Elevated pressure air separation cycles with liquid production

Abstract: The efficiency of producing liquid products from a cryogenic air separation process using a distillation column system having at least a high pressure distillation column (902) and a low pressure distillation column (904) in thermal communication with each other and in which system the low pressure column (904) operates at a pressure of 60 to 520 kPag (9 to 75 psig) and at least 50% of the feed air is removed as a nitrogen product (130) from the low pressure column (904), said product having a nitrogen concentration of at least 95% and is a pressure of at least 60 kPag (9 psig), is improved by partially warming the nitrogen product by heat exchange (918), isentropically expanding the warmed product (920,922) and use of the inherent refrigeration of the expanded nitrogen. The refrigeration can be recovered by heat exchange (916) against a liquid stream (5) from the high pressure column (902) and/or by heat exchange (900) against the feed air (101).

Description: The present invention relates to a cryogenic process for the distillation of air into its constituent components to provide at least liquid argon, liquid nitrogen and liquid oxygen. Particular applications for the constituent components of air often require that components be produced as liquid products from the air separation plant. Elevated pressure cryogenic air separation cycles have the advantages of smaller equipment size and smaller diameter pipelines, as well as energy loss due to pressure drops across these pipelines and equipment. Unfortunately, nitrogen produced by an elevated pressure air separation plant is typically at a higher pressure than is required for its use. The energy of this surplus pressure of the nitrogen from an elevated pressure cycle can be utilized to produce liquid products. With the availability of this excess pressure energy, the quest is to find more efficient ways of utilizing the pressure energy of the nitrogen product from elevated pressure cycles. The conventional way of making liquid oxygen and/or liquid nitrogen is to add a liquefier to the low pressure cycle air separation unit in which the low pressure column operates in the pressure range of 2-9 psig (15-60 kPag). The liquefier may be integrated into the air separation plants, such as is shown in US-A-4,152,130 in which compressed air is expanded to provide the refrigeration needed for liquefaction. Air expansion cycles have the disadvantage that if large quantities of liquid nitrogen product are required, then argon and oxygen recoveries will severely suffer. GB-A-1,199,599 discloses a cryogenic process for separating air which optionally provides 2 to 3% as liquid oxygen and/or liquid nitrogen. It is an essential feature of the process that the majority of the refrigeration is provided by turbo-expansion of nitrogen from the high pressure ("HP") column and extra refrigeration is provided by turbo-expansion of gaseous nitrogen from the low pressure ("LP") column. In the exemplified process, HP nitrogen is warmed in heat exchanger and expanded in turbo-expander to provide reboil for the HP column. It is then heat exchanged against feed air before discharge as product. LP nitrogen is warmed against a portion of HP column bottoms liquid expanded in a turbo-expander, warmed against another portion of HP column bottoms liquid, and then further warmed against feed air before being discharged as a waste stream. Optionally , liquid nitrogen product and/or liquid oxygen product is (are) withdrawn. US-A-4,705,548 teaches the use of heat pumping with nitrogen to help solve this recovery problem, but, unfortunately, this heat pumping step introduces inefficiencies by increasing exergy loss in heat exchangers and increases capital cost. GB-A-1,450,164 discloses a process in which air feed to a cryogenic air distillation system for producing liquid product is compressed in a plurality of stages to 70 kp/cm 2 (6.9 MPa) to 100 kp/cm 2 (9.8 MPa) above atmospheric pressure and the compressed gas cooled to -10°C to -35°C. A portion of the cooled, compressed gas is expanded in an expansion turbine and the remainder is expanded through a throttle. The expanded portions are recombined before rectification. In one embodiment, gaseous nitrogen product from the low pressure column of a dual column distillation system is warmed against bottoms liquid from the high pressure column and then expanded before heat exchange against the compressed air feed. Prior to expansion, the nitrogen product is below the dew point of the compressed feed air and is further cooled on expansion. This cycle is not efficient because of the unnecessary degree of energy degradation in utilizing the refrigeration produced by expansion of the pressurized nitrogen. No information is provided in GB-A-1,450,164 as to the pressure of the expanded air feed or subsequent pressures in the distillation system. US-A-4,543,115 discloses a process for the production of gaseous nitrogen by cryogenic distillation of air in a dual column distillation system in which feed air is supplied to the low pressure column as well as to the high pressure column. A process stream is expanded through an expansion turbine to provide refrigeration. Preferably, the expanded process stream is a portion of the high pressure feed air stream but it can be the nitrogen product from the low pressure column. In the illustrated embodiment using the low pressure nitrogen product, that product is warmed by heat exchange against both bottoms liquid from the high pressure column and feed air to the low pressure column, and then expanded prior to heat exchange against both feed air streams. No liquid product is produced in the process of US-A-4,543,115 and the only exemplified pressure in the low pressure column exceeds 110 psig (750 kPag). Another problem of conventional air separation plants is that typically large amounts of waste nitrogen are used for producing chilled water, which needs to be at a pressure very close to atmospheric pressure (e.g. about 0.5 psi (3 kPa) higher than atmospheric pressure), and for regeneration of the mole sieve beds, which needs to be at a pressure 1-3 psi (7-21 kPa) higher than atmospheric pressure. Conventionally, both streams are produced from the low pressure column, with the pressure of the low pressure column being set by the pressure of the mole sieve regeneration stream, resulting in a higher column pressure and therefore a higher discharge pressure from the main air compressor. The other way to set the pressure of the low pressure column is according to the water chilling nitrogen stream pressure and compress the regeneration stream to the required pressure. This solution requires more capital since the regeneration stream pressure booster and after-cooler adds to the capital cost. According to a first aspect, the present invention provides a cryogenic process for the separation of a feed air stream its constituent components to provide at least liquid argon, liquid nitrogen and liquid oxygen products, wherein the process utilizes a distillation column system having at least a high pressure distillation column and a low pressure distillation column, which are in thermal communication with each other, and an argon column fed from and at the same pressure as the low pressure column, wherein the low pressure column operates at a pressure of 60 to 520 kPag (9 to 75 psig), the low pressure column produces a gaseous nitrogen product from the top thereof, at least 50% of the feed air to the distillation column system is removed from the low pressure column as said nitrogen product and said nitrogen product has a nitrogen concentration of at least 95% and is at a pressure of at least 60 kPag (9 psig), wherein: (a) the gaseous nitrogen product is warmed by heat exchange against at least liquid nitrogen product and high pressure column oxygen-rich bottoms liquid; (b) said warmed, nitrogen product is isentropically expanded to reduce its temperature (i) below the temperature of the oxygen-rich bottoms liquid as removed from the high pressure column or (ii) to or below the dew point of said feed air; and (c1) the oxygen-rich bottoms liquid is subcooled by heat exchange against said expanded nitrogen product prior to isenthalpic reduction of the pressure of said liquid across a valve and feeding to the low pressure column and/or (c2) said feed air is cooled by heat exchange against said expanded nitrogen product, provided that the gaseous nitrogen product is warmed by heat exchange against feed air prior to said expansion. In a second aspect, the invention provides an apparatus for use in a cryogenic process of the invention, said apparatus comprising a distillation column system having at least a high pressure distillation column and a low pressure column, which are in thermal communication with each other and an argon column fed from and at the same pressure as the low pressure column, at least one heat exchanger warming the gaseous nitrogen product against at least liquid nitrogen product and high pressure column oxygen-rich bottoms liquid; an expander isentropically expanding the warmed, nitrogen product; and either or both of a heat exchanger subcooling the oxygen-rich bottoms liquid as removed from the high pressure column against the isentropically expanded nitrogen product prior to isenthalpic reduction of the pressure of said liquid across a valve and feeding to the low pressure column and a heat exchanger warming the gaseous nitrogen product prior to expansion against feed air and cooling the feed air against the isentropically expanded nitrogen product. The improvement to the process is a series of steps which allows for the production of liquid products from the cryogenic process in an efficient manner. An air cleaning bed regeneration stream can be produced separately from other nitrogen products produced by an elevated pressure cycle. This regeneration stream may be expanded from a high pressure column nitrogen product or from a low pressure column nitrogen product. There are numerous ways these two methods of producing a regeneration stream can be incorporated into the cycle. A portion of the warmed nitrogen of step (a) can be separately isentropically expanded to a pressure which is 7 to 21 kPa (1 to 3 psi) lower than the discharge pressure of the isentropically expanded nitrogen of step (b) and is used to regenerate mole sieve beds used to pre-clean the feed air stream. In one preferred embodiment, the warmed nitrogen product is divided into a first substream and a second substream. The first substream is isentropically expanded to reduce its temperature below the temperature of the liquid stream(s) removed from the high pressure column and used to subcool said liquid stream(s) prior to isenthalpic reduction of the pressure of the liquid stream(s) across a valve. The second substream is warmed by heat exchange against feed air and then isentropically expanded to reduce its temperature to or below the dew point of the feed air prior to use to cool the feed air. The second substream can be compressed and aftercooled prior to the isentropic expansion thereof. Additionally or alternatively, at least a portion of the expanded second substream and/or at least a portion of the expanded first substream can be used to regenerate mole sieve beds used to pre-clean the feed air stream. When the expanded nitrogen product is used to cool feed air, the extent of the cooling can be such as to partially condense the feed air. Suitably, the apparatus, described before, comprises two expanders isentropically expanding partially warmed nitrogen product and both of said heat exchangers receiving isentropically expanded nitrogen and wherein one of said expanders isentropically expands a first substream of said nitrogen product, prior to feeding to the heat exchanger subcooling the liquid stream; a further heat exchanger warms a second substream of said nitrogen product against a suitable process stream; and the other of said expanders isentropically expands the partially warmed, second substream product prior to feeding to the heat exchange cooling the air feed. The following is a description by way of example only and with reference to the drawings of several embodiments of the present invention. In the drawings: Figures 1 through 8 and 10 are schematic diagrams of embodiments of the process of the present invention; and Figure 9 is a schematic diagram of a conventional air separation process. The present invention is an improvement to a cryogenic air separation process utilizing a distillation column system wherein the operational pressure of the low pressure column is increased above the conventional 2-9 psig (15-60 kPag) pressure. With the pressure of the low pressure column between 9 to 75 psig (60-520 kPag), a low pressure column nitrogen product is produced at similar pressures. Moreover, at least 50% of the incoming air to the air separation plant is removed as this low pressure column nitrogen product; the removed nitrogen product has a nitrogen concentration of at least 95% and is at a pressure of at least 9 psig (60 kPag). A significant fraction of this elevated pressure nitrogen from the distillation column is isentropically expanded in an expander at a cryogenic temperature to provide refrigeration for the production of liquid nitrogen, liquid oxygen and liquid argon. Figures 1-8 and Figure 10 are the flow diagrams depicting some of the possible embodiments of the process of the present invention. The embodiments shown in Figures 1-4 are respectively referred to as the LEP, SEP, BEP and EP cycles. The embodiments of Figures 1-8 and Figure 10 have numerous common features. For ease of understanding, these features, which present the primary cryogenic distillation portion of the cycles, will be described now. With reference to the subject figures, compressed feed air, which has had any particulate matter, water, carbon dioxide and other components which freeze at cryogenic temperatures removed, is fed to main heat exchanger 900, via line 101, for cooling to a temperature close to its dew point. This cooled, feed air is then fed, via line 110, to high pressure column 902 for rectification into a high pressure nitrogen overhead and an oxygen-rich bottoms liquid. A part of the high pressure nitrogen overhead is removed from high pressure column 902, via line 120, and totally condensed in reboiler-condenser 912, located in the bottom of low pressure column 904 against boiling liquid oxygen. The totally condensed high pressure liquid nitrogen is removed from reboiler-condenser 912, via line 122 and split into two portions. The first portion is returned to the top of high pressure column 902, via line 124, as liquid reflux. The second portion, line 3, is subcooled in subcooler 918 and flashed. The resulting liquid portion is removed from the process, via line 400, as liquid nitrogen product. The remaining part of the high pressure nitrogen overhead is removed from high pressure column 902, via line 135, warmed in main heat exchanger 900 to recover refrigeration and removed as high pressure nitrogen product, via line 139. The oxygen-rich bottoms liquid is removed from high pressure column 902, via line 5, subcooled in subcoolers 914 and 916, flashed and then fed, via line 54, to the appropriate location of low pressure column 904 for distillation into a low pressure column nitrogen overhead and liquid oxygen bottoms. At least a portion of the liquid oxygen bottoms is vaporized in reboiler-condenser 912 to provide boil-up for low pressure column 904. The remaining portion of the liquid oxygen bottoms can be removed from low pressure column 904, via line 117, and subcooled in subcooler 916 thereby producing liquid oxygen product in line 500. A portion of the vaporized oxygen from reboiler-condenser 912 is removed from low pressure column 904, via line 195, and warmed in main heat exchanger 900 to recover refrigeration, thereby producing gaseous oxygen product in line 194. This gaseous oxygen product, line 194, can be further compressed to reach the desired pressure; this oxygen compression procedure is not shown. The embodiments shown in the subject figures also produce pure liquid argon product. An argon-containing vapor side stream is removed, via line 66, from an intermediate and appropriate location of low pressure column 904 and fed to the bottom of argon column 906 for rectification into an argon overhead containing less than 5000 vppm oxygen and an argon-containing bottoms liquid. The argon-containing bottoms liquid is removed from argon column 906, via line 68, and returned to low pressure column 904. The argon overhead is removed from argon column 906, via line 65, and split into two portions. The first portion, line 63, is condensed in reboiler-condenser 908 and returned to the top of argon column 906 as liquid reflux. The second portion, line 64, is purified in adsorber 910 thereby producing a pure argon product. This pure argon product, line 62, is then condensed in reboiler-condenser 908, the condensed argon product, line 60, subcooled in subcooler 918 and removed from the process as pure liquid argon product, via line 600. It should be mentioned that the argon product stream can be purified by technologies other than the adsorption technology discussed above. Examples of these other technologies are "de-oxo" systems or "getter" systems to remove oxygen and distillation to remove nitrogen. Reboiler-condenser 908 is located in low pressure column 904 between side stream draw, line 66, and oxygen-rich liquid feed, line 54. The precise location is chosen so as to provide sufficient refrigeration for the required condensation. In reboiler-condenser 908, this refrigeration is provided by boiling liquid descending low pressure column 904 thereby producing additional boil-up for the upper sections of low pressure column 904. It is worth noting that other known schemes can be used to supply reflux for argon column 906. For example, a portion of the argon overhead, line 63, can be condensed against a portion of the oxygen-rich bottoms liquid, line 5. Finally, to provide liquid reflux for low pressure column 904, an oxygen-lean liquid side stream is removed, via line 4, from an intermediate location of high pressure column 902, subcooled in subcooler 918, flashed and fed, via line 80, to low pressure column 904. As mentioned earlier, the improvement of the present invention is the way the elevated nitrogen stream, line 130, produced at the top of low pressure column 904 is utilized to efficiently and effectively produce and recover refrigeration. This utilization will now be discussed with reference to several specific embodiments thereof. With reference to Figure 1, the LEP cycle, an elevated pressure nitrogen stream, line 130, produced at the top of low pressure column 904 is warmed, in subcooler 918, by heat exchange against the oxygen-lean liquid side stream, line 4, and a liquid nitrogen stream, line 3, and, in subcooler 914, against the oxygen-rich bottoms liquid, line 5. This warmed nitrogen stream, line 133, is then split into two portions. The first portion, line 143, is isentropically expanded in expander 920 and this expander effluent, line 242, and vapor, line 398, from the flash of the liquid nitrogen, line 3, are combined. This combined stream, line 241, is used to subcool the oxygen-rich bottoms liquid, line 5, in subcoolers 914 and 916. The second portion, line 134, is further warmed in main heat exchanger 900 and the warmed stream, line 8, expanded in expander 922. This expander effluent, line 9, is combined with the warmed nitrogen from subcooler 914, line 144. This combined low pressure nitrogen, line 147, is warmed in heat exchanger 900 to recover refrigeration and removed from the process as low pressure gaseous nitrogen product, via line 148. This low pressure gaseous nitrogen product stream 148 can be used for water chilling in a waste tower (not shown). The regeneration stream for the air cleaning molecular sieve beds, line 243, for this cycle, is removed as a side stream from high pressure column 902, via line 7. If desired, this regeneration stream could also be removed from the top of high pressure column 902. This side stream is warmed to a suitable expansion temperature in main heat exchanger 900, the warmed stream, line 20, expanded in expander 924 and further warmed in main heat exchanger to recover any refrigeration produced in the expansion. With reference to Figure 2, the SEP cycle, all of the warmed, elevated pressure nitrogen, line 133, is expanded in expander 920. The remainder of the cycle is essentially as shown in Figure 1. With reference to Figure 3, the BEP cycle, all of the warmed, elevated pressure nitrogen, line 133, is further warmed in main heat exchanger 900 before expansion in expander 922. The expanded nitrogen, line 9, is combined with the nitrogen vapor, line 398, from the flashed liquid nitrogen, line 3, and the combined stream is warmed in main heat exchanger 900 to recover refrigeration. With reference to Figure 4, the EP cycle, the warmed nitrogen stream, line 133, is then split into two portions. The first portion, line 143, is isentropically expanded in expander 920 and this expander effluent, line 242, and vapor, line 398, from the flash of the liquid nitrogen, line 3, are combined. This combined stream, line 241, is used to subcool the oxygen-rich bottoms liquid, line 5, in subcoolers 916 and 914, then warmed in main heat exchanger 900 to recover refrigeration and finally removed as low pressure nitrogen product, via line 148. The second portion, line 134, is further warmed in main heat exchanger 900 and compressed in compressor 926. This warmed, compressed second portion, line 233, is cooled in main heat exchanger 900 to an appropriate expansion temperature and expanded in expander 924. This expanded stream, line 243, is warmed to recover refrigeration and removed as the mole sieve beds regeneration stream. Note that no high pressure nitrogen is expanded from the high pressure column. Variations of the embodiment shown in Figure 4, the EP cycle, are shown in Figures 5-7. These variations, however, do not exhaust all the possible combinations. The cycles shown in Figures 5-7 require three expanders. In these cycles, a fraction, line 930, (typically 5-20%) of the feed air, is further compressed in compressor 932 and then cooled in main heat exchanger 900. The cooled, compressed fraction, line 200, is removed from main heat exchanger 900 at either an interim location or the bottom and isentropically expanded in expander 934. The expanded feed air fraction, line 936, can be combined with the cooled feed air and fed, via line 110, to high pressure column 902 or fed directly to low pressure column 904. In Figures 5-7, this expanded feed air fraction, line 936, is fed to high pressure column 902. In the cycle shown in Figure 5, this fraction, line 930, is cooled in main heat exchanger 900 before expansion, while a fraction (corresponding to about 8-20% of feed air) of the elevated pressure nitrogen, line 134, is warmed to ambient temperature in heat exchanger 900 and isentropically expanded in expander 924 and warmed in heat exchanger 900 to supplement the refrigeration needs for cooling the feed air in the warm end of main heat exchanger 900. This warmed nitrogen is used as the mole sieve beds regeneration stream. In the cycle shown in Figure 6, the expanded air, line 935, is introduced into main heat exchanger 900 and cooled further before introduction into high pressure column 902, while regeneration nitrogen, line 134, (8-20% of feed air) is removed from main heat exchanger 900 before it is warmed to ambient temperature and isentropically expanded in expander 924. The expanded nitrogen is fed to the cold end of main heat exchanger 900. In the cycle shown in Figure 7, nitrogen fraction, line 134, is isentropically expanded in expander 924, warmed respectively in subcoolers 918 and 914 and heat exchanger 900 and then used as regeneration stream. In Figure 7, the inlet temperature and pressure to expanders 920 and 924 are the same. However, since the exhaust from expander 920 is not used for mole sieve beds regeneration, its pressure is about 1-3 psi (7-21 kPa) lower than the discharge pressure of expander 924. This arrangement allows for a greater recovery of refrigeration and hence a greater production of liquid products. The expanded air, line 936, is fed to high pressure column 902 without further cooling. In the cycle shown in Figure 8, all of the elevated pressure nitrogen, line 133, is isentropically expanded after being warmed in main heat exchanger 900. This expansion occurs in expanders 920 and 924. The expanded nitrogen streams, lines 242 and 925, are then fed to subcooler 918 to subcool liquid stream, line 5, and then warmed in main heat exchanger 900. After being heated to ambient temperature, the stream expanded from 924, which is 8-20% of feed air, is used as the regeneration stream, line 243. The cycles of Figures 5-8 are more advantageous than the cycle of Figure 4 in terms of energy consumption and exchanger area. Among them, the cycle shown in Figure 7 allows more liquid nitrogen product without seriously hurting oxygen and argon recoveries. If even more liquid is desired, the cycle shown in Figure 8 is even more suitable. Compressor 932 is driven by air expander 934 or nitrogen expander 920 or 924 or any combination thereof. If argon recovery is not an important issue, then, in Figures 5-8, the expanded feed air fraction should be fed directly to low pressure column 904 (not shown). An example of such is shown in Figure 10 in which the expanded air fraction is fed directly to the low pressure column. Also, in this Figure, air expander 934 and compressor 932 are mechanically linked to form a compander. EXAMPLE Computer simulations were done for embodiments shown in Figures 1-4. The product specifications for simulations in this example are listed in Table 1. Product Production Rate: tons/day (tonnes/day) Pressure: psia (Mpa) Gaseous Oxygen 2531 (2296) 805 (5.55) Liquid Oxygen 64 (58) --- Gaseous Nitrogen 1.51 (1/37) >65 (>0.45) Liquid Nitrogen 255.35 (231/65) --- Liquid Argon Maximum --- Purity: Oxygen: >95 mol% oxygen Nitrogen: <2 vppm oxygen Table 2 presents a comparison of different cycles. Recall that LEP, SEP, BEP and EP are the cycle designations for the embodiments shown in Figures 1-4, respectively. AirComp is the conventional low pressure air compander cycle in which both the water chilling stream and regeneration stream are produced directly from the low pressure column; this conventional cycle is shown in Figure 9. Low pressure cycle Aircomp needs a liquefier for liquefying oxygen and nitrogen in order to produce the desired liquid products. See the note of Table 2. The liquefier is not shown in Figure 9. In Table 2, oxygen recovery is defined as the moles of oxygen recovered per 100 moles of air feed to the distillation column system. The argon recovery is defined as the percentage of argon recovered which is present in the feed air to the distillation column system. From Table 2 it can be seen that the elevated pressure cycles LEP, SEP, and BEP have lower power values than the Aircomp cycle. These power values are 3.8 to 5.5% lower than the conventional Aircomp cycle. The argon recovery for LEP cycle is comparable to Aircomp, and is slightly lower for SEP and BEP. The savings in capital cost and energy consumption, however, will far offset the drops in argon recovery. The EP cycle has higher power consumption, with a very high argon recovery. Process conditions for some of the pertinent streams for LEP, SEP, and BEP cycles are listed in Table 3. As can be seen from the above discussion, the present invention works by expanding the nitrogen stream produced from the low pressure column of an air separation plant using an elevated pressure cycle at the right temperatures and using the generated refrigeration from the expanded stream at the appropriate location in the process. The energy inherent to this nitrogen stream can be used to produce liquid products in an efficient manner with a minimal capital cost increase. Also, by producing the regeneration stream from a separate expander, the expansion ratios of the expanders are optimized, so that the air compression energy is optimized. In all the figures shown, the nitrogen stream from the top of low pressure column 904 is withdrawn and expanded in a prudent manner to recover refrigeration. The present invention has a significant benefit by teaching efficient ways of producing liquid product from the pressure energy inherent in the nitrogen stream produced by the low pressure column of an elevated pressure cycle air separation plant. In the present invention, air separation and liquid production are integrated in a very efficient way. The elevated pressure cycle air separation process of the present invention reduces equipment size, pressure drop loss and air cleaning molecular sieve beds regeneration energy consumption while generating liquid products from the pressure energy of the nitrogen product. The process of the present invention also eliminates the need for separate compressors, heat exchangers and other equipment of a stand alone liquefier. An efficient way of doing this implies such cycles are superior to other cycles not only in capital cost, but also in energy efficiency. Such efficient combinations of elevated pressure air separation and liquefaction should therefore be the choice for air separation when liquid products are also demanded. The same idea is also applicable to other cryogenic gas separation processes. It should be mentioned that, although such cycles alone will have difficulties in producing large quantities of liquid products in terms of the feed air, (eg. exceeding 10% of feed air), the combination of such cycles with liquefiers still results in optimal efficiency as well as capital cost.

Claims: A cryogenic process for the separation of a feed air stream (101) into its constituent components to provide at least liquid argon, liquid nitrogen and liquid oxygen products (600, 400, 500), wherein the process utilizes a distillation column system having at least a high pressure distillation column (902) and a low pressure distillation column (904), which are in thermal communication with each other, and an argon column (906) fed from and at the same pressure as the low pressure column (904), wherein the low pressure column (904) operates at a pressure of 60 to 520 kPag (9 to 75 psig), the low pressure column (904) produces a gaseous nitrogen product (130) from the top thereof, at least 50% of the feed air (101) to the distillation column system is removed from the low pressure column (904) as said nitrogen product (130) and said nitrogen product (130) has a nitrogen concentration of at least 95% and is at a pressure of at least 60 kPag (9 psig), wherein: (a) the gaseous nitrogen product (130) is warmed by heat exchange (914,918) against at least liquid nitrogen product (3) and high pressure column oxygen-rich bottoms liquid (5); (b) said warmed, nitrogen product (8,143) is isentropically expanded (920,922) to reduce its temperature (i) below the temperature of the oxygen-rich bottoms liquid (5) as removed from the high pressure column (902) or (ii) to or below the dew point of said feed air (101); and (c1) the oxygen-rich bottoms liquid (5) is subcooled by heat exchange (914,916) against said expanded nitrogen product (242) prior to isenthalpic reduction of the pressure of said liquid (5) across a valve and feeding to the low pressure column (904) and/or (c2) said feed air (101) is cooled by heat exchange (900) against said expanded nitrogen product (9), provided that the gaseous nitrogen product (9) is warmed by heat exchange (900) against feed air (101) prior to said expansion (922). A process as claimed in Claim 1, wherein said warmed, nitrogen product (143) is isentropically expanded (920) to reduce its temperature below the temperature of the oxygen-rich bottoms liquid (5) as removed from the high pressure column (902) and said liquid (5) is subcooled by heat exchange (916;914) against said expanded nitrogen product (242) prior to isenthalpic reduction of the pressure of said liquid (5) across a valve and feeding to the low pressure column (904). A process as claimed in Claim 1, wherein the warmed nitrogen product (130) is further warmed by heat exchange (900) against feed air (101); the further warmed nitrogen product (8) is isentropically expanded (922) to reduce its temperature to or below the dew point of said feed air (101) and said feed air (101) is cooled by heat exchange (900) against said expanded nitrogen (9). A process as claimed in any one of the preceding claims, wherein a portion (134) of the warmed nitrogen product of step (a) is separately isentropically expanded (924) to a pressure which is 7 to 21 kPa (1 to 3 psi) lower than the discharge pressure of the isentropically expanded nitrogen product (242) of step (b) and is used (243) to regenerate mole sieve beds used to pre-clean the feed air stream (101). A process as claimed in Claim 1, wherein said warmed, nitrogen product (133) is divided into a first substream (143) and a second substream (134); said first substream (143) is isentropically (920) expanded to reduce its temperature below the temperature of the oxygen-rich bottoms liquid (5) as removed from the high pressure column (902); said liquid (5) is subcooled by heat exchange (914,918) against said expanded first substream (242) prior to isenthalpic reduction of the pressure of said liquid (5) across a valve and feeding to the low pressure column (904); said second substream (134) is further warmed by heat exchange (900) against feed air (101); said warmed, second substream product (8) is isentropically expanded (922) to reduce its temperature to or below the dew point of the feed air (101); and the feed air (101) is cooled by heat exchange (900) against the isentropically expanded first and second substreams (147). A process as claimed in Claim 5, which further comprises compressing (926) and aftercooling (900) the second substream (134) prior to the isentropic expansion (924) thereof. A process as claimed in Claim 5 or Claim 6, wherein at least a portion of the warmed expanded second substream (243) is used to regenerate mole sieve beds used to pre-clean the feed air stream (101). A process as claimed in any one of Claims 5 to 7, wherein at least a portion of the expanded first substream (242) is used to regenerate mole sieve beds used to pre-clean the feed air stream. A process as claimed in any one of Claims 1, 3 and 4 to 8, wherein the feed air (101) is partially condensed by said cooling. Apparatus for use in a cryogenic process as claimed in Claim 1, comprising a distillation column system having at least a high pressure distillation column (902) and a low pressure column (904), which are in thermal communication with each other and an argon column (906) fed from and at the same pressure as the low pressure column (904), at least one heat exchanger (914, 918) warming the gaseous nitrogen product against at least liquid nitrogen product (3) and high pressure column oxygen-rich bottoms liquid (5); an expander (920 or 922) isentropically expanding the warmed, nitrogen product; and either or both of a heat exchanger (914) subcooling the oxygen-rich bottoms liquid (5) as removed from the high pressure column (902) against the isentropically expanded nitrogen product prior to isenthalpic reduction of the pressure of said liquid across a valve and feeding to the low pressure column (904) and a heat exchanger (900) warming the gaseous nitrogen product prior to expansion against feed air and cooling the feed air against the isentropically expanded nitrogen product. An apparatus as claimed in Claim 10, comprising two expanders (920,922) isentropically expanding warmed nitrogen product and both of said heat exchangers (914,900) receiving isentropically expanded nitrogen product and wherein one of said expanders (920) isentropically expands a first substream of said gaseous nitrogen product, prior to feeding to the heat exchanger (914) subcooling the oxygen-rich bottoms liquid (5); a further heat exchanger (906) warms a second substream of said gaseous nitrogen product against a feed air; and the other of said expanders (922) isentropically expands the warmed, second substream product prior to feeding to the heat exchanger (900) cooling the air feed.

Inventors: AGRAWAL RAKESH, XU JIANGUO, AGRAWAL, RAKESH, XU, JIANGUO
Applicants: AIR PROD & CHEM, AIR PRODUCTS AND CHEMICALS, INC.
Application year: 1992
Main classification: F25J3
IPC codes: F25J3