Method and apparatus for gas liquefaction with plural work expansion of feed as refrigerant and air separation cycle embodying the same

Abstract: A method of liquefying a low-boiling gas, in which gas is compressed to a high pressure, is cooled in heat exchange structure and is isenthalpically expanded to condense a portion of the same to liquid. The liquid being separated from residual gas and the residual gas is used to cool the heat exchange structure and is then recycled. A portion of the gas is compressed to an intermediate pressure between the high and low pressures, is isentropically expanded at a first temperature and is used to cool a relatively warm portion of heat exchange structure and is then recycled. A portion of the high pressure gas is isentropically expanded at a second temperature and used to cool a relatively cool portion of the heat exchange structure and then again isentropically expanded at a third temperature to that low pressure and returned through the heat exchange structure to cool the same and is then recycled. That first temperature is higher than the second temperature and that second temperature is higher than the third temperature. The gas is preferably nitrogen. The cycle can be part of an air separation unit, whose low pressure nitrogen product is make-up for the liquefaction cycle and whose high pressure nitrogen product is merged with the low pressure cycle gas.

Description: Field of the Invention The present invention relates to the liquefaction of low-boiling gases with plural work expansions of portions of the feed to produce the refrigeration necessary to cool the remainder of the feed by countercurrent heat exchange. Background of the Invention The liquefaction of a low-boiling gas is effected by compression and cooling and then expansion to reduce its temperature to the liquefaction temperature. It is of course not economical to cool the compressed feed to the necessary liquefaction temperature solely by Joule-Thomson expansion; and so for many years it has been standard procedure to divide the feed and expand a portion of it isentropically and use the refrigeration thus produced to cool the remainder of the feed by countercurrent heat exchange. But the low-boiling gases do not cool with constant change of enthalpy per unit decrease in temperature. Instead, the cooling curves of the low-boiling gases are what is known in the art as "S-curves". On the other hand, when warming, the low-boiling gases do not retrace this same S-curve but rather tend to follow a warming "curve" that in fact is substantially rectilinear. It is also a well-known principle in this art, that the greatest thermodynamic efficiency, and hence the least cost of the work necessary to perform the compression from which the required refrigeration is derived, is promoted by maintaining the temperature difference between the warming and cooling streams during indirect heat exchange, as small as possible over the entire length of the heat exchange means. But this is impossible in the case described above, in which an S-shaped cooling curve is juxtaposed with a rectilinear warming curve: the distance between the two curves cannot be kept to a minimum, because the curves depart quite markedly from congruency. This situation, a familiar bane to designers in this field, is shown schematically in Figure 1 of the attached drawings. The Known Prior Art As the cooling curve of the low-boiling gases cannot be changed, designers in this field have sought to change the warming curve, by redistributing the refrigeration provided by a work expanded portion of the feed stream, along intermediate portions of the heat exchange path. Specifically, it is known to expand a portion of the feed isentropically and to apply the refrigeration thus produced to the remainder of the feed along only a portion of the heat exchange path intermediate the cold and warm ends thereof, and then further isentropically to expand this same portion prior to returning it along the heat exchange means to the warm end thereof. Thus, in Smith et al. U.S. patent 3,358,460, a high pressure feed stream is progressively cooled and then isenthalpically expanded to liquefy the same, a portion of this high pressure stream being isentropically expanded, returned in countercurrent heat exchange with the remainder of the feed at an intermediate temperature level, and then again isentropically expanded before being returned in countercurrent heat exchange to the feed, to the warm end of the heat exchange means. But as these two isentropic expansions are insufficient to produce the required refrigeration, a separate external refrigeration unit is provided which must, however, operate at a relatively low temperature of about -74°C. Such a low temperature requires the use of very expensive external refrigerant; and the refrigeration unit becomes very expensive, as cryogenic materials must be used. Marshall et al. U.S. patent 4,638,639 proposes another arrangement for seeking to render the warming curve congruent with the cooling curve. In this latter patent, a dual pressure cycle is provided, in which the feed is at relatively high pressure and a second stream is compressed to intermediate pressure. A portion of the high pressure stream is isentropically expanded, used to cool the feed at an intermediate temperature level, again isentropically expanded and returned, in countercurrent heat exchange with the feed, to the warm end of the heat exchange means. But instead of an external refrigeration unit as in Smith et al., Marshall et al. provides two further isentropic expansions. In a warmer one of these, a portion of the high pressure feed, at a higher temperature level than the first-mentioned portion of the high pressure feed, is isentropically expanded and returned to cool a warmer portion of the heat exchange means than the first-mentioned feed portion. Also, however, the intermediate pressure stream is cooled to a still lower temperature than the first-mentioned portion of the high pressure stream, and is isentropically expanded and returned to cool a cooler portion of the heat exchange means than the first-mentioned portion. In other words, in Marshall et al., three portions of the feed are isentropically expanded at three different temperature levels and used initially to cool three different portions of the heat exchange means at three correspondingly different temperature levels. At least four expansion engines are thus required. This increases the complexity of the cycle significantly and also results in higher capital costs. Finally, in Dobracki et al. U.S. patent No. 4,894,076, a cycle is proposed in which an intermediate pressure stream is divided and a relatively warm portion is isentropically expanded to provide refrigeration at a relatively high temperature level and a relatively cold portion is isentropically expanded to provide refrigeration at a relatively low temperature level. The description of Dobracki et al., U.S. Patent No. 4,894,076 constitutes the basis by which the preamble of the independent claims to the present invention are defined. Objects of the Invention It is accordingly an object of the present invention to provide a method and apparatus for the liquefaction of low-boiling gases, in which no cryogenic external refrigeration is required. Another object of the present invention is to provide such a method and apparatus, in which a minimum number of expansion engines is used. A further object of the present invention is the provision of such a method and apparatus, in which the warming curve of the gas is caused to approach congruency with the cooling curve of the gas. Still another object of the present invention is to provide such a method and apparatus, in which substantial savings of the cost of energy will be enjoyed. A still further object of the present invention is the provision of such a method and apparatus, in combination with an air separation unit. Another object of the present invention is the provision of such a method and apparatus, of particular utility for the liquefaction of nitrogen. Finally, it is an object of the present invention is the provision of such an apparatus which will be dependable and relatively cost effective, simple to maintain and operate, and rugged and durable in use. According to the invention, there is provided a method of liquefying a low-boiling point gas at a low pressure in which all of said gas is compressed to an intermediate pressure, a first part of said intermediate pressure gas is compressed to a high pressure, cooled in heat exchange means and is expanded and partially liquefied to form a two phase mixture in a phase separator from which liquid is withdrawn, a second part of said intermediate pressure gas is isentropically expanded at a first temperature to a first expanded gas temperature and is used to cool a relatively warm portion of said heat exchange means and is then recycled, a portion of said high pressure gas is isentropically expanded at a second temperature to a second expanded gas temperature and at least part of the gas at the second expanded gas temperature is further isentropically expanded at a third temperature to a third expanded gas temperature and returned through the heat exchange means and then recycled, said first expanded gas temperature being higher than said second expanded gas temperature and said second expanded gas temperature being higher than said third expanded gas temperature and said intermediate pressure being between said high and low pressures, characterized in that said at least part of the gas at the second expanded gas temperature cools a relatively cool portion of said heat exchange means before being expanded to said third expanded gas temperature. According to the invention, there is further provided an apparatus for liquefying a low boiling point gas comprising : means for compressing said gas to an intermediate pressure, between a high pressure and a low pressure, means for compressing part of said intermediate pressure gas to a high pressure means for cooling said high pressure gas, means for expanding part of said high pressure gas to a low pressure separating means for separating the partially condensed gas thereby produced means for withdrawing a liquefied gas from said separating means, means for isentropically expanding said intermediate pressure gas at a first temperature to a first expanded gas temperature and for using the isentropically expanded gas to cool a relatively warm portion of said heat exchange means and then recycling said, isentropically expanded gas means for isentropically expanding a portion of said high pressure gas at a second temperature to a second expanded temperature means for further isentropically expanding at least some of the expanded portion of said high pressure gas at a third temperature to a third expanded gas temperature, said first expanded gas temperature being higher than said second expanded gas temperature and said second expanded gas temperature being higher than said third expanded gas temperature characterized in that it comprises means for sending the expanded portion of the high pressure gas at said second expanded gas temperature to cool a relatively cool portion of said heat exchange means. The method and apparatus according to the present invention avoid the use of low temperature external refrigeration, and at the same time keep the number of expansion engines is kept to a minimum, by providing a dual pressure cycle in which an intermediate pressure portion of the feed is isentropically expanded and used to cool a relatively warm portion of the heat exchange means, while a high pressure portion of the feed is isentropically expanded, used to warm a cooler portion of the heat exchange means, and then again isentropically expanded to provide refrigeration for a still cooler portion of the heat exchange means. This third isentropic expansion is preferably to the lowest cycle pressure and temperature and may in some instances also produce liquefied gas. As a result, the warming curve along the entire length of the heat exchange means of the present invention is brought into rather good congruency with the cooling curve, as shown in Fig. 2 of the accompanying drawings. This means, as pointed out above, that the present invention achieves a rather small temperature difference between the countercurrently flowing streams and hence improves the efficiency of operation, which results in substantial saving of the cost of the energy needed to produce the required compression. The saving in energy is at least about 3%; and, when compared to cycles with relatively low pressures below 50 bars, the saving rises to about 5%. Distinctions from the Prior Art Relative to the disclosure of the patent of Smith et al., described above, the present invention presents at least these significant distinctions: 1. No external refrigeration unit operating at low temperature is required, with the advantages recited above. 2. Smith et al. is not a dual pressure cycle: the external refrigeration is applied to the same high pressure feed stream of which a portion is subjected to successive isentropic expansions. Relative to Marshall et al., described above, the present invention has at least the following distinctions: 1. Although the scheme shown by Marshall et al. appears to be a dual pressure cycle, the warmest isentropic expansion is performed on a portion of the high pressure stream, not on the intermediate pressure stream as in the present invention. 2. In Marshall et al., the isentropic expansion of the intermediate pressure stream is performed at the lowest temperature level of the three isentropically expanded streams. 3. In Marshall et al., the refrigeration obtained by isentropic expansion is applied at three different temperature levels, and so four expansion engines are required. 4. In Marshall et al., the products of the two intermediate temperature isothermal expansions are applied to the same temperature level of the heat exchange means; whereas in the present invention the successively expanded material is applied to successively lower temperature portions of the heat exchange means. Relative to Dobracki et al., described above, the present invention includes at least the following distinguishing features: 1. In Dobracki et al., the intermediate pressure stream is divided and isentropically expanded at two different temperature levels to provide refrigeration at two different temperature levels; but in the present invention, the intermediate pressure stream is isentropically expanded and used to provide refrigeration only at a relatively high temperature level. 2. In Dobracki et al., a portion of the high pressure stream is withdrawn and twice expanded isentropically, but with no heat exchange between these expansions. But in the present invention, the twice-expanded portion of the high pressure stream supplies refrigeration at two different temperature levels. 3. In Dobracki et al., the isentropically expanded portion of the high pressure stream and an isentropically expanded portion of the intermediate pressure stream supply refrigeration at the same temperature level, because they are merged; but in the present invention, the three isentropically expanded streams supply refrigeration at three different temperature levels. Brief Description of the Drawings Other features and advantages of the present invention will become apparent from the following description, taken in connection with the accompanying drawings, in which: Figures 1 and 2, as pointed out above, show respectively graphs of heat transfer versus temperature when no correction of the warming curve according to the present invention is achieved, and when such a correction is required; Figure 3 is a schematic diagram of a liquefaction cycle according to the present invention; Figure 4 is a view similar to Figure 2 but which collates Figures 4A-4E, which follow; Figures 4A-4E are views similar to Figure 3, but showing modified embodiments of the cycle according to the present invention; and Figure 5 is a view similar to Figure 3, but showing the incorporation of the liquefaction cycle in an air separation unit. Definitions In the text that follows, all temperatures are given in degrees Centigrade. Pressure is in bars absolute. "Isentropic expansion" refers to expansion with work in an expansion machine which, although shown schematically in the drawings as turbo expanders, could nevertheless be any other type of expansion engine, such as reciprocating, etc. Similarly, although the compressors are shown to be centrifugal compressors in the drawings, they could be screw compressors, reciprocating compressors, axial compressors, etc. "Low-boiling gas" as used herein refers to a gas which, in its broadest sense, boils lower than -80°C. The preferred gases, however, are the atmospheric gases, i.e. those boiling no higher than oxygen, and those gases boiling lower than the atmospheric gases, e.g. hydrogen and helium. Particularly preferred is nitrogen or air, and the following description exemplifies the invention in connection with nitrogen. It is to be understood, however, that except as expressly claimed, the invention is not limited to use in connection with nitrogen. Detailed Description of the Invention Referring now to the drawings in greater detail, and first to Figure 3 thereof, there is shown schematically a cycle for the liquefaction of nitrogen, in which gaseous nitrogen at a pressure only slightly higher than 1 bar enters through conduit 1 and is compressed to about 5 bars in compressor 3. The nitrogen thus leaves compressor 3 through conduit 5 at the lowest cycle pressure. This low pressure nitrogen, flowing through conduit 7, is further compressed to an intermediate pressure in a compressor 9, which it leaves through conduit 11 at a pressure of about 36 bars and a temperature of 25°. This intermediate pressure stream is divided and a portion in conduit 13 is compressed in compressor 15 to a high pressure of 76 bars and a temperature of 25° and then flows via conduit 17 through the heat exchange means, illustrated in the drawings as a series of successively colder heat exchangers 19, 21, 23, 25 and 27. It is of course to be understood that this representation of the heat exchange means is diagrammatic only: separate heat exchangers could be used, or one continuous heat exchanger. They are shown as separate heat exchangers for convenience of description. The high pressure feed leaving the coldest heat exchanger 27 is subjected to isenthalpic expansion in a Joule-Thomson expander 29, in which it is partially liquefied, the mixed liquid and vapor being fed to a phase separator 31 from which liquid nitrogen can be withdrawn through conduit 33. Of course this high pressure feed stream can instead be expanded optionally in a dense-fluid expander to let down the pressure with minimal flash loss. The gaseous nitrogen leaves separator 31 through conduit 35 and is returned in countercurrent heat exchange with the feed to the warm end of the heat exchange means, whence it rejoins the make-up gas in conduit 7. In other words, the unliquefied nitrogen is recycled. The high pressure stream in conduit 17 reaches the expander 29 at a temperature of about -177°, and is expanded almost to the lowest cycle pressure, i.e. to 5 bars, and a temperature of -179°, at which temperature its unliquefied portion from separator 31 enters the coldest heat exchanger 27. It is warmed in exchanger 27 to -140°, is warmed in exchanger 25 to -130°, is warmed in exchanger 23 to -95°, in exchanger 21 to -28° and in exchanger 19 to +22°. A portion of the intermediate pressure feed, instead of passing through conduit 13, is diverted through conduit 37, wherein it has, as previously indicated, a pressure of 36 bars and a temperature of +25°. This intermediate pressure stream is cooled in exchanger 19 to -25°, and then is isentropically expanded in expander 39 to the lowest cycle pressure, 5 bars, and a temperature of -95°. This expanded stream passes through conduit 41 to rejoin the stream in conduit 35 passing to the warm end of the heat exchange means, to be recycled. A portion of the high pressure feed is withdrawn from between exchangers 21 and 23, at a pressure of 76 bars and a temperature of -90°, through a conduit 43 and is isentropically expanded in an expander 45 to a pressure of 24 bars and a temperature of -140°, in which condition it is fed through a conduit 47 to the cold end of exchanger 25, which it leaves through a conduit 49 at a pressure of 24 bars and a temperature of -130°, and enters an expansion engine 51 in which it undergoes further isentropic expansion to the lowest cycle temperature of -179° and almost to the lowest cycle pressure of 5 bars. This stream passes through conduit 53 whence it joins the gas in conduit 35 for return to the warmest end of the heat exchange means; but if this stream contains liquid, then it can instead be fed through conduit 55 to phase separator 31. As previously indicated, Figure 4 shows the collation of Figures 4A-4E and so provides, at a glance, an overview of the various ways in which the cycle can be modified, as well as showing the ways in which Figures 4A-4E differ from Figure 3 and from each other. Referring then to Figure 4A, it will be seen that this cycle differs from that of Figure 3, in that, instead of expanding to the lowest pressure of the cycle in expansion engine 39 and merging the expanded stream with a stream of similar pressure in conduit 35, the intermediate pressure stream is expanded in engine 39 only to a pressure of 10 bars and so is conveyed by conduit 57 separately through the exchangers 21 and 19 in that order, and then, because it is intermediate the pressure in conduits 5 and 13, is fed interstage to the compressor 7 for recycling. Figure 4B differs from Figure 3 in that a portion of the high pressure gas expanded in engine 45 and passing through conduit 47 to cool exchanger 25, is diverted from the conduit 49 that would carry all of it to engine 51; and this diverted portion passes through exchangers 23, 21 and 19 in that order via conduit 59, if it is intermediate in pressure between the pressures prevailing in conduits 5 and 13, in which case it is fed to compressor 7 interstage thereof. But if the material in conduit 47 is at the intermediate pressure prevailing in conduit 37, then after passing through exchangers 23 and 21 in that order, it is merged into conduit 37 for passage through exchanger 19 and recycle. The cycle of Figure 4C differs from that of Figure 3, by the addition of a relatively warm level external refrigeration at 63. A portion of the intermediate pressure stream is diverted from conduit 37 whence it passes through conduit 65 and through external refrigeration 63 and then rejoins conduit 37 prior to entry into expansion engine 39, thereby bypassing heat exchanger 19. It will be recalled that it was pointed out at the outset that the lack of low temperature external refrigeration in the present invention is a distinguishing feature compared to the patent to Smith et al. The presence of external refrigeration 63 does not violate that principle: the outlet temperature of 63 is higher than -45°, and so cryogenic equipment need not be used at this point, with considerable saving of cost. Also, common refrigerants such as ammonia, Freon, mixed hydrocarbons, etc. can be used. The cycle of Figure 4D differs from that of Figure 3 by the treatment of the intermediate pressure stream. In Figure 4D, instead of the entire intermediate pressure stream passing from conduit 37 to expander 39, a portion is branched off after passage through exchanger 19 and proceeds directly through exchangers 21, 23, 25 and 27 in that order, and then is isenthalpically expanded in a Joule-Thomson expander 69 to slightly over 5 bars, and is introduced into liquid separator 31. The cycle of Figure 4E differs from that of Figure 3 in that a portion of the output of expander 45 is diverted from conduit 47 into a conduit 71 in which it passes through exchanger 27 and is isenthalpically expanded in Joule-Thompson expander 73, to slightly over 5 bars, prior to introduction into phase separator 31. Figure 5 shows the combination of a liquefaction cycle according to the present invention with an air separation unit that is otherwise conventional. Beginning at the left of Figure 5, therefore, it will be seen that air introduced through conduit 75 is compressed in compressor 77 and passes via conduit 79 through heat exchanger 81, wherein it is cooled to about the liquefaction temperature of air, whereafter it is introduced into the bottom of a high pressure stage 83 of a two-stage air distillation column 85 of the usual construction, in which a low pressure stage 87 surmounts high pressure stage 83 and shares a common condenser-reboiler between the two. The pressure in high pressure stage 83 is substantially the same as the lowest pressure of the liquefaction cycle, i.e. 5 bars. In conventional fashion, oxygen-rich liquid is withdrawn from the sump of high pressure stage 83 via conduit 89, is expanded isenthalpically in Joule-Thomson expander 91 and introduced into low pressure stage 87 at the appropriate composition level. As is also conventional, liquid nitrogen is withdrawn from the top of high pressure stage 83 via conduit 93, expanded isenthalpically in Joule-Thomson expander 95, to just above atmospheric pressure, and is introduced overhead in low pressure stage 87 as reflux. As is also conventional, liquid oxygen from the sump of low pressure stage 87 is withdrawn via conduit 97 to storage. Gaseous oxygen from the bottom of low pressure stage 87 is withdrawn via conduit 99 and its refrigeration recovered in heat exchanger 81, whence the gaseous oxygen passes to an appropriate utilization. Gaseous nitrogen is withdrawn from the top of high pressure stage 83 via conduit 101 and is merged with a stream of similar composition, temperature and pressure in conduit 35. The liquid nitrogen from phase separator 31 that leaves through conduit 33 is divided, a portion passing via conduit 103 to conventional storage (with any needed pressure adjustment as for example by expansion) and the remainder passing in liquid phase through conduit 105. The liquid in conduit 105, at a pressure of 5 bars, is isenthalpically expanded through Joule-Thompson expander 107 to the lower pressure of low pressure stage 87 and is introduced into the top thereof as further reflux. Gaseous overhead from low pressure stage 87 flows via conduit 109 through heat exchanger 81 and thence to conduit 1 wherein it serves as make-up for the nitrogen refrigeration cycle. A portion of the gaseous nitrogen removed via conduit 101 is branched from conduit 101 through conduit 111, and passes at least part way through exchanger 81 wherein its refrigeration is recovered. Material in conduit 111 then serves as a warm make-up for the intermediate pressure stream. For this purpose, it can be fed directly into conduit 13, as it is already at the required pressure of 5 bars. A portion of the gaseous nitrogen undergoing warming in exchanger 81 can be withdrawn from conduit 111 at an appropriate temperature level via conduit 113 and merged with the material at the corresponding pressure and temperature level in conduit 35, e.g. between exchangers 23 and 25. As indicated above, the temperatures and pressures that have been particularly recited are exemplary only, and of course apply only to a nitrogen cycle. In general, however, the high pressure material leaving compressor 15 should have a pressure in the range of 20 to 100 bars; that leaving compressor 9 should have a pressure in the range of 10 to 50 bars and that leaving expansion engine 45 should have a pressure in the range of 10 to 80 bars. From a consideration of the foregoing disclosure, therefore, it will be evident that all of the initially recited objects of the present invention have been achieved. Although the present invention has been described and illustrated in connection with preferred embodiments, it is to be understood that modifications and variations may be resorted to without departing from the invention, as those skilled in this art will readily understand.

Claims: A method of liquefying a low-boiling point gas at a low pressure in which all of said gas (7) is compressed to an intermediate pressure, a first part (13) of said intermediate pressure gas is compressed to a high pressure, cooled in heat exchange means and is expanded and partially liquefied to form a two phase mixture in a phase separator (31) from which liquid is withdrawn, a second part (37) of said intermediate pressure gas is isentropically expanded at a first temperature to a first expanded gas temperature and is used to cool a relatively warm portion of said heat exchange means (19, 21) and is then recycled, a portion of said high pressure gas (43) is isentropically expanded at a second temperature to a second expanded gas temperature and at least part of the gas (49) at the second expanded gas temperature is further isentropically expanded at a third temperature to a third expanded gas temperature and returned through the heat exchange means and then recycled, said first expanded gas temperature being higher than said second expanded gas temperature and said second expanded gas temperature being higher than said third expanded gas temperature and said intermediate pressure being between said high and low pressures, characterized in that said at least part of the gas (47) at the second expanded gas temperature cools a relatively cool portion of said heat exchange means (25) before being expanded to said third expanded gas temperature. A method according to Claim 1, comprising the step of cooling said second part of said intermediate pressure gas in the warm end of said heat exchange means prior to isentropic expansion thereof. A method according to one of Claims 1 or 2, comprising the step of cooling the high pressure gas to a lower temperature than the said second part of intermediate pressure gas, in said heat exchange means, prior to isentropic expansion of said portion of said high pressure gas. A method according to one of Claims 1 to 3, comprising the step of cooling said high pressure gas in a relatively warm portion of said heat exchange means prior to isentropic expansion of said portion thereof. A method according to Claim 4, comprising the step of separating liquid from the last mentioned isentropically expanded gas. A method according to one of Claims 1 to 5, in which said low boiling point gas has a boiling point no higher than that of oxygen. A method according to one of Claims 1 to 6, in which said low boiling point gas is nitrogen or air. A method according to one of Claims 1 to 7, wherein said intermediate pressure gas undergoes said isentropic expansion to said low pressure. A method according to Claim 8, wherein said intermediate pressure gas undergoes said isentropic expansion to a pressure between said low pressure and said intermediate pressure. A method according to one of Claims 1 to 9, wherein a portion (59) of said gas between the two isentropic expansions at the second and third temperatures is diverted prior to the isentropic expansions at the third temperature and is returned through said heat exchange means to a warm end thereof and recycled. A method according to one of Claims 1 to 10, wherein a portion (61) of said gas between the last two isentropic expansions is diverted prior to the last isentropic expansion and is passed through a portion of said heat exchange means to cool the same but is withdrawn from said heat exchange means prior to reaching a warm end thereof and is recycled with said intermediate pressure gas. A method according to one of Claims 1 to 11 further comprising subjecting the second part of said intermediate pressure gas to external refrigeration at a temperature level above -45°C prior to said isentropic expansion thereof. A method according to Claim 12 wherein the portion of said intermediate gas that is subjected to external refrigeration bypasses said heat exchange means prior to said isentropic expansion thereof and the remainder of said intermediate pressure gas passes through and is cooled in a warm end of said refrigeration means prior to said isentropic expansion thereof. A method according to Claims 12 or 13 wherein a portion (13) of said intermediate pressure gas bypasses said isentropic expansion thereof and instead continues through said heat exchange means to a cold end thereof and is expanded. A method according to one of Claims 1 to 4 wherein a portion (71) of said gas between the isentropic expansions at the second and third temperatures is diverted prior to the last isentropic expansion, cooled in a cold end of said heat exchange means (27) and expanded. A method according to Claim 7, wherein the nitrogen feed to the liquefaction cycle is derived from an air separation method, said air separation method comprising compressing and cooling air, introducing the cooled air into a high pressure stage (83) of a two-stage air distillation column comprising also a low pressure stage (87), withdrawing oxygen-rich liquid (89) from the lower end of the high pressure stage and expanding the same and introducing the same into said low pressure stage for separation in said low pressure stage, withdrawing liquid nitrogen (93) from the high pressure stage and expanding and introducing the same into the low pressure stage as reflux, and withdrawing nitrogen (109) from the top of the low pressure stage. A method according to Claim 16, further comprising withdrawing gaseous nitrogen (101, 111) from the top of the high pressure stage of the air separation, using the same to cool said air, and then merging the same with gas in said liquefaction cycle at said low pressure of said cycle. A method according to one of Claims 16 or 17, wherein liquid nitrogen (105) produced in said liquefaction cycle is expanded and supplied to said low pressure stage (87) of said air separation as reflux. An air separation method according to one of Claims 16 to 18, wherein gaseous nitrogen from said high pressure stage of said air separation is used first to cool incoming air and then to cool a warmer portion of said heat exchange means. A method according to one of Claims 16 to 19, wherein the pressure of said high pressure stage (83) of said air separation approximately equals said low pressure of said liquefaction cycle. Apparatus for liquefying a low boiling point gas comprising : means (9) for compressing said gas to an intermediate pressure, between a high pressure and a low pressure, means (15) for compressing part of said intermediate pressure gas to a high pressure means (19, 21, 23, 25, 27) for cooling said high pressure gas, means (29) for expanding part of said high pressure gas to a low pressure separating means (31) for separating the partially condensed gas thereby produced means (33, 103) for withdrawing a liquefied gas from said separating means (31), means (39) for isentropically expanding said intermediate pressure gas at a first temperature to a first expanded gas temperature and for using the isentropically expanded gas to cool a relatively warm portion (19, 21) of said heat exchange means and then recycling said, isentropically expanded gas means (45) for isentropically expanding a portion of said high pressure gas at a second temperature to a second expanded temperature means (51) for further isentropically expanding at least some of the expanded portion of said high pressure gas at a third temperature to a third expanded gas temperature, said first expanded gas temperature being higher than said second expanded gas temperature and said second expanded gas temperature being higher than said third expanded gas temperature characterized in that it comprises means for sending the expanded portion of the high pressure gas at said second expanded gas temperature to cool a relatively cool portion (28) of said heat exchange means. Apparatus according to Claim 21, further comprising means (19) for cooling said intermediate pressure gas in the warm end of said heat exchange means prior to isentropic expansion of said gas. Apparatus according to one of Claims 21 or 22 wherein said means (19) for cooling said high pressure gas comprise means (21) for cooling the high pressure gas to a lower temperature than the intermediate pressure gas, in said heat exchange means, prior to isentropic expansion of said portion of said high pressure gas. Apparatus according to one of Claims 21 to 23 wherein said means (19) for cooling said high pressure gas comprise means (21) for cooling said high pressure gas in a relatively warm portion of said heat exchange means prior to isentropic expansion of said portion thereof. Apparatus according to one of Claims 21 to 24, wherein said separating means (31) comprise means (31) for separating liquid from the isentropically expanded gas. Apparatus according to one of Claims 21 to 25, wherein said intermediate pressure gas undergoes said isentropic expansion to said low pressure. Apparatus according to one of Claims 21 to 25, wherein said intermediate pressure gas undergoes said isentropic expansion to a pressure between said low pressure and said intermediate pressure. Apparatus according to one of Claims 21 to 27, further comprising means for diverting a portion (53) of said gas between the isentropic expansions at the second and third temperatures and for returning the same through said heat exchange means to a warm end thereof for recycle. Apparatus according to one of Claims 21 to 28 further comprising means for diverting a portion of said gas between the isentropic expansions at the second and third temperatures and for passing the same through a portion of said heat exchange means to cool the same and for withdrawing the same from said heat exchange means prior to reaching a warm end thereof and for recycling the same with said intermediate pressure gas. Apparatus according to one of Claims 21 to 29, further comprising means (C) for subjecting a portion of said intermediate pressure gas to external refrigeration at a temperature level above -45°C prior to said isentropic expansion thereof. Apparatus according to Claim 30 wherein the portion of said intermediate gas that is subjected to external refrigeration bypasses said heat exchange means prior to said isentropic expansion thereof and the remainder of said intermediate pressure gas passes through and is cooled in a warm end of said refrigeration means prior to said isentropic expansion thereof. Apparatus according to one of Claims 21 to 31 further comprising means for bypassing a portion of said intermediate pressure gas past said isentropic expansion thereof and for instead conveying the same through said heat exchange means to a cold end thereof and for expanding the same. Apparatus according to one of Claims 21 to 32 further comprising means for diverting a portion of said gas between the last two isentropic expansions prior to the last isentropic expansion, and for cooling the same in a cold end of said heat exchange means and for expanding the same. An apparatus according to one of Claims 21 to 33 further comprising means (77, 81) for compressing and cooling air to partially liquefy the same, and for introducing the partially liquefied air into a high pressure stage (85) of a two-stage air distillation column having also a low pressure stage (87) and for withdrawing oxygen-rich liquid (89) from the lower end of the high pressure stage and expanding the same and for introducing the same into said low pressure stage for separation in said low pressure stage, and for withdrawing liquid nitrogen (93) from the high pressure stage and for expanding and introducing the same into the low pressure stage as reflux, and for withdrawing nitrogen (109) from the top of the low pressure stage further comprising means for conducting said gaseous nitrogen to said liquefaction apparatus as feed. An apparatus according to Claim 34, further comprising means for withdrawing gaseous nitrogen from the top of the high pressure stage, means (85) (111) for using the same to cool said air, and means for then merging the same with gas in said liquefaction apparatus at said low pressure of said liquefaction apparatus. An apparatus according to one of Claims 34 or 35 further comprising means (105) whereby liquid nitrogen from said phase separation is expanded and supplied to said low pressure stage as reflux. An apparatus according to one of Claims 34 to 36 further comprising means whereby gaseous nitrogen from said high pressure stage is used first to cool incoming air and then to cool a warmer portion of said heat exchange means. An apparatus according to one of Claims 34 to 37, wherein said high pressure stage is at said low pressure of said liquefaction apparatus.

Inventors: HA BAO, TRANIER JEAN-PIERRE, HA, BAO, TRANIER, JEAN-PIERRE
Applicants: AIR LIQUIDE, LIQUID AIR ENG CORP, L'AIR LIQUIDE, SOCIETE ANONYME POUR L'ETUDE ET L'EXPLOITATION DES PROCEDES GEORGES CLAUDE, LIQUID AIR ENGINEERING CORPORATION
Application year: 1993
Main classification: F25J1
IPC codes: F25J1, F25J3