. Steam is provided at a pressure of 30 kPa and a temperature of 71° C.
[0126] Simulations were run, for a same CO.sub.2 desorption efficiency (47%), to determine the impact of the number of steam injection points on two parameters: steam condensation rate into the absorption solution, total steam flow rate required. Results of the simulations are reported in Table 2. Positions of the injection ports are specified as height in (m). A position of 0 m corresponds to the top of the stripping unit.
TABLE-US-00002 TABLE 2 Steam condensation Steam flow Nb injection points/position rate (kg/h) rate (kg/h) 1/(25 m) 740 2 100 2/(12.5, 25 m) 690 1 800 4 (3, 10, 17, 25 m) 600 1 690 9 (3, 5, 7, 9, 12, 15, 18, 22, 25 m) 400 1 476
[0127] The simulations results show that under the process conditions, increasing the number of steam injection points enable to reduce the steam condensation rate in the stripping unit. Another benefit is that the steam flow rate required is importantly reduced.
[0128] In a process where steam condensate in the absorption solution leaving the stripper, process configurations such as those shown in
Example 5: Simulation of CO.SUB.2 .Stripping Unit Comprising a Stripping Gas Loop where the Stripping Liquid is Water and where the Generated Steam is Injected at 9 Different Injection Points—Impact of the Temperature of the Rich Absorption Solution Fed to the Stripper Unit
[0129] Additional simulations were run to determine the feasibility of injecting steam without having the steam condensation issue to manage. One considered strategy is to heat the rich absorption solution, fed at the stripping unit, at a higher temperature. The case considered to illustrate the impact of a higher solution temperature is as described in Example 4 where steam is injected at 9 different injection ports. Simulation results are shown in Table 3.
TABLE-US-00003 TABLE 3 Temperature, rich Steam condensation Steam flow absorption solution (° C.) rate (kg/h) rate (kg/h) 65 400 1 476 68 253 1 450 69 162 1 400 70 67 1 350 71 −35 1 350
[0130] The simulation results shown in Table 3 clearly show that by increasing the temperature of the rich absorption solution entering the stripping unit, the steam condensation rate is decreased as the required steam flow rate. More specifically, simulation results indicate that process conditions might be adjusted to avoid steam condensation and hence the need of an evaporation loop to manage the solution composition.
Example 6: Steam Injection Via a Stripping Gas Loop at the Bottom of the Stripping Unit and Addition of Two Heating Loops (Process Configuration FIG. 3b)
[0131] Simulations were run to determine the impact of adding two heating loops to a stripping unit where steam is injected at the bottom of the packing. Process conditions are as described in Example 4. Regarding the two heating loops, where 15% of the absorption solution is pumped to, they comprise one pump and one heat exchanger. A first loop withdraw the absorption solution at 5 m and returns it back at 5.5 m. The temperature of the solution is increased from 60 to 70° C. The second heating loop withdraw the liquid at 10 m and returns it at 10.5 m. The temperature of the solution is heated from 63 to 70° C.
[0132] The simulation results indicate that under these process conditions, the steam condensation rate is decreased from 740 to 294 kg/h while the steam flow rate required is decreased from 2 100 to 1850. However additional heat duty of 0.85 GJ/h would be required. Additional simulations by adjusting the fraction of solvent flow going through the 2 loops to 25 and then 35%, show that steam condensation rate can be decreased down to 86 kg/h and steam flow rate down to 1700 kg/h while extra heat duty of 1.24 GJ/h would be required.
Example 7: Simulation Air Stripping
[0133] A flue gas containing 15% CO.sub.2 (v/v) is to be treated to capture 90% of its CO.sub.2. The flue gas has a temperature of 30° C. and a pressure of 111 kPa and is fed at a flow rate of 3 250 kg/h to a 15 tonnes per day CO.sub.2 capture unit. The absorption solution fed at the absorption unit is 1.45 M K.sub.2CO.sub.3 at a CO.sub.2 loading of 0.7 mol C/mol K. The absorption unit is operated at an L/G of 10 kg/kg. The design of the stripper unit where air is used as the stripping gas is performed using the Protreat® software (process configuration shown in
[0134] These results show that air stripping is technically feasible and is an interesting alternative to using a reboiler to generate the stripping gas. Moreover, the fact that the enzyme is not exposed to the reboiler in this process configuration will result in an increased enzyme half-life and thus in reduced operation costs.