Methods, systems, and apparatuses for utilizing a fischer-tropsch purge stream

Abstract

Systems, apparatuses and methods of utilizing a Fischer-Tropsch (FT) tail gas purge stream for recycling are disclosed. One or more methods include removing an FT tail gas purge stream from an FT tail gas produced by an FT reactor, treating the FT tail gas purge stream with steam in a water gas shift (WGS) reactor, having a WGS catalyst, to produce a shifted FT purge stream including carbon dioxide and hydrogen, and removing at least a portion of the carbon dioxide from the shifted FT purge stream, producing a carbon dioxide stream and a treated purge stream. Other embodiments are also disclosed.

Claims

1. A method of producing Fischer-Tropsch (FT) hydrocarbons via FT synthesis in an FT reactor having an FT synthesis catalyst, the method comprising: a. producing a syngas comprising hydrogen and carbon monoxide in a syngas preparation unit, comprising a stream methane reformer, using a carbonaceous feed; b. producing a liquid FT hydrocarbon stream, an FT tail gas stream and an FT water stream using the syngas gas as a feed in the FT reactor under FT operating conditions; c. removing an FT tail gas purge stream from the FT tail gas stream, leaving a remainder FT tail gas stream; d. treating the FT tail gas purge stream with steam in a water gas shift (WGS) reactor, having a WGS catalyst, to produce carbon dioxide and hydrogen, which form a shifted FT purge stream; and e. treating the shifted FT purge stream in a carbon dioxide removal unit, which removes carbon dioxide from the shifted FT purge stream, producing a carbon dioxide stream and a treated purge stream; and f. further comprising recycling the carbon dioxide stream as an input to the steam methane reformer.

2. The method of claim 1, wherein the WGS reactor comprises a low temperature water gas shift reactor.

3. The method of claim 1, wherein the WGS reactor comprises a medium temperature water gas shift reactor.

4. The method of claim 1, wherein the WGS reactor comprises a high temperature water gas shift reactor.

5. The method of claim 1, wherein two or more WGS reactors are used in series to treat the FT tail gas purge stream.

6. The method of claim 1, further comprising recycling the remainder FT tail gas stream as an input to the syngas preparation unit.

7. The method of claim 1, further comprising using the treated purge stream as fuel for the syngas preparation unit.

8. The method of claim 1, further comprising using the treated purge stream to sweeten natural gas.

9. The method of claim 1, further comprising using the treated purge stream to hydrotreat FT wax.

10. The method of claim 1, wherein the carbon dioxide removal unit is an amine unit.

11. The method of claim 1, wherein the carbon dioxide removal unit is carbon dioxide removal membrane.

12. A method of enhancing a Fischer-Tropsch (FT) purge stream, comprising: a. removing an FT tail gas purge stream from an FT tail gas produced by an FT reactor, leaving a remainder FT tail gas; b. treating the FT tail gas purge stream with steam in a water gas shift (WGS) reactor, having a WGS catalyst, to produce a shifted FT purge stream comprising carbon dioxide and hydrogen; c. removing at least a portion of the carbon dioxide from the shifted FT purge stream, thereby producing a carbon dioxide stream and a treated purge stream; and d. further comprising using the carbon dioxide stream as an input to a steam methane reformer acting as a syngas preparation unit.

13. The method of claim 12, wherein the water gas shift reactor comprises a low temperature water gas shift reactor.

14. The method of claim 12, wherein the water gas shift reactor comprises a medium temperature water gas shift reactor.

15. The method of claim 12, wherein the water gas shift reactor comprises a high temperature water gas shift reactor.

16. The method of claim 12, wherein two or more WGS reactors are used in series to treat the FT tail gas purge stream.

17. The method of claim 12, further comprising recycling the remainder FT tail gas as an input to a front end of the steam methane reformer.

18. The method of claim 12, further comprising using the treated purge stream as a fuel for the syngas preparation unit.

19. The method of claim 12, wherein the step of removing at least a portion of the carbon dioxide from the shifted FT purge stream is performed using a carbon dioxide removal membrane.

20. The method of claim 12, wherein the step of removing at least a portion of the carbon dioxide from the shifted FT purge stream is performed using an amine unit.

21. The method of claim 1, further comprising removing a second portion of the FT tail gas from the FT tail gas and adding the second portion of the FT tail gas to the shifted purge stream to form a combined stream, prior to treatment of the combined stream in the carbon dioxide removal unit.

22. The method of claim 12, further comprising removing a second portion of the FT tail gas from the FT tail gas and adding the second portion of the FT tail gas to the shifted purge stream to form a combined stream, prior to treatment of the combined stream in the carbon dioxide removal unit.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) For a more detailed description of the present invention, reference will now be made to the accompanying drawings, wherein:

(2) FIG. 1 depicts a simplified block diagram for a conventional Fischer Tropsch system, including a steam methane configuration.

(3) FIG. 2 depicts a more detailed view of the conventional SMR 130 of FIG. 1.

(4) FIG. 3 is a block diagram of a Fisher Tropsch system including utilizing an FT tail gas purge stream, in accordance with one or more embodiments of the present disclosure.

(5) FIG. 4 is a block diagram of a Fisher Tropsch system, wherein a carbon dioxide recycle stream is combined with a portion of an FT tail gas stream before being recycled to a front end of a syngas preparation unit, in accordance with one or more embodiments of the present disclosure.

(6) FIG. 5 is a flowchart for a method of utilizing an FT tail gas purge stream in accordance with one or more embodiments of the present disclosure.

NOTATION AND NOMENCLATURE

(7) As used herein, the term carbonaceous feedstock(s) means carbon-containing energy source(s), such as coal, natural gas, biomass, or carbonaceous waste streams (such as municipal solid waste) that can be converted into syngas. Some carbon energy sources must be pre-treated and/or gasified before use as a feedstock to a syngas preparation unit.

(8) As used herein, the abbreviation FT and/or F-T stand for Fischer-Tropsch (which may be written Fischer Tropsch).

(9) As used herein, the term FT tail gas means gas produced from an FT reactor. The FT tail gas may typically contain unreacted hydrogen and carbon monoxide, as well as carbon dioxide, some light hydrocarbons, and other light reaction byproducts.

(10) As used herein, the terms FT purge stream or FT tail gas purge stream have an identical meaning and mean excess FT tail gas removed from the primary FT tail gas stream. The FT purge stream typically has the same composition as the FT tail gas.

(11) As used herein, the term FT water means water produced by an FT reaction. The water will typically include dissolved oxygenated species, such as alcohols, and light hydrocarbons.

(12) As used herein, with respect to an FT plant, (1) the abbreviation GTL stands for gas-to-liquids; (2) the abbreviation CTL stands for coal-to-liquids; (3) the abbreviation BTL stands for biomass-to-liquids; and (4) the abbreviation WTL stands for waste-to-liquids. The first letter of each abbreviation stands for the respective carbonaceous feedstock used to create syngas that is used as a feed to an FT reactor to make liquid FT products. Thus, for example, GTL plants use natural gas to make the syngas used as a feed for the FT reactor.

(13) As used herein, the phrase a high-temperature Fischer-Tropsch (or HTFT) reactor means an FT reactor that is typically operated at temperatures of 330 C.-350 C., which typically employs an iron-based catalyst. This process has been put to use extensively by Sasol in their Coal-to-Liquid (CTL) plants. As used herein, the phrase a low-temperature Fischer-Tropsch (or LTFT) reactor means an FT reactor that is operated at lower temperatures, generally in a range between 170 C.-235 C., which typically employs a cobalt-based catalyst. As used herein, the phrase a low-temperature, high-pressure Fischer-Tropsch (or LTHP FT) reactor means an LTFT reactor that is operated at high pressures, such as between 300 psig and 600 psig.

(14) As used herein, the term liquid FT hydrocarbon products means liquid hydrocarbons produced by an FT reactor.

(15) As used herein, the terms reformed gas or synthesis gas or syngas means the effluent from a syngas preparation unit, such as (without limitation) a steam methane reformer, autothermal reformer, hybrid reformer, or partial oxidation reformer. Steam methane reformers do not use oxygen as part of the process; autothermal reformers do. Both use reformer catalysts. Hybrid reformers are a combination of steam methane reforming, as a first step, and an autothermal reforming with oxidation as a second step. Partial oxidation reformers are similar to autothermal reformers, but do not include the use of a reformer catalyst.

(16) As used herein, the term sweet natural gas means natural gas from which any excess sulfur or sulfur compounds such as, for example, H.sub.2S has been previously removed.

(17) As used herein, the term to superheat a fluid means to heat the fluid above its steam dew point (or saturation point). Specific preferred temperature ranges are noted, although other temperatures typically may be used.

(18) As used herein, the term tubular reactor refers to Fischer-Tropsch reactors containing one or more tubes containing FT catalyst, wherein the inner diameter or average width of the one or more tubes is typically greater than about 0.5.

(19) Use of the term tubular is not meant to be limiting to a specific cross sectional shape. For example, tubes may have a cross-sectional shape that is not circular. Accordingly, the tubes of a tubular reactor may, in one or more embodiments, have a circular, oval, rectangular, and/or other cross sectional shape(s).

(20) As used herein and as mentioned above, the abbreviation WGS stands for water gas shift and the abbreviation WGSR stands for water-gas-shift reaction.

DETAILED DESCRIPTION

(21) FIG. 3 depicts a simplified flow diagram for a Fischer Tropsch system in accordance with one or more embodiments of the present disclosure. Natural gas 302 and a first steam stream 304 enter a syngas preparation unit 330 as feeds. The natural gas 302 entering the syngas preparation unit 330 is preferably sweet natural gas, from which any excess sulfur or sulfur compounds such as H.sub.2S has been previously removed. In alternate embodiments, one or more other carbonaceous feedstocks may be used instead of or in addition to the natural gas 302. The syngas preparation unit 330 may comprise, for example, a steam methane reformer, an autothermal reformer, a hybrid reformer, or a partial oxidation reformer. As is known in the art, different types of syngas preparation units have different requirements and may be configured differently. Fox example, an autothermal syngas preparation unit would require an oxygen source, which is not depicted on FIG. 3. A flue gas 332 and a reformed gas (syngas) 334 exit the syngas preparation unit 330 via a first flowline and a second flowline respectively. (Flowlines in FIG. 3 are not separately numbered or depicted, except with the fluids they carry.) The reformed gas 334 passes to a syngas conditioning unit 360, whereby a process condensate stream 362 is collected and the hydrogen and carbon monoxide ratios are adjusted to pre-determined levels, if needed. Conditioned reformed syngas 365 is sent via a third flowline to an FT synthesis reactor 370 (or FT reactor) as a feed for use in creating FT hydrocarbons. The FT reactor 370 includes an FT catalyst and operates under FT conditions, which may vary somewhat depending on the type of FT reactor used. The FT reactor produces liquid FT hydrocarbons 380, with byproducts including an FT tail gas 371, and an FT water stream 374, and.

(22) In one or more embodiments, the FT reactor 370 comprises a fixed bed Fischer-Tropsch reactor. In one or more embodiments, the FT reactor 370 comprises a tubular Fischer-Tropsch reactor. In one or more embodiments, the FT reactor 370 comprises a fluidized bed Fischer-Tropsch reactor. In one or more embodiments, the FT reactor 370 comprises a slurry bed Fischer-Tropsch reactor, such as, but not limited to, a slurry bubble column Fischer-Tropsch reactor. In one or more embodiments, the FT reactor 370 comprises an FT reactor of any type.

(23) The disclosed FT reactor 370 of FIG. 1 and system and method used therewith may employ one or more of a variety of FT catalytic metals, such as Group 8-10 metals, including, but not limited to, iron, nickel, ruthenium, and/or cobalt. As discussed further herein below, in one or more embodiments of the present disclosure, cobalt-based catalysts may be employed. As known in the art, a cobalt-based FT catalyst may comprise cobalt impregnated into or onto any convenient catalyst carrier or support material, including, but not limited to, alumina (Al.sub.2O.sub.3), titania (TiO.sub.2), and silica (SiO.sub.2). Exotic carriers and promoters, such as platinum (Pt), palladium (Pd), rhenium (Re), and ruthenium (Ru) may also be employed. Other suitable catalyst carrier(s) and promoter(s) are known in the art and may be incorporated. The FT catalyst carrier may be in any convenient shape (e.g., spheres, pellets, trilobes, etc.).

(24) Referring again to FIG. 3, in one or more embodiments of the present disclosure, an FT purge stream 380 is removed from the FT tail gas 371. This may be performed in different ways. For example, a pressure regulator, a pressure-activated control value or a diverting line could be used. The FT purge stream 380 is sent to a water gas shift (WGS) reactor 382. The WGS reactor may be a low temperature WGS reactor, a medium temperature WGS reactor, or a high temperature WGS reactor. In one or more embodiments, two or more WGS reactors may be used in series, with or without intermediate cooling. The WGS reactor may use a WGS catalyst (not separately depicted in FIG. 3), such as a copper-based low temperature shift catalyst, such as Shiftmax 230 low temperature shift catalyst offered by Clariant. For a high temperature WGS reactor, an iron-based high temperature shift catalyst might be used. A second steam stream 381 is added to the WGS reactor 382. By exposing the FT purge stream 380 to the second steam stream 381 and the WGS catalyst in the WGS reactor 382, carbon monoxide and water of the FT purge stream 380 are converted into carbon dioxide and hydrogen, forming a shifted FT purge stream 386. The WGS reactor 382 would likely not consume all of the water from the added second steam stream 381. Unused water from the second steam stream 381 not consumed by the WGS reactor 382 may be condensed to form a second stream of process condensate 384.

(25) Continuing to refer to FIG. 3, the shifted FT purge stream 386 is sent to a carbon dioxide removal unit 390, which removes carbon dioxide from the shifted FT purge stream 386. The carbon dioxide removal unit may be any appropriate carbon dioxide removal unit, including but not limited to an amine unit or a carbon dioxide removal membrane.

(26) The removed carbon dioxide forms a carbon dioxide recycle stream 392, which may be sent as an additional input to the syngas preparation unit 330, as depicted in FIG. 3. Alternatively, the removed carbon dioxide may be sequestered or otherwise properly disposed of or may be recycled to the FT reactor. In embodiments wherein the syngas preparation unit comprises a steam methane reformer, additional CO.sub.2 in the feed to the steam methane reformer is believed to suppress the formation in the steam methane reformer of undesirable excess hydrogen by facilitating the reverse shift reaction:
CO.sub.2+H.sub.2<=>CO+H.sub.2O.(4)

(27) Accordingly, provision of additional CO.sub.2 to a steam methane reformer, for example through recycling of CO.sub.2, may be beneficial.

(28) The carbon dioxide removal unit 390 also produces a treated purge stream 394. The treated purge stream 394 may contain hydrogen and may be used for fuel for the steam methane reformer 330 or for other plant purposes, such as hydrotreating FT wax.

(29) In one or more embodiments of the present disclosure, as depicted in FIG. 3, at least a first portion 372 of the FT tail gas, from which the FT purge stream 380 has been removed, is sent via a fourth flowline to the syngas preparation unit 330, where the first portion of the FT tail gas is used as an additional feed. The FT water 374 may be treated for disposal or may be recycled. Such recycling of the FT tail gas and the FT water are described in the previously mentioned, U.S. Provisional Application No. 62/005,102.

(30) FIG. 4 depicts a block diagram of one or more embodiments of the present disclosure. A feed 400, including a natural gas feedstock 402 and a first steam stream 404, enters a syngas preparation unit 430. The syngas preparation unit 430 may comprise, for example, a steam methane reformer, an autothermal reformer, a hybrid reformer, or a partial oxidation reformer. The feed 400 is further described below. A flue gas 432 and a syngas 434 exit the syngas preparation unit 330 via a first flowline and a second flowline respectively. (Flowlines in FIG. 4 are not numbered separately from the fluids carried therein.) The reformed gas 434 passes to a syngas conditioning unit 460, whereby a stream of clean process condensate 462 is collected and the hydrogen and carbon monoxide ratios may be adjusted to pre-determined levels, if needed. Conditioned syngas 465 is sent from syngas conditioning unit 460 via a third flowline to an FT synthesis reactor 470 as a feed for use in creating FT hydrocarbons. The FT synthesis reactor 470 includes an FT catalyst (not separately depicted) and operates under FT operating conditions. Product and by-products of the FT reactor 470 include liquid FT hydrocarbons 480, an FT tail gas 471, and an FT water stream 474.

(31) Referring again to FIG. 4, an FT purge stream 480 is removed from the FT tail gas 471. This may be performed in different ways. For example, a pressure regulator, a pressure-activated control value or a diverting line could be used. The FT purge stream 480 is sent to a water gas shift (WGS) reactor 482. The WGS reactor 482 may be a low temperature WGS reactor, a medium temperature WGS reactor, or a high temperature WGS reactor. In one or more embodiments, two or more WGS reactors 482 may be used in series, with or without intermediate cooling. The WGS reactor 482 may use a WGS catalyst (not separately depicted in FIG. 4), such as a copper-based low temperature shift catalyst, such as Shiftmax 230 low temperature shift catalyst offered by Clariant. For a high temperature WGS reactor, an iron-based high temperature shift catalyst might be used. A second steam 481 is added to the WGS reactor 482. By exposing the FT purge stream 480 to the second steam 481 and the WGS catalyst in the WGS reactor 482, carbon monoxide and water in the FT purge stream 480 are converted into carbon dioxide and hydrogen, forming a shifted FT purge stream 486. The WGS reactor 482 would likely not consume all of the water from the added second steam 481. Unused water from the second steam 481 not consumed by the WGS reactor 482 may be condensed to form a third stream of process condensate 484.

(32) As in FIG. 3, a first portion 472 of the FT tail gas is recycled via a fourth flowline to become part of the feed 400 to the syngas preparation unit 430. By contrast with the embodiment(s) depicted in FIG. 3, in FIG. 4, a second portion 473 of the FT tail gas is sent via a sixth flowline to join with the shifted FT purge stream 486 to form a combined stream 495. The combined stream 495 is sent to a carbon dioxide removal unit 490, where carbon dioxide is removed from the combined stream 495, resulting in a CO.sub.2 recycle stream 492 and a treated purge stream 494, carried by seventh and eighth flowlines respectively. The carbon dioxide removal unit 490 may be any appropriate carbon dioxide removal unit, including but not limited to an amine unit or a carbon dioxide removal membrane. The CO.sub.2 recycle stream 492 is added to the first portion 472 of the FT tail gas upstream of the syngas preparation unit 430. (Alternatively, the removed carbon dioxide may be sequestered or otherwise disposed of or may be recycled to the FT reactor.) In FIG. 4, the sweet natural gas feedstock 402 is also combined with the CO.sub.2 recycle stream 492 and the first portion 472 of the FT tail gas upstream of the syngas preparation unit 430. In alternate embodiments, one or more other carbonaceous feedstocks may be used instead of or in addition to the sweet natural gas 402. As in FIG. 3, in FIG. 4, the carbon dioxide removal unit 490 also produces a treated purge stream 494. The treated purge stream 494 may contain hydrogen and may be used for fuel for the steam methane reformer 430 or for other plant purposes, such as for hydrotreating FT wax.

(33) The FT water stream 474 may be treated for disposal or may be recycled into the feed 400 for the syngas preparation unit 430. Such recycling of the FT tail gas and the FT water stream are described in the previously mentioned, U.S. Provisional Application No. 62/005,102. In FIG. 4, the FT water stream 474 is injected into the combination of the sweet natural gas feedstock 402, the CO.sub.2 recycle stream 492, and the first portion 472 of the FT tail gas upstream of the syngas preparation unit 430. Injecting the FT water stream 474 into the combination of the sweet natural gas 402, the CO.sub.2 recycle stream 492 and the first portion 472 of the FT tail gas upstream of the syngas preparation unit 430 may be advantageous, as the combination provides a greater volume of gas into which the FT water is injected than there would be if the FT water 474 were injected into the first portion 472 of the FT tail gas alone.

(34) FIG. 5 is flowchart for utilizing an FT tail gas purge stream in accordance with one or more embodiments of the present disclosure. Step 500 is to collect an FT tail gas purge stream from a stream of FT tail gas made in an FT process including a syngas preparation unit and an FT reactor. The FT tail gas purge stream is shifted 510 to create a shifted FT purge stream by sending the FT tail gas purge stream, with an addition of steam, through a water-gas shift (WGS) reactor having a WGS catalyst. In step 520, a carbon dioxide stream is removed from the shifted FT purge stream. The carbon dioxide removal may be performed, for example, by using an amine unit. At least a portion of the removed carbon dioxide stream is recycled in step 530, by being sent as an input (or as a part of a feed which is an input) to either the syngas preparation unit or the FT reactor or both. Preferably, all of the removed carbon dioxide is recycled, but that may depend on the specifics of the particular FT process being used. The treated purge stream may contain hydrogen and may be used for fuel for the steam methane reformer or for other plant purposes, such as hydrotreating FT wax.

(35) While some preferred embodiments of the invention have been shown and described, modifications thereof can be made by one skilled in the art without departing from the spirit and teachings of the invention. The embodiments described herein are exemplary only, and are not intended to be limiting. Many variations and modifications of the invention disclosed herein are possible and are within the scope of the invention. Where numerical ranges or limitations are expressly stated, such express ranges or limitations should be understood to include iterative ranges or limitations of like magnitude falling within the expressly stated ranges or limitations. The use of the term optionally with respect to any element of a claim is intended to mean that the subject element is required, or alternatively, is not required. Both alternatives are intended to be within the scope of the claim. Use of broader terms such as comprises, includes, having, etc. should be understood to provide support for narrower terms such as consisting of, consisting essentially of, comprised substantially of, and the like.

(36) Accordingly, the scope of protection is not limited by the description set out above but is only limited by the claims that follow, that scope including all equivalents of the subject matter of the claims. Each and every claim is incorporated into the specification as an embodiment of the present invention. Thus, the claims are a further description and are an addition to the preferred embodiments of the present invention. The inclusion or discussion of a reference is not an admission that it is prior art to the present invention, especially any reference that may have a publication date after the priority date of this application. The disclosures of all patents, patent applications, and publications cited herein are hereby incorporated by reference, to the extent that they provide background knowledge; or exemplary, procedural or other details supplementary to those set forth herein.