Patent Grant
10145609
The present invention is related to a method and apparatus for argon recovery in which argon is separated from air within a cryogenic air separation plant having an argon rejection or rectification column integrated with an adsorbent based argon refining and purification subsystem.
Argon is a highly inert element used in the some 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 growing processes. 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 the oxygen and nitrogen products that are also recovered from air separation plants. Argon is typically recovered in a Linde-type double column cryogenic air separation arrangement by extracting an argon rich vapor draw from the lower pressure column and directing the stream to a “superstaged” column or crude argon column to recover the argon. This argon distillation process typically includes an argon condensing unit situated above the argon column. The argon condensation load is typically imparted to at least a portion of the oxygen rich column bottoms or kettle stream prior to its introduction into the lower pressure distillation column. Argon can be produced directly by this “superstaged” distillation process to merchant liquid purities (e.g. about 1000 ppm to 1 ppm oxygen) in roughly 90 to 180 stages of separation or produced to intermediary purities (e.g. about 15% to 1% oxygen) in roughly 20 to 50 stages of separation. In some applications, the intermediate purity argon is then often subsequently refined by catalytic oxidation process employing hydrogen.
Modern air separation plants almost exclusively employ a superstaged distillation process for high purity argon recovery. Drawbacks of the typical three column argon producing air separation unit are the additional capital costs associated with argon recovery and the resulting column and coldbox heights, often in excess of 200 feet, are required to recover the high purity argon product. As a consequence, considerable capital expense is incurred to attain the high purity argon, including capital expense for the separate argon columns, multiple coldbox sections, liquid reflux/return pumps, etc.
An alternative method of producing high purity argon is to take a lower purity argon-containing stream from an air separation plant and purify the argon-containing stream using an adsorbent based purification system. There have been combinations of cryogenic air separation units and adsorbent based purification systems with the objective to remove oxygen, nitrogen and other contaminants from the argon-containing streams. See, for example U.S. Pat. Nos. 4,717,406; 5,685,172; 7,501,009; and 5,601,634; each of which are briefly described in the paragraphs that follow.
U.S. Pat. No. 4,717,406 discloses a liquid phase adsorption process wherein a feed stream from a cryogenic plant is directed to an adsorption based purification system. The adsorption based purification system serves to purify the liquefied gas prior to introducing it into a liquid storage tank. The targeted applications include the removal of water and carbon dioxide from electronics grade gases and the disclosed regeneration method of the adsorbent beds is a temperature swing process.
U.S. Pat. No. 5,685,172 details a process targeting the removal of trace oxygen and carbon monoxide from a variety of inert gases. The process also notes direct liquid processing and argon is cited as an example fluid. Metal oxides (CuO, MnO2) are detailed as adsorbents for oxygen. Regeneration is accomplished through the use of a reducing gas such as hydrogen at modest temperatures (e.g., 150° C. to 250° C.). The use of a reducing gas makes it difficult to integrate the adsorbent beds with the air separation units because the reducing gas is not made in the air separation unit and but must be externally supplied to regenerate the adsorbents. More importantly, during regeneration of the adsorbent beds, argon rich fluids will be lost from the process.
U.S. Pat. No. 7,501,009 discloses a cyclic adsorption process for the purification of argon. The process may be operated at cryogenic temperature while processing crude argon in the gaseous state. Zeolites are noted as possible adsorbents for the disclosed pressure swing adsorption (PSA) system. Regeneration gas is directed back to the argon-oxygen rectification column.
U.S. Pat. No. 5,601,634 combines a typical cryogenic air separation unit and pressure swing adsorption (PSA) system in which both nitrogen and oxygen contained in the argon feed from the distillation column of the cryogenic air separation unit are removed in adsorbent beds.
All of the above-identified prior art solutions focus only on improvements in the adsorbent based purification system of the combined cryogenic air separation unit and adsorption based purification arrangement and do not address improvements needed to the cryogenic air separation unit, including the use of specially designed argon rectification or rejection columns and various argon condensers, as contemplated in the present solution.
The use of divided wall columns within the prior art literature is clear, including some prior art references that teach the use of divided wall columns for argon rejection. See, for example, U.S. Pat. Nos. 8,480,860; 7,234,691; 6,250,106; 6,240,744; and 6,023,945. In addition, U.S. Pat. No. 5,114,445 teaches an improvement to the recovery of argon through the placement of an argon condenser within the lower pressure column as part of a means to thermally link the top of the crude argon column with the lower pressure column and which teaches that the most suitable location for the argon condenser is as an intermediate location within the lower pressure column, particularly, the section of the lower pressure column bounded by the feed point of the crude liquid oxygen bottoms from the higher pressure column and the vapor feed draw line for the crude argon column.
In addition, the general use of reflux condensers and or columns with pasteurization sections within the prior art literature for conventional air separation plants is also well known. However, such uses of reflux condensers and or columns with pasteurization sections have not contemplated integration with argon rejection and refining systems and, more particularly, with an adsorption based argon recovery and purification subsystem coupled to a cryogenic air separation unit.
Each of the above-identified prior art methods and systems, make incremental improvements to the operating efficiency of cryogenic air separation plants, and in some cases to the recovery of argon. However, each of the prior art references have notable short-comings or design challenges that drive increased capital costs, plant configuration, and/or argon recovery inefficiencies. As a result, there is a continuing need to develop further improvements to existing argon rejection and recovery processes or arrangements that are fully integrated with the distillation column and cycles of cryogenic air separation units. In particular, for some cryogenic air separation units there is a need to design an argon rejection and recovery process within the air separation cycles that is flexible in that it avoids or defers some of the up-front capital costs associated with argon recovery but allows argon recovery to be easily added to the cryogenic air separation unit at a later date when the argon production requirements change.
The present invention may be characterized as a method of producing a purified argon product stream in a cryogenic air separation unit, the method comprising the steps of: (a) separating argon from an oxygen-argon containing stream within a lower pressure column of the cryogenic air separation unit using an argon rectification column arrangement disposed within the lower pressure column, the separation of the argon from the oxygen-argon containing stream producing an impure argon stream having between about and 4% and 25% of oxygen impurities; (b) warming the impure argon stream against the purified argon product stream and pressurizing the impure argon stream; (c) purifying the warm, pressurized, impure argon stream by introducing the warm, pressurized impure argon stream into a pressure swing adsorption system to produce the purified argon product stream and a waste gas stream containing nitrogen impurities; and (d) recycling the waste gas stream from the pressure swing adsorption system to the argon rectification column arrangement. The argon rectification column arrangement includes an argon rejection column disposed within the lower pressure column and an argon condensing assembly disposed within the lower pressure column at a location above the argon rejection column. The argon rejection column is preferably configured to receive a portion of the ascending vapor from within the lower pressure column as the oxygen-argon containing stream, the waste gas stream, and an argon-rich reflux stream from the argon condensing assembly and produce one or more argon-rich vapor streams, the impure argon stream and a descending oxygen rich liquid stream which is released into the lower pressure column. The argon condensing assembly is configured to receive an argon-rich vapor stream from the argon rejection column and condense the argon-rich vapor stream against an oxygen enriched liquid stream to produce the argon-rich reflux stream.
The present invention may also be characterized as an air separation system for producing a purified argon product stream comprising: (i) an incoming air purification and compression train or subsystem configured for receiving a feed air stream and producing a compressed and pre-purified air stream; (ii) a main heat exchange subsystem coupled to the incoming air purification and compression train or subsystem and configured to cool the compressed and pre-purified feed air stream to temperatures suitable for rectification; (iii) a distillation column subsystem having a higher pressure column, a lower pressure column, and an argon rectification column arrangement configured to rectify the cooled, compressed and pre-purified feed air stream into oxygen-rich product stream, one or more nitrogen-rich streams, and an impure argon stream having between about and 4% and 25% of oxygen impurities; (iv) an auxiliary heat exchanger configured to warm the impure argon stream against a stream of a purified argon product stream; (v) an argon compressor or pump disposed downstream of the argon rectification column arrangement and configured for pressurizing the impure argon stream; (vi) a pressure swing adsorption system disposed downstream of the argon compressor or pump and configured for purifying the pressurized impure argon stream to produce the purified argon stream and a waste gas stream containing oxygen impurities and nitrogen impurities; and (vii) a recycling circuit connecting the pressure swing adsorption system with the argon rectification column arrangement and configured to direct the waste gas stream from the pressure swing adsorption system to the argon rectification column arrangement. The argon rectification column arrangement preferably includes or comprises an argon rejection column disposed within the lower pressure column configured to receive a portion of the ascending vapor from within the lower pressure column as an oxygen-argon containing stream, the waste stream, and an argon reflux stream and produce an argon-rich vapor stream, the impure argon stream, and a descending oxygen rich liquid stream which is released into the lower pressure column. The present argon rectification column arrangement further comprises an argon condensing assembly disposed within the lower pressure column at a location above the argon rejection column configured to receive the argon-rich vapor stream from the argon rejection column and condense the argon-rich vapor stream to produce the argon-rich reflux stream.
In various embodiments of the present invention, the argon condensing assembly is a reflux type argon condenser, and more preferably a falling film type microchannel tube condenser configured to remove the nitrogen impurities from the oxygen-argon containing stream and the waste gas stream, and release the nitrogen impurities into the lower pressure column or vent the nitrogen impurities. The present reflux type argon condenser is further designed so as to provide an equivalent to about 2 stages and 10 stages of separation.
In other embodiments of the present invention, the purified argon product stream is subcooled via indirect heat with a liquid nitrogen stream from the distillation column subsystem either in the auxiliary heat exchanger or in a separate subcooler to produce a purified liquid argon product stream. In addition, a balancing air stream from the incoming air purification and compression train or subsystem may be employed to as part of the warming streams used to warm the impure argon stream. If used, the balancing air stream is preferably recycled or returned to a location upstream of a lower column turbine system or to a location upstream of the higher pressure column of the distillation column subsystem after warming the impure argon stream.
While the preferred embodiments of the present method and system use a single reflux type argon condensing assembly, disposed within the lower pressure column, an alternate embodiment contemplates using a separate and auxiliary argon condenser disposed in operative association with the argon rejection column at a location above the argon rejection column. In such embodiment separate argon-rich vapor streams are extracted from the argon rejection column with the first argon-rich vapor stream directed to a conventional argon condenser where it is condensed against an oxygen enriched liquid stream to produce a portion of the argon-rich reflux stream. The second argon-rich overhead vapor stream is directed to the reflux type auxiliary argon condenser where the nitrogen impurities are stripped and vented and the resulting condensed argon-rich stream is returned to the argon rejection column.
While the specification concludes with claims specifically pointing out the subject matter that Applicant regards as his invention, it is believed that the invention will be better understood when taken in connection with the accompanying drawings in which:
For sake of clarity, the drawings use like reference numerals for like components shown in the different illustrated embodiments.
In reference to
In the incoming air purification and compression train or subsystem 20 shown in
Prior to such distillation however, the compressed, pre-purified feed air stream 28 is cooled to temperatures suitable for rectification within a primary or main heat exchanger 42 using refrigeration from the various oxygen, nitrogen and/or argon streams produced by the air separation plant together with supplemental refrigeration generated as a result of turbo-expansion of various streams in an upper column turbine (UCT) arrangement (shown in
In the illustrated embodiment of
In the illustrated embodiment of
The high pressure liquid air stream 34 in the embodiment of
It should be noted that higher pressure column 52, the lower pressure column 54, and the argon rectification/rejection column 56 represent distillation columns in which vapor and liquid are counter-currently contacted in order to affect a gas/liquid mass-transfer based separation of the respective feed streams. Such columns will preferably employ structured packing or trays.
As shown in
The oxygen-rich kettle liquid stream 53 composed of the bottoms liquid of the higher pressure column 52, the shelf draw 59, and remaining portion of the liquid nitrogen stream 64 are preferably cooled against warming nitrogen streams 57, 58 derived or taken from lower pressure column 54 within subcooler/heat exchangers 70A, 70B. The warmed nitrogen-rich vapor streams 67, 68 are then directed to the main heat exchanger 42 where it is further warmed to produce a nitrogen product stream 78 and/or nitrogen waste stream 77. Although not shown, a portion of the warmed nitrogen streams often finds use as a purge/sweep fluid for purposes of regenerating the warm end adsorbent systems of the pre-purification unit 26.
Within the lower pressure column 54, the oxygen-rich kettle liquid, liquid air stream, and nitrogen-rich shelf are further separated into a nitrogen-rich overhead stream 58 and into an oxygen-rich bottoms liquid 55, typically of greater than about 99.5% purity. This liquid oxygen stream 55 is extracted from the base of the lower pressure column 54 and then elevated in pressure by a combination of gravitational head and/or mechanical pump 75. A first portion of this pressurized liquid oxygen stream 80 is split into a liquid oxygen product fraction 82 which is directed through valve 84 into suitable storage vessel (not shown). This oxygen may alternatively be withdrawn before the pump. The remaining liquid oxygen fraction 86 is vaporized and warmed within main heat exchanger 42 and emerges as high pressure gaseous oxygen product stream 88 that may be used directly or directed to a distribution pipeline. In many embodiments, the bulk of the high pressure air stream 33 is liquefied for purposes of vaporizing the liquid oxygen 86. The resulting liquid air stream 34 is distributed into the distillation column system 50, as generally described above. The high pressure air 34 and pumped oxygen 86 can be above their critical pressure. In such cases the liquefaction of the high pressure air 34 and vaporization of the liquid oxygen 86 are not discrete phase changes.
Divided Wall Argon Rectification Column
With reference to
The additional capital cost typically associated with a separate argon rejection column is greatly reduced if, as contemplated in the present embodiments, the argon rectification column 56 is combined with and disposed within the lower pressure column 54 structure as a divided wall column arrangement 90. It is important to note that when making an argon product in many conventional cryogenic air separation units, a defined section of the lower pressure column is typically under-utilized or unloaded because some of the vapor is “bypassed” to the external crude argon or ‘superstaged’ column so that the flow area of this underutilized or unloaded section of the lower pressure column required for distillation can be reduced and somewhat less than the flow area for the remainder of the lower pressure column sections. As a result, an argon rectification column can be co-located in this under-utilized or unloaded section of the lower pressure column structure by designing a divided wall column having a main distillation section and a partitioned argon rejection section at this location of the lower pressure column structure. In such arrangement, a portion of the vapor from the adjacent section of the lower pressure column immediately below the divided wall column flows to the partitioned argon rejection section 92. The remaining portion of the vapor from the adjacent section of the lower pressure column immediately below the divided wall column arrangement 90 flows upward through to the main distillation section 91.
The divided wall argon rectification column disposed within partitioned argon rejection section 92 of the lower pressure column structure operates at a pressure comparable to the pressure within the lower pressure column. The partitioned argon rejection section 92 receives an upward flowing argon and oxygen containing vapor feed 94 from the lower pressure column, typically having a concentration of about 8% to 15% by volume argon, and a down-flowing argon rich reflux 98 received from an argon condensing assembly 99. The partitioned argon rejection section 92 serves to rectify the argon and oxygen containing vapor feed 94 by separating argon from the oxygen into an argon enriched overhead vapor stream 95 and an oxygen-rich liquid stream 96 that that is released or returned into the lower pressure column 54 at a point below the divided wall column arrangement 90. The mass transfer contacting elements within the divided wall argon rectification column arrangement could be trays or other packing. Possible column packing arrangements include structured packing, strip packing, or silicon carbide foam packing.
The resulting argon-rich vapor overhead stream 95 is then preferably directed to the argon condensing assembly 99 or argon condenser also disposed within the structure of the lower pressure column where all or a portion of the argon-rich vapor overhead stream 95 is condensed into a crude liquid argon stream 98. The resulting crude liquid argon stream 98 is used as an argon-rich reflux stream for the partitioned argon rejection section 92 and optionally taken an impure or crude liquid argon stream (not shown). In the depicted embodiments, the argon-rich reflux stream 98 is directed back to the uppermost portion of the partitioned section 92 and initiates the descending argon liquid phase that contacts the ascending argon and oxygen containing vapor feed 94. In some alternate embodiments, a portion of the argon-rich reflux stream 98 may be directed as a crude argon-rich liquid stream 98B to a downstream adsorption based argon refining and purification subsystem 150 in air separation plants having specific argon product requirements. Likewise, a portion of the argon-rich vapor overhead stream 97 may be diverted and directed to the main heat exchanger 42 to recover refrigeration or the portion of the argon-rich vapor overhead stream 97 can be diverted and directed as a crude argon-rich stream 97B to the adsorption based argon refining and purification subsystem 150.
In the illustrated embodiments, the height of the partitioned argon rejection section 92 is preferably limited to accommodate between about 15 and 40 stages of separation, and more preferably between 20 and 30 stages of separation. While such limited number of separation stages is sufficient for argon rectification needed to improve the oxygen recovery of the cryogenic air separation unit, the resulting purity of the argon rectification vapor stream exiting the partitioned argon rejection section 92 is relatively low at about 4% to 25% oxygen, and more preferably between 10% and 15% oxygen, with up to 1% nitrogen impurities.
The partitioned section 92 of the divided wall column arrangements of
Similarly, the main distillation section 91 of the illustrated divided wall column arrangements include a plurality of mass transfer elements configured continue the air separation occurring within the lower pressure column. In the preferred annular divided wall configuration of
As described in more detail below, the argon condensing assembly 99 is preferably configured as a once-through argon condenser and is disposed internal to the lower pressure column 54, just above the divided wall arrangement 90 of the lower pressure column structure that forms the argon rectification column. This location of the argon condensing assembly 99 or argon condenser is the natural feed point for the kettle liquid and vapor, and the natural point to condense the argon overhead vapor 95. As a result, this location is an ideal location to house the argon condenser 99 to minimizing piping and avoiding the need for a separator vessel for the two phase partially boiled kettle stream. Alternatively, the argon condenser 99 may be disposed at the uppermost portion of lower pressure column 54, although additional piping may be required.
Internal Argon Condenser
The illustrated embodiments provide an improved method and arrangement for argon recovery from a cryogenic air separation unit configured with a higher pressure column 52, a lower pressure column 54 and a divided wall argon rectification column 56. As seen therein, the improved method and arrangement for argon recovery comprises condensing the argon-rich, overhead vapor 95 from the top of the divided wall argon rectification column in an argon condensing assembly 99 disposed at an intermediate location within the lower pressure column 54. In the preferred embodiment, the argon-rich overhead vapor 95 is directed to the argon condenser 99 via via line 109 and is condensed in the argon condensing assembly 99 via indirect heat exchange with the entire kettle liquid stream 53 fed from the higher pressure column 52 and subcooled in subcooler 70B. Control of this flow is preferably accomplished via flow control valve 115. Alternatively, the latent heat of the argon condensation may be imparted to only a portion of kettle liquid stream wherein the remaining kettle liquid stream may be directed into the lower pressure column.
The argon condensing assembly 99 preferably comprises one or more once-through argon condenser cores and disposed at an intermediate location within the lower pressure column 54 where the argon-rich overhead vapor 95 from the partitioned section 92 of the divided wall argon rectification column arrangement 90 flows in a counter flow arrangement against sub-cooled and lower pressure kettle liquid or bottoms liquid 53 from the higher pressure column 52. The boil-up stream 112 from the argon condensing assembly 99 is a two phase (vapor/liquid) stream that is released into lower pressure column 54 for further rectification or separated in phase separator 114 into a vapor stream 116 and liquid stream 118 prior to being released or returned to the lower pressure column 54. The condensed, argon-rich liquid 98 is removed from a location proximate the bottom of the argon condensing assembly 99 and may be split into two portions. The main portion is fed to the top of the partitioned section 92 of the divided wall argon rectification column arrangement to provide reflux for the divided wall argon rectification column while the optional, second portion may be taken as a crude liquid argon product. A portion of the argon-rich overhead vapor 95 from the partitioned section 92 of divided wall argon rectification column arrangement can also be withdrawn as crude vapor argon product 97.
With the argon condenser 99 preferably disposed internal to the lower pressure column 54, there is the opportunity to use a portion of the down-flowing liquid within the lower pressure column 54 combined with kettle liquid 53 as the boiling side fluid in the argon condenser. However, it may be advantageous to use only kettle liquid directly here because the kettle liquid is normally higher in nitrogen, and thus provides a larger temperature difference in the internal argon condenser 99. However, persons skilled in the art will also recognize that alternate liquid streams such as a condensed air stream or a liquid nitrogen stream may be used in lieu of the crude liquid oxygen stream or the down flowing liquid as the source of refrigeration. Furthermore, the entire crude liquid oxygen stream could be fed into the lower pressure column and the internal argon condenser could be situated lower in the lower pressure column, but still immediately above the partitioned section 92 of the divided wall argon rectification column arrangement 90.
As described above, prior to entering the internally disposed argon condenser 99, the kettle liquid stream 53 is preferably subcooled within a subcooling heat exchangers 70B and 70A along with the reflux stream through indirect heat exchange with a nitrogen-rich vapor stream 57, 58 produced in the lower pressure column 54. The warmed nitrogen-rich vapor streams 67, 68 are then directed to the main heat exchanger 42 where it is further warmed to produce a gaseous nitrogen product stream 78 and a waste nitrogen stream 77.
Argon Rejection and Recovery
Employing the present divided wall argon rectification column arrangement and argon condensing assembly within the shell of the lower pressure column of a cryogenic air separation unit can enable power savings and may also serve to increase oxygen recovery within the cryogenic air separation unit. Preferably, an impure argon-rich stream withdrawn from the argon rectification column can be rejected or can be recovered by diverting all or a portion of the impure argon-rich stream to an adsorption based argon purification or refining subsystem 150. In some embodiments, discussed in more detail below, an impure argon-rich liquid stream can be withdrawn from the argon condensing assembly 99 disposed within the lower pressure column 54 and recovered by diverting a portion of the argon-rich liquid stream to an adsorption based argon purification or refining subsystem 150.
In the embodiment contemplating argon rejection shown in
In an embodiment contemplating high purity argon recovery shown in
Other embodiments contemplating argon recovery shown in
Advantageously, since the key differences between the argon rejection arrangements and argon recovery arrangements lie outside the air separation unit coldbox, it becomes relatively easy and not overly capital intensive to change or retrofit the air separation plant from an argon rejection based plant to an argon recovery based plant, depending on the near-term argon product requirements. For example, the present arrangements for argon production would be particularly suitable for use in cryogenic air separation plants initially designed for argon rejection that can be easily modified to provide for argon recovery at a later date when the argon production requirements for the air separation plant change.
Argon Refining
In the embodiments employing argon recovery, the impure or crude argon-rich stream 97 in gaseous form is preferably introduced into argon refining and purification subsystem 150 having one or more adsorbent beds containing an adsorbent that is designed to remove oxygen impurities and optionally nitrogen impurities from the impure or crude argon-rich stream 97. Pressure elevation of the impure argon-rich stream 97 is accomplished with a compressor or pump 151. The adsorption of the impurities produces a purified argon stream that may be delivered as a purified argon vapor stream 170. Liquefaction of the purified argon vapor stream 170 produced from the PSA system is necessary for liquid argon production. As is well known in the art, the adsorption based argon refining or purification subsystems generally employ an alternating adsorption cycle having an on-line phase where the impure or crude argon-rich stream 97 is purified within one or more adsorbent beds and an off-line phase where the adsorbent contained in the adsorbent beds is regenerated through desorption of the previously adsorbed impurities.
One such adsorption based argon refining or purification subsystem is a cryogenic or liquid phase adsorption based argon refining or purification subsystem as generally described in U.S. patent application Ser. No. 14/192,003 filed on Feb. 27, 2014, the disclosure of which is incorporated by reference herein.
Another adsorption based argon refining or purification subsystem 150 is the non-cryogenic adsorption based argon refining or purification subsystem as shown generally in
The PSA system preferably is a carbon molecular sieve (CMS), a zeolite 4A, an ion-exchanged form of zeolite 4A or other kind of zeolite based adsorbent to remove the oxygen impurities. The typical adsorption pressure within the vessels during adsorption steps is in the range of about 80 psig to about 120 psig, and preferably between about 100 psig and 110 psig, and the temperature during the adsorption operation is near ambient temperatures. Removal of nitrogen can be accomplished within in the PSA system with the inclusion of a LiX layer in the adsorption beds. Alternatively, nitrogen impurities may be removed downstream of the PSA system using a high ratio column as a separate purifying step. In such alternate high ratio column embodiments (See
A crude argon compressor 159 is preferably included upstream of adsorption vessels 162, 164 to provide the warmed impure or crude argon-rich stream at the proper pressure required for the adsorption process. Alternatively, a liquid impure argon-rich stream may be pumped and vaporized. The gaseous argon product can be delivered as argon product, or liquefied and stored as a liquid argon product while the waste gas or blowdown gas 172 from the PSA system is preferably recycled. In the case of recycling, the waste gas or blowdown gas 172 from the PSA system may be recycled as stream 172A back to the argon rejection column 56 of the air separation plant 10 or as recycle stream 172B back to the feed of the PSA system. In some embodiments, the recycle stream 172C may be vented.
The embodiment of the adsorption based argon refining and purification subsystem shown in
In the embodiments illustrated in
In the embodiment of
In
For the configurations schematically illustrated in
The configuration of
As an alternative to the withdrawal of a portion of the intermediate temperature air stream prior to turbine expansion, an intermediate temperature stream from the booster air compressor may be used. This alternative stream may be a portion of the stream delivered at the final discharge pressure of the booster air compressor, or it may be a stream withdrawn at an intermediate pressure from the booster air compressor. In the configuration of
A still further embodiment of the adsorption based argon refining and purification subsystem is shown in
Specifically,
Similarly, an optional third 2-bed PSA stage is configured to receive the blowdown or waste stream 222 of the second 2-bed PSA stage via tank 236 and compressor 238 and enriches it to form another low grade argon product stream 235 having the same or similar argon concentration as crude argon rejection stream feed 161. Again, the size of the third 2-bed PSA stage is smaller than both the first and second 2-bed PSA stages. The enriched low grade argon product stream 235 produced by the third 2-bed PSA stage is also recycled back to the crude argon rejection stream feed 161 directed to the first 2-bed PSA stage. Although
Process modeling has shown that using an impure or crude argon-rich feed having a concentration of about 90% argon and about 10% oxygen impurities, a two stage PSA system could achieve argon recovery of 71% while a three stage PSA system shown in
In the example highlighted in Table 1, the impure or crude argon-rich feed from the distillation column is 90% argon and 10% oxygen impurities. For easy demonstration, the impure or crude argon-rich feed flow is set at about 1.0 NCFH. As shown in Table 1, the process conditions such as concentrations and flowrates are calculated based on modeled argon process recovery for each of the three stages in the multi-stage, adsorption based argon refining and purification subsystem. The feed stream to PSA stage 2 is the waste stream from PSA stage 1 at a concentration of about 88% argon and 12% oxygen impurities. A compressor is required to compress this waste stream to the selected PSA system pressure of about 110 psig and a flowrate of about 0.82 NCFH. The compressed waste stream from the PSA stage 1 is directed to PSA stage 2. The enrichment product produced by the PSA stage 2 is about 90% argon and 10% oxygen impurities, the same as the impure or crude argon-rich feed to PSA stage 1. This low grade product stream from PSA stage 2 is at a flow rate of about 0.72 NCFH and is recycled back to and combined with the impure or crude argon-rich feed fresh crude feed to PSA stage 1.
When the optional stage 3 is used, the feed stream to PSA stage 3 is the waste stream from PSA stage 2 at a concentration of about 72% argon and 28% oxygen impurities and a flowrate of about 0.10 NCFH. As discussed in more detail below, this waste stream is further compressed using a compressor prior to entering PSA stage 3 beds. The argon enrichment product produced by PSA stage 3 is also about 90% argon and 10% oxygen impurities, the same as the impure or crude argon-rich feed to PSA stage 1. This low grade product stream from PSA stage 2 is at a flow rate of only about 0.05 NCFH and, like the waste stream from PSA stage 2 is recycled back to and combined with the impure or crude argon-rich feed fresh crude feed to PSA stage 1. It should be noted that the argon feed flow to PSA stage 1 in this example is constant at about 1.0 NCFH and the argon product flow from PSA stage 1 is fairly constant at about 0.18 NCFH. As a result, the recovery of argon for the overall process is increased to 86% for the three stage PSA system with the argon feed concentration at 90% argon and 10% oxygen impurities while the overall argon recovery for a two stage PSA system at these feed conditions is about 71%.
As indicated above, for the waste stream recycle process in a multi-stage PSA system described herein, one or more compressors 228, 238 may be required to compress the waste streams and feed the downstream adsorbent beds. Depending on the oxygen concentration in the waste stream, extra compressor cost may be incurred for this recycle process, particularly where the oxygen impurity concentration is greater than about 23.5%. To minimize capital costs and improve the safety characteristics of the present adsorption based argon refining and purification subsystem, it is desirable to avoid use of the higher cost compressors. As a result, it may be advantageous to design or configure the argon refining and purification process to keep the oxygen concentration in any waste stream requiring compression to a concentration of less than about 23.5%.
As shown in Table 1, the oxygen concentration in the waste stream from PSA stage 1 in the above example is only about 12%, so a standard compressor design is sufficient for this waste stream in the multi-stage PSA system and process. However, the waste stream from PSA stage 2 has an oxygen concentration of about 28%, which means a more expensive compressor may be needed if this waste stream is to be safely directed to PSA stage 3. Although additional stages of the multi-stage PSA system or arrangement will enable higher argon recoveries, the additional capital costs for additional stages may adversely impact the economics of the argon refining and purification process. In the present example shown in Table 1, the flow of waste stream from PSA stage 2 to PSA stage 3 is only about 10% of the impure or crude argon-rich feed flow to the multi-stage PSA system. Thus, it may be more economical to recycle this waste stream back to argon rejection column to recover argon.
Another example of the present multi-stage adsorption based argon refining and purification subsystem with three PSA stages, each stage comprising a 2-bed PSA system is provided in Table 2. This example shows the performance of multi-stage adsorption based argon refining and purification subsystem of
The improved PSA system argon recoveries of the
Nitrogen Removal
As discussed above, nitrogen removal from the crude argon-rich stream can be effected by including a layer or layers of material such as LiX in the adsorption beds as described above with reference to
Turning now to
Within the argon rejection column 56 and at a location above the argon vapor product draw 97B, a small separation section is provided for enhanced nitrogen removal. This section is referred to as the pasteurization section 258. In the shown embodiment, the overhead vapor 95 from the argon rejection column 56 is partially condensed in the argon condensing assembly 99. This partially condensed stream 98A is directed to a downstream phase separator 260 where the small amount of remaining vapor is removed or vented as the nitrogen rich vent stream 262. The resulting argon-rich liquid is sent back to the argon rejection column 56 as part of the reflux stream 98C. Although shown in
The argon product draw 97B from the argon rejection column 56 is preferably removed from the top of the distillation section 256 which is disposed below the pasteurization section 258. Although shown as an argon vapor product draw, the product stream can actually be a vapor stream, liquid stream or two-phase stream. Preferably, the waste stream or blowdown 172A, 180 from the adsorption based argon recovery and purification subsystem 150 is fed at the top of the pasteurization section 258 of the argon rejection column 56, just below the argon condensing assembly 99. Since an elevated feed pressure of greater than about 80 psig and more preferably about 120 psig is desired for the adsorption based argon recovery and purification subsystem 150, an auxiliary compressor or pump 151 may be required if the argon product draw is a vapor draw. In applications where the argon product draw is a liquid draw, a pump may be needed, although liquid head may be sufficient to achieve the desired operating pressure for the adsorption based argon recovery and purification subsystem 150.
With the pasteurizing section 258 at the top of the argon rejection column 56, the nitrogen content of the overhead stream 95 directed to the argon condensing assembly 99 is higher. As a result, the pinch ‘delta T’ (ΔT) of the argon condensing assembly 99 is smaller and the required heat transfer surface area will generally be larger. In addition, the argon recovery is slightly reduced due to the small argon content in the vented stream. However, to mitigate or offset these disadvantages, the argon condensing assembly 99 in the present embodiment is preferably a once-through argon condenser and the argon product draw 97B has oxygen impurities on the order of between 4% and 25%, and preferably at least 10% oxygen impurities such that the resulting overhead stream (or condensing stream) is warmer. Also, to effectively operate the illustrated embodiment, the pasteurization section 258 of the argon rejection column 56 should include at least three stages of separation and the argon condensing assembly 99 should be designed to achieve the partial condensation of the overhead stream 95. Also, the use of structured packing within the argon rejection column 56 would be very beneficial as the resultant pressure at the top of the argon rejection column 56 is generally higher when using structured packing.
Another embodiment of the air separation plant having an argon rejection column with a distillation section and a pasteurization section for enhanced nitrogen removal is depicted in
In the illustrated embodiment of
The primary argon condensing assembly 99 receives an argon-rich vapor stream 94 from the top of the distillation section 256 and below the pasteurization section 258 of the argon rejection column 56. The condensed argon-rich liquid stream 95 is returned to the argon rejection column 56 at a location near the top of the distillation section 256 and below the pasteurization section 258. The overhead nitrogen and argon-rich vapor 295 from the top of the pasteurization section 258 is directed to an auxiliary argon condenser 289 where it is partially condensed against a stream of shelf liquid nitrogen liquid 280 instead of kettle liquid nitrogen. The partially condensed stream 282 is then directed to the phase separator 260 where the remaining vapor is removed or vented as the nitrogen rich vent stream 262. The resulting nitrogen and argon-rich liquid is then sent back to the argon rejection column 56 as reflux stream 98C. As with the earlier described embodiment, the phase separation may be a separate device or may be integrated into the auxiliary argon condenser.
In this embodiment, the heat transfer area of the auxiliary argon condenser is very low, the ‘delta T (ΔT) is large, and its duty is small. Also, the reduced duty of the primary argon condensing assembly will tend to increase the liquid to vapor ratio of the exiting boiling stream which in turn improves the operating safety of the system. Also, with the primary argon condensing assembly being larger in duty than the auxiliary argon condenser, the remaining vapor flow in the pasteurization section of the argon rejection column is much lower, which means more separation stages (e.g. about nine separation stages) are required in the pasteurization section. This arrangement however has the benefit of reducing the heat exchange surface area required by the auxiliary argon condenser, while eliminating the need for the high ratio column.
A still further embodiment contemplates combining or integrating the auxiliary argon condenser 289 into the primary argon condensing assembly 99. The combined or integrated argon condenser would also preferably disposed or housed within in the lower pressure column 54 but could also be housed external to the lower pressure column. In such contemplated embodiment, the recycled waste stream 172B, 180 of the adsorption based argon recovery and purification subsystem 150 would be preferably returned to the distillation section 256 of the argon rejection column 56 at an intermediate location near or above the middle of the argon rejection column 56, as it is undesirable to feed the recycled waste gas to the pasteurization section 258 or proximate the pasteurization section here because of the very low flows in pasteurization section 258.
An alternative embodiment to that described with reference to
The oxygen-enriched mixed liquid stream preferably comprises the oxygen-enriched kettle liquid 53 from higher pressure column 52 of the cryogenic air separation unit, and optionally, a down-flowing liquid in the upper distillation section of the lower pressure column. The crude liquid oxygen-enriched kettle liquid 53 from the higher pressure column 52 is sub-cooled in heat exchanger (not shown), reduced in pressure via valve 115, and directed to lower pressure column 54 where it is mixed with the down-flowing liquid in the lower pressure column 54 from above the reflux argon condenser. The oxygen-enriched kettle liquid and the down-flowing liquid are preferably mixed in a collection trough (not shown) and fed into the boiling passages of the reflux argon condenser 300. The boiling passages are preferably configured to allow the boiling vapor to exit near the top of the reflux argon condenser 300.
The reflux argon condenser 300 preferably comprises one or more once-through argon condenser cores and is disposed at an intermediate location within the low pressure column 54. As indicated above, the oxygen-enriched mixed liquid stream is partially vaporized within the reflux argon condenser 300 and the resulting vapor portion 112 is released at an intermediate location of lower pressure column for further rectification. Similarly, the liquid portion 113 of the partially vaporized stream is also released at an intermediate location of lower pressure column 54 for further rectification. As the argon-rich overhead vapor 295 partially condenses within the reflux argon condenser 300, a nitrogen-rich vapor stream is stripped therefrom and vented internally to the lower pressure column 54.
Since there is already a high nitrogen content at the venting location within the lower pressure column 54, the introduction of the nitrogen-rich vent stream 112 from the argon reflux condenser 301 does not adversely affect the composition profile within the lower pressure column 54. However, internally venting the nitrogen-rich vent stream avoids the costs and refrigeration loss associated with external venting and avoids any argon loss associated with external venting.
From an argon recovery control standpoint, the embodiment of
An advantage of this alternative embodiment compared to the previously disclosed embodiments is that the liquid to vapor ratio (L/V) exiting the once through reflux argon condenser is much greater since the volume of liquid passing through the boiling side of the condenser (i.e. down-flowing liquid from the lower pressure column together with kettle liquid from the higher pressure column) is greater and most of the resulting boiling vapor exits the top of the condenser. This increased liquid to vapor ratio exiting the argon condenser greatly increases the safety aspects of the argon condenser in that it prevents boiling to dryness and keeps the condensing surfaces sufficiently wetted.
In the arrangements using the reflux argon condenser 300, 301 disposed within the lower pressure column 54, it may be beneficial to have a portion of the down-coming liquid from the lower pressure column bypass the collection trough and also thereby bypass the reflux argon condenser. Similarly, it is also possible to divert a portion of the liquid stream discharged from the collection trough so as to bypass the reflux argon condenser. Such bypassing arrangements may be employed to optimize the size and/or girth of the internally disposed reflux argon condenser. Also, the amount of liquid to be diverted or to bypass the reflux argon condenser will be limited so as to ensure sufficient wetting of the argon condenser surfaces is maintained.
The embodiment illustrated in
In the embodiment of
While the present invention has been described with reference to several embodiments and operating methods associated therewith, it is understood that numerous additions, changes and omissions to the disclosed systems and methods can be made without departing from the spirit and scope of the present invention as set forth in the appended claims.
The present application is a continuation application of U.S. patent application Ser. No. 15/057,160 filed on Mar. 1, 2016, which claims the benefit of and priority to U.S. provisional patent application Ser. No. 62/199,483 filed on Jul. 31, 2015, the disclosure of which is incorporated by reference herein.
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| Number | Date | Country | |
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| 20180292130 A1 | Oct 2018 | US |
| Number | Date | Country | |
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| Number | Date | Country | |
|---|---|---|---|
| Parent | 15057160 | Mar 2016 | US |
| Child | 16009635 | US |
