NOVEL PROCESS DESIGNS FOR INCREASED SELECTIVITY AND CAPACITY FOR HYDROGEN SULFIDE CAPTURE FROM ACID GASES

Abstract

A system and process for selectively separating H.sub.2S from a gas mixture which also comprises CO.sub.2 is disclosed. A water recycle stream is fed to the absorber in order to create a higher concentration absorbent above the recycle feed and having a greater H.sub.2S selectivity at lower acid gas loadings, and a more dilute absorbent below the recycle feed and having a greater H.sub.2S selectivity at higher acid gas loadings. Also disclosed is a system and process for selectively separating H.sub.2S by utilizing two different absorbents, one absorbent for the upper section of the absorber, tailored to have a greater H.sub.2S selectivity at lower acid gas loadings, and a second absorbent for the lower section of the absorber, tailored to have a greater H.sub.2S selectivity at higher acid gas loadings.

Claims

1. A process for selectively separating H.sub.2S from a sour gas stream which also comprises CO.sub.2, the process comprising the steps of: providing an absorber column and an absorbent regenerator column; feeding the sour gas stream near the bottom of the absorber; feeding an absorbent comprising one or more amines near the top of the absorber; and feeding a water stream to the absorber above the sour gas stream feed point and below the absorbent feed point.

2. The process of claim 1, wherein the one or more amines is selected from the group consisting of amines, alkanolamines, sterically hindered akanolamines, and mixtures thereof.

3. The process of claim 1, wherein the water stream comprises at least a portion of the condensed water from the regenerator overhead condenser.

4. The process of claim 3, wherein the water stream further comprises fresh water.

5. The process of claim 1, wherein the water stream is cooled prior to feeding to the absorber.

6. A process for selectively separating H.sub.2S from a sour gas stream which also comprises CO.sub.2, the process comprising the steps of: providing an absorber column having an upper section and a lower section; feeding the sour gas stream near the bottom of the absorber; feeding a first absorbent comprising one or more amines near the top of the upper section of the absorber; and feeding a second absorbent comprising one or more amines near the top of the lower section of the absorber.

7. The process of claim 6, wherein the one or more amines is selected from the group consisting of amines, alkanolamines, sterically hindered akanolamines, and mixtures thereof.

8. The process of claim 6, wherein the first absorbent and the second absorbent have the same composition.

9. The process of claim 6, wherein the first absorbent has a higher amine concentration than the second absorbent.

10. The process of claim 6, further comprising removing the first absorbent as a first rich absorbent near the bottom of the upper section of the absorber.

11. The process of claim 6, further comprising removing the second absorbent as a second rich absorbent near the bottom of the absorber.

12. The process of claims 10 and 11, wherein the first absorbent and the second absorbent are regenerated in a double wall regenerator.

13. The process of claim 6, wherein the first absorbent and the second absorbent comprise different amines.

14. The process of claim 13, wherein the first absorbent has a higher H.sub.2S selectivity than the second absorbent at a low acid gas loading.

15. The process of claim 13, wherein the second absorbent has a higher H.sub.2S selectivity than the first absorbent at a high acid gas loading.

16. A system for selectively absorbing H.sub.2S from a raw gas stream which also comprises CO.sub.2, the system comprising: absorbing means for contacting the raw gas stream with a lean amine stream to create a rich amine stream comprising at least a portion of the H.sub.2S from the raw gas stream; and regenerating means for stripping H.sub.2S from the rich amine stream to create the lean amine stream; wherein a water stream is fed to the absorbing means so as to increase the amount of H.sub.2S in the rich amine stream.

17. The system of claim 16, wherein the water stream is derived from the regenerating means.

18. The system of claim 16, wherein the water stream comprises fresh water.

19. The system of claim 17, wherein the water stream is cooled before being fed to the absorbing means.

20. A system for selectively absorbing H.sub.2S from a raw gas stream which also comprises CO.sub.2, the system comprising: first absorbing means for contacting the raw gas stream with a first lean amine stream to create a treated gas stream and a first rich amine stream comprising at least a first portion of the H.sub.2S from the raw gas stream; and second absorbing means for contacting the treated gas stream with a second lean amine stream to create a sweet gas stream and a second rich amine stream comprising at least a second portion of the H.sub.2S from the raw gas stream.

21. The system of claim 20, further comprising first regenerating means for stripping H.sub.2S from the first rich amine stream to create the first lean amine stream.

22. The system of claim 20, further comprising second regenerating means for stripping H.sub.2S from the second rich amine stream to create the second lean amine stream.

23. The system of claim 20, wherein the first and second absorbing means are in the same tower.

24. The system of claims 21 and 22, wherein the first and second regenerating means are in the same tower.

25. The system of claim 20, wherein the first lean amine stream and the second lean amine stream have the same amine composition.

26. The system of claim 20, wherein the first lean amine stream has a higher amine concentration than the second lean amine stream.

27. The system of claim 20, wherein the first lean amine stream and the second lean amine stream have different amine compositions.

28. The process of claim 20, wherein the first lean amine stream has a higher H.sub.2S selectivity than the second lean amine stream at a low acid gas loading.

29. The process of claim 20, wherein the second lean amine stream has a higher H.sub.2S selectivity than the first lean amine stream at a high acid gas loading.

Description

BRIEF DESCRIPTION OF THE FIGURES

[0010] FIG. 1 is a prior art schematic representation of a typical absorption-regeneration unit used for the selective removal of H.sub.2S.

[0011] FIG. 2 is a plot of the selectivity of H.sub.2S over CO.sub.2 as a function of acid gas loading with different concentrations of M3ETB aqueous solutions.

[0012] FIG. 3 is a schematic representation of an absorption-regeneration unit for the selective removal of H.sub.2S in accordance with a first embodiment of the present invention.

[0013] FIG. 4 is a plot of the selectivity of H.sub.2S over CO.sub.2 as a function of total acid gas loading at different absorber temperatures.

[0014] FIG. 5a is a plot of the CO.sub.2 uptake as a function of treatment time by 36 wt % EETB aqueous solutions at different absorber temperatures.

[0015] FIG. 5b is a plot of the H.sub.2S uptake as a function of treatment time by 36 wt % EETB aqueous solutions at different absorber temperatures.

[0016] FIG. 6 is a schematic representation of an absorption-regeneration unit for the selective removal of H.sub.2S in accordance with a second embodiment of the present invention.

DETAILED DESCRIPTION

[0017] A key finding in U.S. application Ser. No. 14/980,634, which is incorporated by reference in its entirety herein, is that reducing the amine concentration generally favors selectivity of H.sub.2S removal over a wide range of acid gas loadings. FIG. 1 of that patent, reproduced as FIG. 2 here, demonstrates this principle. Specifically, FIG. 2 demonstrates that the 30 wt % M3ETB solution yields an overall higher selectivity of H.sub.2S over CO.sub.2 for the commercially desirable acid gas loading range of 0.2 to 0.6, when compared to the 49.5 and 35.8 wt % M3ETB solutions. However, FIG. 2 also demonstrates that the 35.8 wt % M3ETB solution yields higher selectivity of H.sub.2S over CO.sub.2 for gas loadings below 0.2.

[0018] To implement the teachings of U.S. application Ser. No. 14/980,634, a first preferred embodiment of the present invention is illustrated in FIG. 3, a schematic representation of a novel absorption-regeneration unit process design. As with FIG. 1, FIG. 3 depicts contacting the sour gas mixture 20 countercurrently with an aqueous solution of the lean amine 22 in absorber tower 200, producing sweet gas mixture 21. The rich amine stream 24 is then regenerated by desorption of the absorbed gases in regenerator tower 210 with the regenerated lean amine 22, the desorbed gases 26, and an additional water recycle stream 28 leaving regenerator tower 210 as separate streams. Water recycle stream 28 consists essentially of condensed water, and may include up to 100% of the condensed water from the top of regenerator tower 210. Water recycle stream 28, after being cooled, is fed to absorber tower 200 between the lean amine 22 and the sour gas 20 feed points, at an optimal feed location. Fresh water 29 may also be added to water recycle stream 28 prior to feeding to absorber tower 200, although a person of ordinary skill in the art will appreciate that water balance must be managed depending on the amount of water lost and added to the system. The temperature of water recycle stream 28, which may be controlled in the range of about 5° C. up to the absorber operating temperature, controls the exothermicity of the acid gas-amine reaction, and improves the overall performance of the absorber as discussed below with respect to FIGS. 4 and 5.

[0019] Water recycle stream 28, with or without fresh water 29 addition, creates an amine concentration gradient in absorber tower 200 that improves the overall H.sub.2S removal selectivity by taking advantage of FIG. 2. First, the top section of absorber tower 200, above the water recycle 28 feed point, has a more concentrated amine solution and therefore gives higher selectivity for lower acid gas loadings (see 35.8 wt % M3ETB in FIG. 2). Meanwhile, the bottom section of absorber tower 200, below the water recycle 28 feed point, has a more diluted amine solution because of the additional water added, and therefore gives higher selectivity for higher acid gas loadings (see 30 wt % M3ETB in FIG. 2).

[0020] In addition to improved H.sub.2S selectivity, the novel process design of FIG. 3 has further benefits due to the reduced bulge temperature in the absorber. Specifically, the bulge temperature of the absorber (due to the exothermic character of the acid-base reactions) is reduced, thereby allowing the absorber to operate at higher acid gas loadings and maximize H.sub.2S removal. The reduced bulge temperature also has a significant positive impact on selectivity and loading as demonstrated by FIGS. 4 and 5a/b, discussed below. The reduced bulge temperature also lowers corrosion rates, which is a synergistic effect of operating with lower amine concentrations.

[0021] The data for FIGS. 4 and 5a/b was obtained from a process absorption unit (PAU) operating in a semi-batch system, comprising a water saturator, a stirred autoclave to which gas can be fed in up-flow mode, and a condenser. The autoclave is equipped with a pressure gauge and a type J thermocouple. A safety rupture disc is attached to the autoclave head. A high wattage ceramic fiber heater is used to supply heat to the autoclave. The gas flows are regulated by Brooks mass flow controllers and the temperature of the condenser is maintained by a chiller. The maximum PAU working pressure and temperature are 1000 psi (69 bar) and 350° C., respectively. A custom LabVIEW program is used to control the PAU operation and to acquire experimental data (temperature, pressure, stirrer speed, pH, gas flow rate, and off-gas concentration).

[0022] The data was collected by flowing the test acid gas mixture through the autoclave in which the amine solution was previously loaded. The acid gas mixture was fed to the bottom of the reactor by-passing the water saturator. The gases leaving the autoclave were transferred through the condenser (maintained at 10° C.) in order to remove any entrained liquids. A slip-stream of the off-gas leaving the condenser was piped to a micron-GC (Inficon) for analysis while the main gas flow passed through a scrubber. After reaching breakthrough, nitrogen was used to purge the system. The off-gas composition was measured using a custom-built micro GC. The micro GC is configured as a refinery Gas Analyzer and includes four columns (Mole Sieve, PLOT U, OV-1, PLOT Q) and four TCD detectors. A slip stream of the off-gas was injected into the micro GC approximately every 2 minutes. A small internal vacuum pump was used to transfer the sample into the micro GC. The nominal pump rate was ˜20 mL/min in order to achieve 10× the volume of line flushes between the sample tee and the micro GC. The actual gas injected into the micro GC was ˜1 μL. The PLOT U column was used to separate and identify H.sub.2S and CO.sub.2, and the micro TCD was used to quantify H.sub.2S and CO.sub.2.

[0023] Test conditions for FIGS. 4 and 5a/b were as follows: gas feed composition: 31.6 mol % CO.sub.2, 0.25 mol % H.sub.2S, balance N.sub.2; gas flow rate: 1004 sccm; temperature: varied, pressure: 56 bar; volume: 15 mL; stirring rate: 200 rpm; amine solution: 36 wt % EETB.

[0024] FIG. 4 is a plot of the selectivity of H.sub.2S over CO.sub.2 as a function of total acid gas loading at different absorber temperatures. The data demonstrates that the lower bulge temperatures provide an increased H.sub.2S selectivity, with the increased H.sub.2S selectivity occurring at lower acid gas loadings. This is consistent with the novel process design of FIG. 3, in which the water recycle 28 incrementally lowers the bulge temperature, which necessarily occurs at the bottom of absorber 200 (i.e., below the water recycle feed point) where the acid gas loading is the lowest. As such, the reduced bulge temperature and the reduced amine concentration act together to improve H.sub.2S selectivity in the lower portion of absorber 200.

[0025] FIGS. 5a and 5b demonstrate the effect of CO.sub.2 and H.sub.2S uptake, respectively, as a function of treatment time at different absorber temperatures. FIG. 5a demonstrates that lower temperatures specifically lowers the CO.sub.2 uptake over longer treatment times (i.e., in the top section of the absorber). FIG. 5b demonstrates that a lower temperature increases H.sub.2S uptake, especially at shorter treatment times (i.e. in the bottom section of the absorber). Both of these conclusions favor maximum H.sub.2S removal in absorber 200 of FIG. 3.

[0026] A second embodiment of the present invention is illustrated in FIG. 6, a schematic representation of a novel absorption-regeneration unit process design, utilizing an absorber 300 and a double wall regenerator 310. In this embodiment, two different amines or the same amine with two different concentrations are deployed in the upper and lower sections of a single amine scrubber. In this embodiment, the terminology Amine A and Amine B encompass a difference in amine type or a difference in amine concentration.

[0027] FIG. 6 depicts the gas-liquid counter-current contacting column (absorber 300) is divided into an upper section and a lower section. Sour gas 30 is introduced into the lower section of absorber 300 and up-flows through the entire column. Amine A [32] is introduced near the top of the upper section of absorber 300. Amine A down-flows through the column to the bottom of the upper section, contacting the pre-treated sour gas that arises from the lower section. The rich Amine A stream [35] is collected from the bottom of the upper section of absorber 300, and is regenerated in double wall stripper regenerator 310 in accordance with the scheme shown in FIG. 6. Amine B [33] is introduced near the top of the lower section of absorber 300. Amine B down-flows through the column to the bottom of the lower section, contacting the more concentrated sour gas. The Rich Amine B stream [34] is collected at the bottom of absorber 300 and is regenerated in double wall stripper regenerator 310 in accordance with the scheme shown in FIG. 6.

[0028] In this embodiment of the present invention, if Amine A and Amine B are different concentrations of the same amine, Amine A has a higher concentration than Amine B. As with the water recycle embodiment of the present invention, the more concentrated Amine A solution gives higher H.sub.2S selectivity for lower acid gas loadings (see 35.8 wt % M3ETB in FIG. 2), as is found in the upper section of absorber 300. The more diluted Amine B solution gives a higher H.sub.2S selectivity for higher acid gas loadings (see 30 wt % M3ETB in FIG. 2), as is found in the lower section of absorber 300.

[0029] Similarly, if Amine A and Amine B are two different amines with different performance characteristics, Amine A and Amine B can be selected and optimized based on relative H.sub.2S selectivities for lower and higher acid gas loadings, respectively, to maximize the removal of H.sub.2S. It is also envisioned that one or both of Amine A and Amine B are selected from aqueous amines, as described above, or non-aqueous amine systems, such as those described in U.S. patent application Ser. No. 14/339,768, which is incorporated by reference in its entirety herein.

Additional Embodiments

[0030] According to certain teachings of the present invention, a process is provided for selectively separating H.sub.2S from a sour gas stream which also comprises CO.sub.2. The process comprises the steps of providing an absorber column and an absorbent regenerator column, feeding the sour gas stream near the bottom of the absorber, feeding an absorbent comprising one or more amines near the top of the absorber, and feeding a water stream to the absorber above the sour gas stream feed point and below the absorbent feed point. The one or more amines is selected from amines, alkanolamines, sterically hindered akanolamines, or mixtures thereof. The water stream comprises at least a portion of the condensed water from the regenerator overhead condenser, which may be cooled prior to feeding to the absorber, and may also comprise fresh water.

[0031] Another embodiment of the present invention is a process for selectively separating H.sub.2S from a sour gas stream which also comprises CO.sub.2. The process comprises the steps of providing an absorber column having an upper section and a lower section, feeding the sour gas stream near the bottom of the absorber, feeding a first absorbent comprising one or more amines near the top of the upper section of the absorber, and feeding a second absorbent comprising one or more amines near the top of the lower section of the absorber. The first absorbent is removed as a first rich absorbent near the bottom of the upper section of the absorber. The second absorbent is removed as a second rich absorbent near the bottom of the absorber. Both the first and the second absorbent may be regenerated in a double wall regenerator. The one or more amines is selected from amines, alkanolamines, sterically hindered akanolamines, or mixtures thereof. In one aspect of this embodiment, the first absorbent and the second absorbent have the same composition, with the first absorbent having a higher amine concentration than the second absorbent. In another aspect of this embodiment, the first absorbent and the second absorbent comprise different amines, with the first absorbent having a higher H.sub.2S selectivity than the second absorbent at a low acid gas loading, and the second absorbent having a higher H.sub.2S selectivity than the first absorbent at a high acid gas loading.

[0032] Yet another embodiment of the present invention is a system for selectively absorbing H.sub.2S from a raw gas stream which also comprises CO.sub.2. The system comprises an absorbing means for contacting the raw gas stream with a lean amine stream to create a rich amine stream comprising at least a portion of the H.sub.2S from the raw gas stream, and a regenerating means for stripping H.sub.2S from the rich amine stream to create the lean amine stream. A water stream is fed to the absorbing means in order to increase the amount of H.sub.2S in the rich amine stream. The water stream is derived from the regenerating means, cooled before being fed to the absorbing means, and may further comprise additional fresh water.

[0033] Still another embodiment of the present invention is a system for selectively absorbing H.sub.2S from a raw gas stream which also comprises CO.sub.2. The system comprises a first absorbing means for contacting the raw gas stream with a first lean amine stream to create a treated gas stream and a first rich amine stream comprising at least a first portion of the H.sub.2S from the raw gas stream, and a second absorbing means for contacting the treated gas stream with a second lean amine stream to create a sweet gas stream and a second rich amine stream comprising at least a second portion of the H.sub.2S from the raw gas stream. A first regenerating means is provided for stripping H.sub.2S from the first rich amine stream to create the first lean amine stream. A second regenerating means is provided for stripping H.sub.2S from the second rich amine stream to create the second lean amine stream. The first and second absorbing means may be in the same tower. The first and second regenerating means may be in the same tower. In one aspect of this embodiment, the first lean amine stream and the second lean amine stream have the same composition, with the first lean amine stream having a higher amine concentration than the second lean amine stream. In another aspect of this embodiment, the first lean amine stream and the second lean amine stream comprise different amines, with the first lean amine stream having a higher H.sub.2S selectivity than the second lean amine stream at a low acid gas loading, and the second lean amine stream having a higher H.sub.2S selectivity than the first lean amine stream at a high acid gas loading.

[0034] Therefore, the present invention is well adapted to attain the ends and advantages mentioned as well as those that are inherent therein. The particular embodiments disclosed above are illustrative only, as the present invention may be modified and practiced in different but equivalent manners apparent to those skilled in the art having the benefit of the teachings therein. Furthermore, no limitations are intended to the details of construction or design herein shown, other than as described in the claims below. It is therefore evident that the particular illustrative embodiments disclosed above may be altered or modified and all such variations are considered within the scope and sprit of the present invention. Unless otherwise indicated, all numbers expressing quantities of ingredients, properties, reaction conditions, and so forth, used in the specification and claims are to be understood as approximations based on the desired properties sought to be obtained by the present invention, and the error of measurement, etc., and should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. Whenever a numerical range with a lower limit and an upper limit is disclosed, a number falling within the range is specifically disclosed. Moreover, the indefinite articles “a” or “an”, as use in the claims, are defined herein to mean one or more than one of the element that it introduces.