The present invention relates to a system and method for rare gas recovery from a feed gas comprising hydrogen, nitrogen, methane, argon, and one or more rare gases.
Argon is a highly inert element used in high-temperature industrial processes, such as steel-making. Argon is also used in various types of metal fabrication processes such as arc welding as well as in the electronics industry, for example in silicon crystals production. Still other uses of argon include medical, scientific, preservation and lighting applications. While argon constitutes only a minor portion of ambient air (i.e. 0.93% by volume), it possesses a relatively high value compared to other major atmospheric constituents (oxygen and nitrogen) which may be recovered from air separation plants. Argon is typically recovered in a cryogenic air separation process as a byproduct of high purity oxygen production. In such processes, an argon rich vapor draw from the lower pressure column is directed to an argon rectification column where crude or product grade argon is recovered overhead.
The availability of low cost natural gas has led to the restart and construction of numerous ammonia production facilities throughout North America. One of the byproducts of ammonia production plants is a tail gas that may be comprised of methane, nitrogen, argon, and hydrogen. This tail gas is often utilized as fuel to fire various reactors within the ammonia production plant. However, if this argon-containing tail gas can be cost-effectively handled and purified, it could be used as an alternative source of argon production.
Ammonia is typically produced through steam methane reforming. In such a process air serves to auto-fire the reaction and to supply nitrogen for the synthesis reaction. In general, the steam methane reforming based process consists of primary steam reforming, secondary ‘auto-thermal’ steam reforming followed by a water-gas shift reaction and carbon dioxide removal process to produce a synthesis gas. The synthesis gas is subsequently methanated and dried to produce a raw nitrogen-hydrogen process gas which is then fed to an ammonia synthesis reaction. In many ammonia production plants, the raw nitrogen-hydrogen process gas is often subjected to a number of purification or additional process steps prior to the ammonia synthesis reaction. In one such purification process, the methane contained in the nitrogen-hydrogen process gas is cryogenically rejected prior to the nitrogen-hydrogen process gas compression. The rejected gas is a tail gas comprising the bulk of the contained methane as well as argon, nitrogen and some hydrogen. This tail gas is often used as a fuel to supply the endothermic heat of reaction to the primary steam reformer.
Argon is present in ammonia tail gas generally contains between about 3% to 6% argon. After hydrogen recovery from the tail gas, the relative concentration of argon increases to between about 12% to 20% argon which makes the argon recovery an economically viable process. In an effort to reduce costs and increase process efficiency, the conventional argon recovery processes from ammonia tail gas are typically integrated with the hydrogen recovery process The conventional argon recovery processes are relatively complex and involves multiple columns, vaporizers, compressors, and heat exchangers, as described for example in W. H Isalski, “Separation of Gases” (1989) pages 84-88. Other relatively complex argon recovery systems and process are disclosed in U.S. Pat. Nos. 3,442,613; 5,775,128; 6,620,399; 7,090,816; and 8,307,671.
In addition to the argon recovery, certain rare gases such as krypton and neon are also present in trace amounts in the tail gas from an ammonia production plant. What is needed is a cost-effective system and method for the recovery of the rare gases in addition to recovery of the argon and nitrogen contained within the tail gas of an ammonia production plant.
The present invention may be characterized as a method recovering rare gases from a pre-purified feed gas comprising hydrogen, nitrogen, methane, argon, and one or more rare gases, the method comprising the steps of: (a) directing the pre-purified and conditioned feed gas to a rectification column; (b) separating the pre-purified feed gas in a rectification column to produce a methane-rich liquid column bottoms containing the one or more rare gases and an hydrogen-nitrogen rich gas overhead; (c) conditioning the methane-rich liquid column bottoms containing rare gases to produce a stream having a vapor fraction greater than 90% and preferably at or near saturation; (d) directing the two phase methane rich stream and a rare gas lean stream to an auxiliary wash/rectifying column; (e) rectifying the two phase methane rich stream and the rare gas lean stream to produce a liquid bottoms rare gas concentrate and a methane-rich overhead; and (f) separating one or more rare gases from the liquid bottoms rare gas concentrate to produce a rare gas product stream.
The present invention may also be characterized as a system for separating a pre-purified feed gas comprising hydrogen, nitrogen, methane, argon, and one or more rare gases, the system comprising: (i) a refrigeration system configured to cool the pre-purified feed gas to a near saturated vapor state; (ii) a primary rectification column coupled to the refrigeration system and configured to receive the cooled feed gas and to separate the cooled feed gas to produce a methane-rich liquid column bottoms containing the one or more rare gases and hydrogen-nitrogen gas overhead; (iii) a conditioning system configured to partially vaporize the methane-rich liquid column bottoms containing the one or more rare gases to produce a two phase methane rich stream having between about 60% and about 90% vapor fraction at a temperature near saturation; (iv) an auxiliary wash/rectifying column coupled to the conditioning system and configured to receive the two phase methane rich stream and a rare gas lean stream, the auxiliary wash/rectifying column further configured to rectify the two phase methane rich stream and the rare gas lean stream to produce a liquid bottoms rare gas concentrate and a methane-rich overhead; and (v) a post-processing separation and purification system configured to recover the one or more rare gases from the liquid bottoms rare gas concentrate to produce a rare gas product stream.
Preferably, the feed gas is a tail gas from an ammonia plant and may generally contain greater than about 50% nitrogen by mole fraction. The feed gas may be a typical high pressure feed gas (between about 300 psia and 450+ psia) or a lower pressure feed gas. Conditioning of the feed gas in the refrigeration system may involve cooling the feed gas; warming the feed gas, compressing the feed gas; and/or expanding the feed gas in a plurality of discrete steps. Where the system and method are integrated or coupled to an ammonia plant, recycling of one or more of the streams back to the ammonia plant is contemplated. For example, hydrogen-nitrogen gas overhead may be recycled back to the ammonia plant, and preferably recycled back to either a cryogenic purifier in the ammonia plant or other locations within the synthesis gas stream of the ammonia plant. The methane-rich overhead is also preferably recycled back to the ammonia plant, and preferably employed as fuel gas.
While the specification concludes with claims specifically pointing out the subject matter that Applicant regards as the invention, it is believed that the invention will be better understood when taken in connection with the accompanying drawings in which;
The following detailed description provides one or more illustrative embodiments and associated methods for separating a feed gas comprising hydrogen, nitrogen, methane and argon into its major constituents. The disclosed system and methods are particularly suitable for gas recovery from a tail gas of an ammonia production plant comprising hydrogen, nitrogen, methane and inert gases, such as argon krypton and xenon, and involves four (4) key steps or subsystems, namely: (i) conditioning the feed gas in a refrigeration circuit or subsystem; (ii) separating the conditioned feed gas in a rectification column to produce a methane-rich liquid column bottoms; hydrogen-nitrogen gas overhead; and an argon-rich stream having trace amounts of hydrogen; (iii) stripping the trace amounts of hydrogen from the argon-rich stream to produce an argon depleted stream and a hydrogen-free, nitrogen and argon containing stream; and (iv) separating the argon from the hydrogen-free, nitrogen and argon containing stream in a distillation column system to produce at least an argon product stream and a nitrogen product stream.
Turning now to
A common part of the ammonia processing train employs a cryogenic purification process 30 known by those skilled in the art as the “Braun Purifier”. Since the secondary reformer 16 is fed with an air flow that is larger than that required by the stoichiometry of the ammonia synthesis reaction, excess nitrogen and inert gases must be removed or rejected prior to the ammonia synthesis step 36. In order to reject the excess nitrogen and inerts, a cryogenic purification process 30 is introduced after the methanation 26 reaction. The primary purpose of this cryogenic purification process 30 is to generate an overhead ammonia synthesis gas stream 31 with a stoichiometric ratio of hydrogen to nitrogen (H2:N2) of about 3:1. The cryogenic purification step of the Braun Purifier employs a single stage of refrigerated rectification. The overhead synthesis gas stream from the single stage of refrigerated rectification is free of unconverted methane and a substantial portion of the inerts, such as argon, are rejected into the fuel gas stream-bottoms liquid. In the Braun Purifier process, the feed gas 29 is first cooled and dehydrated. The feed gas 29 is then partially cooled and expanded to a lower pressure. The feed gas 29 may be further cooled to near saturation and then directed to the base of the single stage rectifier. The rectifier overhead is the resulting ammonia synthesis gas 31 that is processed for ammonia synthesis, whereas the rectifier bottoms are partially vaporized by passage through the rectifier condenser and warmed to ambient temperatures. This fuel/waste stream 35 is typically directed back to the reform and serves as fuel. See Bhakta, M., Grotz, B., Gosnell, J., Madhavan, S., “Techniques for Increase Capacity and Efficiency of Ammonia Plants”, Ammonia Technical Manual 1998, which provides additional details of this Braun Purifier process. The waste gas 33 from the Braun Purifier process step is predominantly a mixture of hydrogen (6.3 mole %), nitrogen (76.3 mole %), methane (15.1 mole %) and argon (2.3 mole %) The Braun Purifier waste gas represents a distinct departure from typical ammonia plant tail gas streams and requires new techniques and processes for recovering valuable constituents of the waste gas in a simple, cost effective and efficient manner.
In
The resulting products from the present recovery process and system 50 include: a liquid argon product stream 45; and a liquid nitrogen product stream 55; a hydrogen-nitrogen product gas stream 65 that may be recycled back to the ammonia plant synthesis section, and more particularly the ammonia synthesis gas stream upstream of the compressor or of the ammonia plant; a high methane content fuel gas 75 that may be recycled back to the ammonia production plant and preferably to the steam reforming section of the ammonia plant, and more specifically to the furnace by which the primary reformer is fired; and a substantially pure nitrogen gaseous overhead stream 85 that is also preferably recycled back to the ammonia plant.
Referring again to
It should be noted that in some instances that residual carbon oxides at levels less than about 10.0 ppm or other unwanted impurities may accompany the feed stream 52 being directed to the auxiliary rectification column 60. In such circumstances, adsorbents and associated purification systems (not shown) can be employed to further remove such impurities from the feed streams 35, 52. Such purification may be conducted while a portion of the feed stream 35 is in the liquid phase upstream of the vaporization step or when the feed stream 52 in the predominately gas phase downstream of the vaporization step.
In a preferred mode of operation, the feed stream 35 exiting the Braun Purifier overhead condenser of the ammonia plant is conditioned in a refrigeration circuit or system 100 by first warming and substantially vaporizing the feed stream 35 and then subsequently cooling the vaporized stream to bring the feed stream to a point near saturation and suitable for entry into the rectification column 60. Alternatively, the step of conditioning the feed stream may comprise any combination of warming, cooling, compressing or expanding the feed gas to a near saturated vapor state at a pressure of less than or equal to about 150 psia and a temperature near saturation. Preferably the pressure is less than or equal to about 50 psia, and more preferably to a range of between about 25 psia and 40 psia.
The conditioned and cooled feed gas 52 is then directed to an auxiliary rectification column 60 where it is rectified into an argon-depleted, hydrogen-nitrogen gas overhead 62 and a methane-rich liquid column bottoms 64. The argon-depleted, hydrogen-nitrogen gas overhead 62 contains primarily nitrogen and hydrogen in a molar ratio (N2:H2) of greater than about 3:1 and preferably greater than about 7:1. The exact composition of the argon-depleted, hydrogen-nitrogen gas overhead 62 will depend upon the level of argon recovery desired. In addition, an argon-rich side draw 66 is produced at an intermediate location 67 of the auxiliary rectification column 60, where it is extracted to form an argon-rich stream 68 having trace amounts of hydrogen.
A portion of the argon-depleted, hydrogen-nitrogen gas overhead 62 is preferably directed or recycled back to the ammonia plant as a hydrogen-nitrogen product gas stream 65 while another portion 69 is directed to the refrigeration system 100 where it is condensed and reintroduced as a reflux stream 63 to the auxiliary rectification column 60. Specifically, the portion of the hydrogen-nitrogen product stream 65 is directed back to the cryogenic purifier (e.g. Braun Purifier) in the ammonia plant or recycled back to the synthesis gas stream in the ammonia plant upstream of the compressor. Similarly, all or a portion of the methane-rich liquid column bottoms 64 is preferably subcooled and directed back or recycled back to fire the reformer as fuel gas stream 75.
A key element of the present recovery process and system 50 is the extraction of an argon rich side draw 66 at a location above the point where methane is present in any appreciable amount, for example a location of the auxiliary rectification column where the methane concentration is less than about 1.0 part per million (ppm) and more preferably less than about 0.1 ppm. The argon-rich liquid stream 68 with trace amounts of hydrogen is extracted from an intermediate location 67 of the auxiliary rectification column 60 and directed to a hydrogen rejection arrangement shown as a hydrogen stripping column 70 which serves to reject trace hydrogen from the descending liquid. The resulting hydrogen free stream 72 exiting the hydrogen rejection arrangement comprises argon and nitrogen containing stream that is free of both methane and hydrogen.
An optional feature of the hydrogen rejection arrangement, and more specifically the hydrogen stripping column 70, is that the resulting overhead vapor 73 or the rejected hydrogen and methane can be returned to the auxiliary rectification column 60. Alternatively, the rejected hydrogen and methane stream 73 can be vented or combined with virtually any other exiting process stream.
The argon-rich liquid stream 72 free of both methane and hydrogen is then directed to a further separation wherein at least an argon stream is generated by way of distillation. Alternatively the argon-rich stream 72 could be taken directly as a merchant product or transported to an offsite refinement process, where it could later be separated into a merchant argon product and optionally nitrogen products. However, in the presently disclosed embodiment shown in
In the double column distillation system 80, the hydrogen-free, nitrogen and argon containing stream 74 is first rectified in a higher pressure column 82 to produce a substantially nitrogen rich overhead 81 and an argon enriched bottoms fluid 83. The nitrogen rich overhead 81 is directed to the condenser reboiler 84 disposed in the lower pressure column 86 where it is condensed to a liquid nitrogen stream 87. This liquid nitrogen stream 87 from the condenser-reboiler 84 and argon enriched bottoms fluid 83 from the higher pressure column 82 are preferably subcooled in subcooler 91 against a cold stream which could be a low pressure nitrogen rich stream 85 or a separate refrigeration stream. Portions of the liquid nitrogen stream exiting condenser/reboiler 8488, 89 are used as reflux to the lower pressure column 86 and higher pressure column 82 while another portion of the liquid nitrogen stream may be diverted to storage (not shown) as a liquid nitrogen product 55. A portion of the nitrogen reflux stream 88 and the subcooled argon enriched bottoms fluid 83 are then directed to the lower pressure distillation column 86 where they are distilled into a substantially pure nitrogen overhead gas 85 and an argon rich liquid product 45. The argon rich liquid product 45 can optionally be further subcooled prior to flashing to storage (not shown).
The substantially pure nitrogen overhead 85 may be directed to a warming vent, an expansion circuit, or may be directed as a make-up gas to a refrigeration circuit 100 associated with the present system 50 to produce the refrigeration required for the disclosed process. Alternatively, the substantially pure nitrogen overhead 85 could be directly taken as cold nitrogen gaseous product, liquefied and taken as a cold liquid nitrogen product, or recycled back to the ammonia plant.
The resulting substantially pure nitrogen overhead 85 from the lower pressure column 86 can be directed to any number of locations/uses including: (i) to sub-cool the liquid nitrogen reflux streams and/or the argon enriched bottoms fluid; (ii) directly taken as cold nitrogen gaseous product; (iii) to a liquefaction system and taken as a cold liquid nitrogen product; (iii) as a make-up working fluid or component thereof in a refrigeration system; (iv) to the cryogenic purifier (e.g. Braun Purifier) of the ammonia plant. Preferably, the separated nitrogen stream can returned to the point of origin without a substantial portion of the original argon content. In a preferred mode of operation of the present nitrogen-argon separation system 50 depicted in
Advantageously, the above-described system and method is configured to capture the bulk of the contained argon contained in the feed gas and can recover liquid nitrogen or even gaseous nitrogen on an as needed basis. The base level of argon recovery of the presently illustrated and described systems and processes are in the range of about 85% to about 90%. Another advantage of the present system and method is that the initial rejection of methane by way of the auxiliary rectification column and rejection of hydrogen by the hydrogen stripping column is accomplished at or near the feed gas pressures (i.e. less than or equal to about 150 psia, and more preferably less than or equal to 50 psia, and still more preferably in the range of about 25 to 40 psia) which promotes the simplicity and cost effectiveness of argon recovery.
Turning now to
It should also be noted that the above refrigeration circuit or system 100 can also be operated as a liquefaction system. The key difference in the liquefaction system being that a portion of the working fluid may also be delivered as a liquid product 150. In particular, the use of the substantially pure nitrogen overhead 85 from the lower pressure column 86 of the double column distillation system 80 as a working fluid or make-up gas 152 is ideal. In such liquefaction embodiment, a liquid nitrogen product stream 150 could be extracted from the refrigeration system 100 rather than from the double column distillation system 80 and equivalent volume of make-up refrigerant 152, such as a portion of the nitrogen overhead 85 from the double column distillation system 80 would be added to the refrigeration system 100.
With respect to the above-described refrigeration system, it is also possible to incorporate multiple stages of compression and/or use multiple compressors arranged in parallel for purposes of accommodating multiple return pressures. In addition, the turbo-expanded refrigerant stream 121 can be configured interior with respect to temperature in the heat exchanger 106 as the turbine discharge or exhaust does not have to be near saturation. The shaft work of expansion can be directed to an additional process stream or may be used to “self-boost” the expansion stream. Alternatively, the shaft work of expansion may also be loaded to a generator or dissipated by a suitable break.
As for the composition of the working fluid in the refrigeration circuit or system, a stream of high purity nitrogen is a natural choice. However it may be advantageous to use a combination of nitrogen and argon or even pure argon. It should also be noted that the presence of air compression for secondary reforming in the ammonia plant can be exploited to supply a working fluid for refrigeration, with such working fluid being air or constituents of air. As noted, a liquid product stream can be generated directly from the working fluid of the refrigeration system. Refrigerant makeup for liquid production or turbo-expander leakage may be supplied by the nitrogen-argon separation system or it may be supplied externally from a storage tank or nearby air separation plant.
It is also possible to supplement refrigeration generation of the disclosed refrigeration system with the inclusion of a Rankine cycle, vapor compression type refrigeration circuit to provide supplemental warm level refrigeration. Alternatively, a second turbo-expander or warm turbine can be employed which may also use the subject working fluid or a different working fluid, such as carbon dioxide or ammonia to supply yet additional refrigeration (alone and in combination). Such gases can be easily derived from the base ammonia processing sequence in the ammonia plant.
With reference again to
Alternatively, in a new ammonia production facility, it is possible to design the cryogenic purifier to independently warm the streams returning from the above-described separation process using a customized or specially designed heat exchanger. Furthermore, the ratio of turbo-expansion of the expander used in the Braun Purifier process can be reduced or perhaps even eliminated by way of the refrigeration generated from the present system and method. In essence, the refrigeration systems of the present nitrogen-argon separation process and system may be integrated with the refrigeration system in the Braun Purifier process.
Turning now to
The refrigeration circuit or system of the embodiment of
In the embodiment of
A stream of liquid nitrogen 224 is generated from the heat exchanger 210 by cooling and condensing a fraction of the higher pressure nitrogen recycle stream. The liquid nitrogen stream is extracted from the cold end of the heat exchanger 210 and, as described in more detail below, serves to refrigerate condenser 225 associated with rectification column 260. Alternatively, a portion of the condensed liquid nitrogen stream from the heat exchanger 210 may be directed to storage or used as reflux 289 in the distillation column 280.
In some applications of the present system and methods, where liquid nitrogen production exceeds the local demand, the excess liquid nitrogen can be directed to condenser 225 (shown as the dotted line) and vaporized in condenser 225 with a resulting decrease in overall power consumption. Conversely, depending upon local gaseous nitrogen product demands, it is possible to configure the recycle compression circuit 250 to provide gaseous nitrogen product at a range of pressures in lieu of simple lower pressure venting 299, as shown and described.
Within the methane removal subsystem, methane is removed from the ascending vapor within rectification column 260 and extracted as a bottoms liquid 264. The extracted methane-rich bottoms liquid 264 comprising about 84% methane is preferably subcooled and the subcooled methane-rich liquid stream 275 directed back to the heat exchanger 210 where it is vaporized. Cold end refrigeration is thus effectively generated by way of the vaporization of the methane-rich (e.g., ˜84% methane) bottoms liquid of rectification column 260. The vaporized methane-rich stream 275 is then preferably recycled as a fuel gas back to the steam reforming section of the ammonia product plant (not shown).
The rectification column 260 is further staged to remove essentially all of the argon from the feed gas leaving a nitrogen-rich overhead gas 262. A portion of the nitrogen-rich overhead gas 269, which contains roughly 90% nitrogen, is directed to a condenser-reboiler 215 where it is condensed against a liquid nitrogen stream to produce a nitrogen rich reflux 263 that is re-introduced to rectification column 260. Another portion of the nitrogen-rich overhead gas from rectification column 260 is diverted as the hydrogen-nitrogen product gas 265 that warmed in the heat exchanger 210 and then may be recycled back to the ammonia synthesis section of the ammonia product plant. The vaporized portion of the nitrogen stream 233 from the condenser-reboiler 215 is combined with the waste nitrogen gas 285 and directed to the heat exchanger 210 where it is warmed to about ambient temperature.
Given sufficient staging in the rectification column 260, argon accumulates above the methane removal sections, which are generally the bottommost 15 to 20 stages in rectification column 260. A side liquid argon draw is extracted from a point above the methane removal section approximately midway up the rectification column 260 to form an argon-rich stream 267. The argon-rich stream 267 is preferably in liquid form and will typically contain trace amounts of hydrogen. The argon recovery can be enhanced even further by way of reboiling within rectification column, albeit at the expense of additional operating costs associated with the additional compression power required.
As seen in
The hydrogen-free, argon and nitrogen containing liquid is then directed to a distillation column 280 which serves to separate the nitrogen and argon. This distillation column 280 is preferably comprised of both a stripping section and a rectification section. The distillation column 280 produces a pure nitrogen overhead stream 285 a portion of which is preferably recycled to the heat exchanger 210 and then returned to the ammonia production plant. Distillation column 280 also includes a reboiler 284 configured to reboil the argon with a moderate pressure nitrogen gas stream to produce an ascending argon vapor and a liquefied nitrogen stream 287. A first portion of the liquefied nitrogen stream may be depressurized via valve 292 and then directed to combined phase separator-subcooler vessel 294 or outside use. A second portion of the liquefied nitrogen 289 is employed as reflux to distillation column 280. An additional fraction of the liquid nitrogen may be used supplement the refrigeration for the condenser 225. A liquid argon product stream 245 is extracted from a location near the bottom of distillation column 280. The liquid argon 245 may be further subcooled prior to being directed to suitable storage means or outside use. Also, while distillation column 280 typically operates at low pressure of between about 25 psia to about 30 psia, it is possible to operate distillation column 280 at an even lower pressure with an increase in the complexity and size of the recycle compression circuit.
In some embodiments, the methane, nitrogen, hydrogen and argon containing feed stream 235 may be pre-purified and/or compressed prior to entry to the heat exchanger. Similarly, the methane-rich bottoms liquid 264 may be adjusted in pressure prior to vaporization in the heat exchanger, by way of a pump, valve or static head. Also, depending upon the reforming train in the ammonia production plant, the hydrogen-nitrogen overhead from rectification column 260 could be recombined with the methane-rich bottoms liquid 264 and then recycled back to the ammonia production plant as a fuel gas to fire the primary steam reformer. This mixing of the hydrogen-nitrogen overhead stream with the methane-rich stream can be done prior to or after warming in the primary or main heat exchanger. Alternatively, the hydrogen-nitrogen overhead stream may be compressed and reintroduced into the synthesis gas train.
Another alternative embodiment of the present system and method of argon recovery from the tail gas of an ammonia production plant is contemplated wherein the hydrogen stripping or rejection column 270 may be simplified or even replaced with a phase separator or phase separation supplemented with a small amount of heat. It is also conceivable that the refrigeration circuit composition can be made to be independent from the distillation column 280 overhead composition. However, this will require an additional condenser associated with distillation column 280 as well as a reconfiguration of the liquid nitrogen process draw. Although not preferred, the operating pressure of distillation column 280 can be higher than the operating pressure of rectification column 260 if a liquid pump is used to direct the hydrogen free, argon and nitrogen containing liquid stream from side stripping column 270 to distillation column 280.
Turning now to
In order to extract rare gases like krypton and xenon from this Braun purifier process, the methane-rich bottoms liquid 264 from the primary rectification column 260 is expanded in expansion valve 301 and/or partially evaporated to yield a two phase stream 303 having between about 60% and 90% vapor fraction, and more preferably greater than 90% vapor fraction. It is then necessary to warm the two-phase stream 303 to near saturation. This is preferably accomplished by a partial traversal of the stream through the primary heat exchanger 210 or use of an auxiliary heat exchanger. The near saturated stream 304 is then sent to a rectification/wash column 306 where it is counter-currently contacted with a rare gas lean liquid 302. As seen in
The gas overhead 308 of the rectification/wash column 306 is then fully warmed to ambient temperatures, preferably via the primary heat exchanger 210 and the resulting vaporized methane-rich stream 275 is then preferably recycled as a fuel gas back to the steam reforming section of the ammonia product plant (not shown). The bottoms liquid 310 of the rectification/wash column 306 is concentrated with krypton and/or xenon and is extracted for further separation and purification.
While the embodiment shown in
Numerous options exist within this disclosed process to recover rare gases such as krypton and xenon. For example, the feed gas may be a tail gas from an ammonia plant or other methane containing process gas that contains greater than about 50% nitrogen by mole fraction. The feed gas may be a typical high pressure feed gas for Braun purifiers having a pressure of between about 300 psia to 500 psia or may be a lower pressure feed gas described with reference to
Further variations and options regarding the manner by which the two-phase methane-rich stream is brought to near saturation are contemplated. For example, the two-phase methane-rich stream may be warmed, compressed and subsequently cooled. It may also be expanded to low pressure. Alternatively, the residual liquid from the overhead condenser may be directed to an additional exchanger/vaporizer that is separate from the primary heat exchanger.
Subsequent processing of the rare gas concentrate will require the bulk removal of methane. This can be effectively accomplished by way of distillation given the disparity of boiling points between the rare gases and the methane. The rare gas concentrate stream may also be subjected to trace light removal (e.g. argon, nitrogen, hydrogen) by distillation and/or gettering and adsorption. Alternatively, the methane removal can be accomplished by way of reaction with oxygen with the resulting carbon oxides removed by adsorption or absorption. Although not preferred, the rare gas containing stream may be subjected to pyrolysis or reforming reactions for purposes of removing the methane. It should be noted that the rare gas concentrate may be taken as a liquid or gas. The concentrated rare gas stream may be stored and directed offsite for further refinement. The liquid/gas may also be blended with other rare gas sources for purposes of refinement. Although the presents system and method for rare gas recovery is described within the context of the Braun Purifier process, a similar stream/processing sequence is contemplated for any cryogenic tail gas process wherein a methane-rich stream (or other rare gas containing stream) is rejected.
While the present invention has been described with reference to one or more preferred embodiments and operating methods associated therewith, it should be understood that numerous additions, changes and omissions to the disclosed system and method can be made without departing from the spirit and scope of the present invention as set forth in the appended claims.
The present application claims the benefit of and priority to Patent Cooperation Treaty (PCT) application serial number PCT/US2017/012078 filed on Jan. 4, 2017 which claims the benefit of and priority to U.S. provisional patent application Ser. No. 62/277,041 filed Jan. 11, 2016.
Filing Document | Filing Date | Country | Kind |
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PCT/US2017/012078 | 1/4/2017 | WO | 00 |
Publishing Document | Publishing Date | Country | Kind |
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WO2017/123434 | 7/20/2017 | WO | A |
Number | Name | Date | Kind |
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2545778 | Haringhuizen | Mar 1951 | A |
3037359 | Knapp | Jun 1962 | A |
3442613 | Grotz, Jr. | May 1969 | A |
5775128 | Drnevich et al. | Jul 1998 | A |
6620399 | Jungerhans | Sep 2003 | B1 |
7090816 | Malhotra et al. | Aug 2006 | B2 |
8307671 | Jungerhans | Nov 2012 | B2 |
Number | Date | Country |
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102014008770 | Dec 2015 | DE |
966725 | May 1963 | GB |
Entry |
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Chemical Abstracts, No. 20, May 20, 1991, XP000187544, ISSN: 0009-2258, Abstract. |
W.H. Isalski, “Separation of Gases” (1989), pp. 84-88. |
Bhakta, M., Grotz, B., Gosnell, J., Madhavan, S., “Techniques for Increase Capacity and Efficiency of Ammonia Plants”, Ammonia Technical Manual 1998. |
Number | Date | Country | |
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20190003766 A1 | Jan 2019 | US |
Number | Date | Country | |
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62277041 | Jan 2016 | US |