Patent Application
20120036891
The present invention relates to a method and apparatus for separating air in which oxygen-rich liquid is pumped to produce a pumped liquid oxygen stream having a supercritical pressure that is in turn warmed to a supercritical temperature through indirect heat exchange with a boosted pressure air stream to produce an oxygen product as a supercritical fluid. More particularly, the present invention relates to such a method and apparatus in which a liquid nitrogen stream is simultaneously vaporized while the pressurized liquid stream is heated, so as to depress the pressure that would otherwise be required of the boosted pressure air stream to heat the pumped liquid oxygen stream alone.
There exists an emerging market for very high pressure supercritical oxygen that is being driven primarily by requirements of gasifiers for such oxygen. Typically, the oxygen is produced from the cryogenic separation of air. Although oxygen produced by such cryogenic rectification can be produced at moderate operational pressures and then compressed, more often, a liquid oxygen stream is pumped to a supercritical pressure within a cryogenic rectification plant and then heated to a supercritical temperature through indirect heat exchange with a boosted pressure air stream to produce an oxygen product as a supercritical fluid.
In a cryogenic rectification plant, a feed air stream is compressed and purified of higher boiling contaminants such as moisture, carbon dioxide, carbon monoxide and hydrocarbons to produce a compressed and purified air stream. Part of such air stream can be cooled within a lower pressure heat exchanger of a banked heat exchanger arrangement consisting of at least one higher pressure heat exchanger and at least one lower pressure heat exchanger. In the banked heat exchanger arrangement the higher pressure heat exchanger is provided for heating the pumped liquid oxygen stream to a supercritical temperature through indirect heat transfer with a high pressure boosted air stream. The use of such heat exchanger banking saves fabrication costs in that it is only the higher pressure heat exchanger that must be fabricated to withstand the high oxygen pressure and the even higher pressures of the boosted air stream that are necessary to heat the oxygen. In any case, the cooled air from the lower pressure heat exchanger is then introduced into an air separation unit that has a higher pressure column and a lower pressure column in a heat transfer relationship to rectify the air into nitrogen and oxygen-rich fractions. Such air separation units can also include an argon column connected to the lower pressure column to rectify an argon containing vapor stream into an argon-rich product or an intermediate argon product known in the art as crude argon.
The higher and lower pressure columns contain mass transfer contacting elements such as trays or structured packing or a combination of such elements to contact liquid and vapor phases and thereby accomplish a continuous distillation within such columns. The air entering the higher pressure column produces an ascending vapor phase that becomes evermore rich in nitrogen as it ascends the higher pressure column to produce a nitrogen-rich vapor as a column overhead. The nitrogen-rich vapor is then condensed to produce a nitrogen-rich liquid that in part is used to reflux the higher pressure column and initiate a descending liquid phase that contacts the ascending vapor phase within the mass transfer contacting elements and becomes ever more richer in oxygen as such liquid phase descends. As a result, a crude liquid oxygen column bottoms is produced in the higher pressure column that is also known as kettle liquid. Such liquid bottoms is further refined in the lower pressure column and in case an argon column is present, also serves as a heat transfer media to condense the argon-rich vapor in the argon column prior to being introduced into the lower pressure column. The further refinement produces an oxygen-rich liquid column bottoms in the lower pressure column and a tower overhead that is rich in nitrogen. A stream of the oxygen-rich liquid is then removed and pumped to produce the pumped liquid oxygen stream that at least in part is introduced into the higher pressure heat exchanger to form the oxygen product.
The heat transfer relationship between the higher and lower pressure column is produced by a condenser reboiler that can be situated in the sump of the lower pressure columns. A stream of the nitrogen-rich vapor column overhead of the higher pressure column is condensed to produce the nitrogen-rich liquid that serves in part as reflux to the higher pressure column. The condensation is through indirect heat exchange with the oxygen-rich liquid column bottoms of the lower pressure column that causes such liquid to boil and produce boilup in the lower pressure column. Part of the nitrogen-rich liquid can be taken as a product and in fact, can be pumped and also introduced into the higher pressure heat exchanger along with the pumped liquid oxygen stream. In U.S. Patent Application Publication No. 2008/0307828 both pumped oxygen and nitrogen streams are passed through a higher pressure heat exchanger of a banked heat exchange arrangement to produce an oxygen product as a supercritical fluid and to vaporize the pumped nitrogen stream and thereby produce a nitrogen vapor product at pressure.
In producing oxygen at supercritical pressures, the higher pressure heat exchanger must be built to withstand even higher pressures than the oxygen stream to be heated. For example, if 120 bar absolute oxygen is to be heated to a supercritical temperature, the boosted pressure air stream will optimally have a pressure in the order of 160 bar absolute. The problem with this is that the cost in fabricating such a heat exchanger to withstand the pressure of the boosted air stream can become prohibitively expensive, as well as the cost of the associated pipework and valves which must also be rated to the same very high pressure. In addition, there can be increased energy costs in that an inline barrel compressor might be required, depending on the pressure, that has an efficiency that is less than an integrally geared compressor that could be employed at a lower pressure. Finally, during the startup of such a system the consequences of a failed pressure test at very high pressures can be quite severe.
There is therefore, a need to minimize the pressure of the boosted pressure air stream that is required in heating the pumped liquid oxygen to a supercritical temperature.
As will be discussed, the present invention provides a method and apparatus for separating air involving warming both a pumped liquid oxygen stream at supercritical pressure and a liquid nitrogen stream within a heat exchanger in a manner in which the flow rate of the liquid nitrogen to be vaporized is sufficient to allow for operation at a pressure that is lower than that which would otherwise be required of the boosted pressure air stream.
In one aspect, the present invention provides a method of separating air in which the air is separated in a cryogenic rectification process. In such process, compressed, purified and cooled air is rectified in an air separation unit having a higher pressure column and a lower pressure column and at least part of a pumped liquid oxygen stream is heated and a liquid nitrogen stream is vaporized through indirect heat exchange with a boosted pressure air stream. At least part of an oxygen-rich stream composed of an oxygen-rich liquid column bottoms produced in the lower pressure column is pumped to produce the pumped liquid oxygen stream. The liquid nitrogen stream is produced from part of a nitrogen-rich liquid stream that is formed by condensing a nitrogen-rich vapor column overhead of the higher pressure column against partly vaporizing the oxygen-rich liquid column bottoms and that is not used as reflux.
The at least part of the pumped liquid oxygen stream has a supercritical pressure and is heated to a supercritical temperature to produce an oxygen product as a supercritical fluid. The at least part of the pumped liquid oxygen stream constitutes at least about 90 percent of the oxygen-rich stream and the at least part of the liquid nitrogen stream has a subcritical pressure and constitutes at least about 90 percent of the part of the nitrogen-rich liquid stream. The liquid nitrogen stream and the at least part of the pumped liquid oxygen stream have flow rates in a ratio of between 0.3 and 0.90. The boosted pressure air stream has a boosted pressure and a flow rate. The boosted pressure is lower than that which would otherwise have been required at the flow rate had there been no indirect heat exchange within the heat exchanger with the liquid nitrogen stream.
The inventors herein have found that under certain operation conditions, vaporizing a liquid nitrogen stream together with the heating of the pumped liquid oxygen stream will have a substantial effect on the shape of the composite cooling curve. The upper ratio limit of 0.90 is selected to ensure that there will be sufficient reflux as not to severely effect oxygen recovery and the lower ratio limit of 0.3 represents a limitation where there is not a sufficient depression of the required pressure for the boosted pressure air stream.
It is to be noted that the heating and cooling curves represent the aggregate heat transfer from the boosted pressure air stream and any other streams to be cooled to the warming oxygen and warming/vaporizing nitrogen stream and any other streams to be warmed. The composite curves combine multiple cooling streams (“hot” streams) into a single curve and multiple warming streams (“cold” streams) into a single stream. At a given temperature within the heat exchanger, the composite curve is defined such that the sum of the energy change of each hot or cold stream defines the duty for the hot or cold composite curve, respectively. Composite curves are used to simplify and idealize the analysis of heat exchangers with more than two streams transferring heat simultaneously.
The effect of simultaneously vaporizing a liquid nitrogen stream in the higher pressure heat exchanger, in addition to heating the pumped liquid oxygen stream is to alter the shape of the composite cooling curve such that it enables the designer to lessen the pressure that would otherwise be required of the boosted pressure air stream to heat an oxygen stream at a supercritical pressure to a supercritical temperature if such oxygen stream were the only stream being heated within the higher pressure heat exchanger. In this regard, in a non-banked heat exchanger arrangement, all of the streams to be warmed and cooled are passed in indirect heat exchange within a single heat exchanger that in most practical applications is a series of heat exchangers run in parallel. Where the designer desires to decrease the pressure of the boosted pressure air stream, a problem that arises is that the flow rate of such stream must be increased. Where the liquid nitrogen stream is vaporized, the change in shape of such curves allows the flow rate of the boosted pressure air stream to be lower than that had such liquid nitrogen stream not been present. The higher flow rate results in more liquid air being produced that will result in a loss of column performance and at an extreme, will not allow column operation. In the banked case in which all of such heat exchange takes place within a higher pressure heat exchanger, the liquid nitrogen vaporization allows such heat exchanger to function at a reasonable approach temperature at the point within the heat exchanger at which the liquid oxygen becomes a supercritical fluid, typically 5 degrees Kelvin or less. If the liquid nitrogen were not present, not only would the heat exchanger not function at the flow rate required with the liquid nitrogen, but at an extreme of operation, the heating and cooling curves would in fact cross preventing any operation of the heat exchanger.
As indicated above, the at least part of the pumped liquid oxygen stream can be heated and the liquid nitrogen stream can be vaporized within a higher pressure heat exchanger of a banked heat exchanger arrangement through indirect heat exchange with the boosted pressure air stream.
An argon containing vapor stream can be removed from the lower pressure column and rectified in an argon column to produce an argon-rich vapor column overhead and an oxygen containing liquid column bottoms. The argon-rich vapor column overhead is condensed to produce an argon reflux stream that is introduced into the argon column. An argon-rich product stream is removed from the argon column and an oxygen containing liquid stream, composed of the oxygen containing liquid column bottoms, is introduced into the lower pressure column. In a specific embodiment, a crude liquid oxygen stream, composed of a crude liquid oxygen column bottoms produced in the higher pressure column, is subcooled. At least part of the crude liquid oxygen stream, after having been subcooled, is valve expanded and introduced into an argon condenser connected to the argon column to condense the argon-rich vapor stream, thereby to partially vaporize the crude liquid oxygen stream and form a vapor phase and a liquid phase. A vapor phase stream and a liquid phase stream, composed of the vapor phase and the liquid phase, respectively, are introduced into the lower pressure column and a liquid air stream, formed from liquefaction of the boosted pressure air stream, is expanded and divided into a first subsidiary liquid air stream and a second subsidiary liquid air stream. The first subsidiary liquid air stream is introduced into the higher pressure column and the second subsidiary liquid air stream is introduced into the argon condenser and is thereby subcooled. The second subsidiary liquid air stream, after having been subcooled, is expanded and introduced into the lower pressure column.
The air can be compressed and purified by compressing a feed air stream in a main air compressor and purifying the air after the compression thereof in a pre-purification unit to form a compressed and purified air stream. A first part of the compressed and purified air stream is cooled in a lower pressure heat exchanger of the banked heat exchanger arrangement to a temperature suitable for its rectification and introduced into the higher pressure column. At least a portion of a second part of the compressed and purified air stream is compressed in a booster compressor to form the boosted pressure air stream. A third part of the compressed and purified air stream can be further compressed, partially cooled in the lower pressure heat exchanger and expanded in a turboexpander to produce an exhaust stream. The exhaust stream, along with the first part of the compressed and purified air stream, is rectified within the higher pressure column. The portion of the second part of the compressed and purified air stream can be compressed in the booster compressor in forming the boosted pressure air stream. In such case, the third part of the compressed and purified air stream is composed of another portion of the second part of the compressed and purified air stream after having been partially compressed in an intermediate stage of the booster compressor and is further compressed in another booster compressor.
A further part of the nitrogen-rich liquid stream can be introduced into the higher pressure column as reflux and a nitrogen containing reflux stream having a lower nitrogen purity than the nitrogen-rich liquid stream can be subcooled, expanded and introduced as reflux to the lower pressure column. A lower pressure nitrogen vapor stream, composed of column overhead of the lower pressure column, can be used to subcool the nitrogen containing reflux stream and the crude liquid oxygen stream in a subcooler through indirect heat exchange. The lower pressure nitrogen vapor stream is divided into a first and second subsidiary lower pressure nitrogen vapor streams that are introduced, respectively, into the higher pressure heat exchanger and the lower pressure heat exchanger to balance cold end temperatures.
In any embodiment of the present invention, the liquid nitrogen stream and the nitrogen-rich liquid stream may have the same pressure. It is understood, however, that the present invention contemplates that the liquid nitrogen stream may be raised in pressure by liquid head or a pump.
In another aspect of the present invention, an apparatus is provided for separating air that comprises a cryogenic air separation plant. Such plant includes an air separation unit having a higher pressure column and a lower pressure column to rectify the air, a heat exchanger in flow communication with the air separation unit and a pump. The heat exchanger is configured to indirectly exchange heat from a boosted pressure air stream to at least part of a pumped liquid oxygen stream having a supercritical pressure and a liquid nitrogen stream, thereby to heat the pumped liquid oxygen stream to a supercritical temperature and form an oxygen product as a supercritical fluid and to vaporize the liquid nitrogen stream and form a nitrogen product as a vapor. The pump is positioned between the heat exchanger and the lower pressure column such that at least part of an oxygen-rich stream composed of an oxygen-rich liquid column bottoms produced in the lower pressure column is pressurized to the supercritical pressure and the at least part of the pumped liquid oxygen stream constitutes at least about 90 percent of the oxygen-rich stream.
The heat exchanger is in flow communication with a condenser reboiler operatively associated with the higher pressure column and the lower pressure column such that the liquid nitrogen stream is composed of at least about 90 percent of a part of a nitrogen-rich liquid stream produced by condensing a nitrogen-rich vapor column overhead of the higher pressure column against partly vaporizing the oxygen-rich liquid column bottoms within the condenser reboiler that is not used as reflux for the columns. Such liquid nitrogen stream has a subcritical pressure. The air separation plant is configured such that the liquid nitrogen stream and the at least part of the pumped liquid oxygen stream having flow rates in a ratio of between 0.3 and 0.90. The boosted pressure air stream is produced by a booster compressor that is configured such that the boosted pressure air stream has a flow rate and a boosted pressure lower than that which would otherwise have been required at the flow rate had there been no indirect heat exchange within the heat exchanger with the liquid nitrogen stream.
The heat exchanger can be a higher pressure heat exchanger of a banked heat exchanger arrangement also having a lower pressure heat exchanger.
An argon column can be connected to the lower pressure column such that an argon containing vapor stream is removed from the lower pressure column and is rectified in the argon column to produce an argon-rich vapor column overhead and an oxygen containing liquid column bottoms. An oxygen containing liquid stream composed of the oxygen containing liquid column bottoms is introduced into the lower pressure column. An argon condenser is connected to the argon column such that the argon-rich vapor column overhead is condensed to produce an argon reflux stream that is introduced into the argon column and the argon column having an outlet to discharge an argon-rich product stream from the argon column. In a specific embodiment, a subcooling unit can be connected to the higher pressure column such that a crude liquid oxygen stream, composed of a crude liquid oxygen column bottoms produced in the higher pressure column, is subcooled. The argon condenser is connected to the subcooling unit and a first expansion valve is positioned between the argon condenser and the subcooling unit such that at least part of the crude liquid oxygen stream, after having been subcooled, is valve expanded in the first expansion valve and introduced into the argon condenser to condense the argon-rich vapor stream and thereby to partially vaporize the at least part of the crude liquid oxygen stream and form a vapor phase and a liquid phase. The argon condenser is also connected to the lower pressure column such that a vapor phase stream and a liquid phase stream, composed of the vapor phase and the liquid phase, respectively, are introduced into the lower pressure column. A liquid expander is connected to the higher pressure heat exchanger such that a liquid air stream produced as a result of the liquefaction of the boosted pressure air stream is expanded. The liquid expander connected to the higher pressure column and the argon condenser such that a first subsidiary liquid air stream composed of part of the liquid air stream is introduced into the higher pressure column and a second subsidiary liquid air stream composed of another part of the liquid air stream is introduced into the argon condenser. The argon condenser is configured to subcool the second subsidiary liquid air stream and is connected to the lower pressure column such that the second subsidiary liquid air stream, after having been subcooled is introduced into the lower pressure column. A second expansion valve positioned between the argon condenser and the lower pressure column to valve expand the second subsidiary liquid air stream.
A main air compressor can be provided to compress a feed air stream and a pre-purification unit can be connected to the main air compressor to form a compressed and purified air stream from the feed air stream after having been compressed. The banked heat exchanger arrangement has a lower pressure heat exchanger positioned between the pre-purification unit and the higher pressure column such that a first part of the compressed and purified air stream is cooled to a temperature suitable for the rectification thereof and is introduced into the higher pressure column. A booster compressor is positioned between the pre-purification unit and the higher pressure heat exchanger such that at least a portion of a second part of the compressed and purified air is further compressed in the booster compressor to form the boosted pressure air stream. The booster compressor can be configured to compress a portion of the second part of the compressed and purified air stream to produce the boosted pressure air stream and to discharge a third part of the compressed and purified air stream, composed of another portion of the second part of the compressed and purified air stream from an intermediate stage of the booster compressor. Another booster compressor is positioned between the intermediate stage and the lower pressure heat exchanger such that the third part of the compressed and purified air stream is further compressed and introduced into the lower pressure heat exchanger. The lower pressure heat exchanger is configured to partially cool the third part of the compressed and purified air stream and a turboexpander is connected to the lower pressure heat exchanger to expand the third part of the compressed and purified air stream and thereby produce an exhaust stream. The turboexpander is in flow communication with the higher pressure column such that the exhaust stream, along with the first part of the compressed and purified air stream, is rectified within the higher pressure column.
The condenser reboiler is connected to the higher pressure column such that a further part of the nitrogen-rich liquid stream is introduced into the higher pressure column as reflux. The subcooling unit is connected to the higher pressure column such that a nitrogen containing reflux stream is discharged from the higher pressure column having a lower nitrogen purity than the nitrogen-rich liquid stream and is subcooled in the subcooling unit. The subcooling unit is connected to the lower pressure column such that the nitrogen containing reflux stream is introduced as reflux to the lower pressure column. A third expansion valve is positioned between the subcooler and the lower pressure column such that the nitrogen containing reflux stream is expanded within the third expansion valve. The subcooler is also connected to the lower pressure column such that a lower pressure nitrogen vapor stream, composed of column overhead of the lower pressure column, subcools the nitrogen containing reflux stream and the crude liquid oxygen stream through indirect heat exchange. The higher pressure heat exchanger is connected to the low pressure column and the lower pressure heat exchanger is connected to the subcooler such that first and second subsidiary lower pressure nitrogen vapor streams, composed of the lower pressure nitrogen vapor stream, are introduced, respectively, into the higher pressure heat exchanger and the lower pressure heat exchanger to balance temperatures.
The higher pressure heat exchanger can be in flow communication with the condenser reboiler such that the liquid nitrogen stream and the nitrogen-rich liquid stream have the same pressure.
While the specification concludes with claims distinctly pointing out the subject matter that Applicants regard as their invention, it is believed that the present invention will be better understood when taken in connection with the accompanying drawings in which:
With reference to
In cryogenic rectification plant 1, a feed air stream 10 is compressed in a compressor 12 to produce a compressed air stream 14. The heat of compression is removed from compressed air stream 14 by an aftercooler 16. It is understood that compressor 12 may constitute a multi-stage intercooled integral gear compressor with condensate removal and consequently, aftercooler 16 could be part of compressor 12. In any case aftercooler 16 as well as other aftercoolers mentioned will allow the performance of downstream unit operations such as prepurifiers and heat exchangers to be improved. However, it is possible that an embodiment of the present invention could be constructed without such aftercoolers.
The compressed air stream 14 is then introduced into a prepurification unit 18 to remove higher boiling impurities such as water vapor, carbon dioxide and hydrocarbons from the air and thereby produce a compressed and purified air stream 20. As well known in the art, such unit 16 can incorporate adsorbent beds operating in a cycle that is a combination of temperature and pressure swing adsorption or that is purely a temperature swing adsorption cycle or a pressure swing adsorption cycle.
The banked heat exchanger arrangement 2 has a lower pressure heat exchanger 22 positioned between the pre-purification unit 18 and a higher pressure column 58 of the air separation unit 3 such that a first part 24 of the compressed and purified air stream 20 is cooled to a temperature suitable for the rectification thereof and is introduced into the higher pressure column 58. A booster compressor 26 is positioned between the pre-purification unit 18 and a higher pressure heat exchanger 28 of the banked heat exchanger arrangement 2 such that a portion of a second part 30 of the compressed and purified air is further compressed in the booster compressor 26 to form a boosted pressure air stream 32. Booster compressor 26 is a multi-stage integral geared compressor. After removal of the heat of compression by an aftercooler 34, the boosted pressure air stream 32 is introduced into the higher pressure heat exchanger 28. The booster compressor 26 is configured to produce the flow rates and pressure of the boosted pressure air stream 32 that are required by the present invention in a manner well known in the art. In this regard, the booster compressor 26 has to be appropriately sized to have the capability of delivering the required pressure and flow and will incorporate suitable controls for controlling its pressure output and flow but such means as inlet guide vanes and downstream controls.
It is to be noted that main air compressor 12 and booster compressor 26 are shown as single units. However, as is known in the art, two or more compressors can be installed in parallel to form either the main air compressor 12 or the booster compressor 26. The two compressors can be of equal size or unequal size. For example, the capacity can be split 70/30 or 60/40 in order to better match customer demand. Typically, the second part 30 of the compressed and purified air stream 20 will have a flow that ranges from between about 25 percent and about 40 percent of the flow of the compressed and purified air stream 20.
Both the higher pressure heat exchanger 28 and the lower pressure heat exchanger 22 are preferably of brazed aluminum construction and consist of layers of parting sheets separated by side bars to produce flow passages for the streams to be heated and cooled. Each of the flow passages are provided with fins as well known in the art to enhance the surface area for heat transfer within said heat exchangers. The higher pressure heat exchanger 28 is so named due to the fact that it has a higher maximum allowable working pressure as compared with lower pressure heat exchanger 22. The higher pressure heat exchanger 28 is configured to fully cool the boosted pressure air stream 32 to produce a liquid air stream 36 and the lower pressure heat exchanger 22 is configured to fully cool the first part 24 of the compressed and purified air stream 20 to produce a main feed air stream 38. In this regard, the term “fully cooled” as used herein and in the claims means cooled to a temperature at the cold end of either the lower pressure heat exchanger 22 or the higher pressure heat exchanger 28.
Other types of heat exchangers could be used, for example, higher pressure heat exchanger 28 could be a copper or stainless steel spiral wound, a stainless steel printed circuit or of stainless steel plate-fin construction. Furthermore, as indicated above, the present invention is applicable to a non-banked arrangement in which a heat exchanger or a set of heat exchangers in parallel are each used both in the liquefaction of the boosted pressure air stream 32 and the cooling of the first part 24 of the compressed and purified air stream 20. Moreover, although each of the higher pressure heat exchanger 28 and the lower pressure heat exchanger 22 are illustrated as single units, in practice, each could consist of several individual heat exchanger blocks or cores linked together in parallel.
A third part 40 of the compressed and purified air stream 20, that constitutes another portion of the second part 30 of the compressed and purified air stream 20, is partly compressed within booster compressor 26 and then removed from an intermediate stage thereof. The third part 40 of the compressed and purified air stream 20 is then introduced into another booster compressor 42, cooled within an aftercooler 44 to remove the heat of compression, partially cooled within lower pressure heat exchanger 22 and then introduced into turboexpander 46 to produce an exhaust stream 48. The term, “partially cooled”, as used herein and in the claims, means cooled to a temperature between the warm and cold end temperatures of the lower pressure heat exchanger 22. Exhaust stream 48 is introduced into the higher pressure column 58 along with first part 24 of the compressed and purified air stream 20 as a combined stream 50. Energy is recovered from the turboexpander and applied to the booster compressor 42. The purpose of this is to generate part of the refrigeration requirements of the cryogenic air separation plant. As known in the art, such refrigeration is imparted due to warm end losses in the lower and higher pressure heat exchangers 22 and 28, heat in-leak losses, and in order to allow the plant to produce liquids. It is possible to construct an embodiment of the present invention in which the third part 40 of the compressed and purified air stream 20 is partially cooled within the higher pressure heat exchanger 28. However, this would not be preferable in that more power would have to be supplied to booster compressor 26.
As will be discussed, the liquid air stream 36 produced through liquefaction of the boosted pressure air stream 32 can be introduced into a liquid expander 52 to generate further refrigeration requirements for the plant. Liquid air stream 36, after the expansion thereof, can be divided into first and second subsidiary liquid air streams 54 and 56. First subsidiary liquid air stream 54 is introduced into higher pressure column 58 and second subsidiary liquid air stream 56 is introduced into lower pressure column 60 in a manner that will be discussed hereinafter.
Air separation unit 3 is provided with a higher pressure column 58, a lower pressure column 60 and an argon column 62. All of such columns contain mass transfer contacting elements such as trays or packing, for instance structured packing or a combination of trays and packing. An ascending vapor phase originated from the combined stream 50 that is introduced into the higher pressure column 58 becomes evermore rich in nitrogen to produce a nitrogen-rich vapor column overhead that is withdrawn as a nitrogen-rich vapor stream 64 and condensed within a condenser reboiler 66 located in the sump of the lower pressure column 60 to produce a nitrogen-rich liquid stream 68. An oxygen-rich liquid column bottoms 70 is in part vaporized in connection with the condensation of the nitrogen-rich vapor stream 64. A part 72 of the nitrogen-rich liquid stream 68 is returned to the higher pressure distillation column 58 as reflux and thereby establish a descending liquid phase that becomes evermore rich in oxygen through contact with the ascending vapor phase and thereby to produce a crude liquid oxygen column bottoms 74 of the higher pressure column 58.
A crude liquid oxygen stream 75, composed of the crude liquid oxygen column bottoms 74 is further refined in the lower pressure column 60. For such purposes, the crude liquid oxygen stream 75 is subcooled within a subcooling unit 76 and then divided. A part 78 of the crude liquid oxygen stream 74, after expansion within expansion valve 80, is introduced into lower pressure column 60. A part 82 of the crude liquid oxygen stream 75 is then valve expanded in expansion valve 84 and introduced into argon condenser 102 where it partially vaporizes into vapor and liquid phases. Liquid and vapor phase streams 86 and 88, composed of the liquid and vapor phases, respectively, are introduced into the lower pressure column 60. Lower pressure column 60 is refluxed with an nitrogen containing reflux stream 90 removed from the higher pressure column 58 at a level at which such stream has a lower nitrogen content than the part 72 of the nitrogen-rich liquid stream 68. Nitrogen containing liquid stream 90 is subcooled in the subcooling unit 76, expanded in an expansion valve 92 and then introduced into lower pressure column 60.
The advantage of argon column 60 is that oxygen recovery will be improved because argon is being separated from the downcoming liquid phase. An argon containing vapor stream 94 is removed from the lower pressure column 60 and introduced into the argon column 62 and rectified to produce an argon-rich column overhead and an oxygen containing liquid column bottoms 96. An oxygen containing liquid stream 98 composed of the oxygen containing liquid column bottoms 96 is returned to the lower pressure column 60. The argon-rich vapor column overhead is removed as an argon-rich vapor stream 100 and condensed in an argon condenser 102 to produce reflux for the argon column 62. The argon condenser illustrated herein has a shell 104 and a heat exchanger 106 within the shell 104. The part 82 of the crude liquid oxygen stream 75, after having been subcooled and expanded is introduced into the shell 104 where it is partially vaporized into liquid and vapor phases against condensing the argon-rich vapor containing in the argon-rich vapor stream 100 that is passed through the heat exchanger 106. Liquid phase and vapor phase streams 86 and 88 composed of such liquid and vapor phases, are reintroduced into the lower pressure column 60. The resulting argon-rich liquid stream 108 is passed into a phase separator 110 to produce a vapor phase that is discharged as a vapor phase stream 112 and a liquid phase that is discharged from the phase separator 110 as a liquid reflux stream 114 that is reintroduced into the argon column 62. The purpose of this is to prevent the build-up of nitrogen in stream 100 in case of an operational excursion. Too much nitrogen could result in ceasing operation of condenser 106 due to a reduction of the temperature difference, as is known in the art. An argon product stream 116 can be removed from the argon column as a liquid or a vapor.
In the illustrated embodiment, the heat exchanger 106 is provided with a set of passages to subcool second subsidiary liquid air stream 56. The resulting subcooled second subsidiary liquid air stream 118 is valve expanded to the pressure of lower pressure column 62 in an expansion valve 120 and introduced into the lower pressure column 62. The advantage here is that oxygen recovery will be improved along with argon recovery.
An oxygen-rich liquid stream 122, composed of the oxygen-rich liquid column bottoms 70, can be divided into first and second oxygen-rich liquid streams 124 and 126. First oxygen-rich liquid stream 124 is pumped in a pump 128 to a supercritical pressure to produce a pumped liquid oxygen stream 130. Second oxygen-rich liquid stream 126 is optional and can be taken as a product. Alternatively and/or in addition, part of the pumped liquid oxygen could be taken as a product. Pumped liquid oxygen stream 130 is thereafter heated within the higher pressure heat exchanger 28 to a supercritical temperature so that an oxygen product stream 132 is discharged as a supercritical fluid.
As mentioned above, in order to reduce the pressure required for the boosted pressure of air stream, a liquid nitrogen stream 133 formed of part of the nitrogen-rich liquid stream 68 is vaporized within the higher pressure heat exchanger 28 to produce a nitrogen product stream 134 at pressure. Although such stream is illustrated as having the same pressure as nitrogen-rich liquid stream 68, the liquid nitrogen stream 133 could be pumped to a pressure below the supercritical pressure of the nitrogen contained in such stream if higher pressure nitrogen were required. However, it is important that the nitrogen be at a pressure so that it in fact vaporizes during heating. It is also to be noted that another liquid nitrogen stream 136 composed of another part of the nitrogen-rich liquid stream 68 can be subcooled within subcooling unit 76 and taken as an optional liquid nitrogen product stream 138. However, liquid nitrogen stream 133 should constitute at least 90 percent of the part of the nitrogen-rich liquid stream 68 that is not returned to the higher pressure column 58 as the reflux stream 72. Moreover, flow rates of the liquid nitrogen stream 133 and the pumped liquid oxygen stream 130 should be in a ratio of between about 0.3 and about 0.90. In this regard, pumped liquid oxygen stream or the part thereof that is heated within the higher pressure heat exchanger 28 should constitute at least 90 percent of the flow rate of the oxygen-rich liquid stream 122. Above a ratio of 0.90, oxygen production will fall to about 94 percent of that which would otherwise be produced without the production of vaporized nitrogen. As will be discussed, the lower limit is a limit where there will not be a meaningful effect of being able to reduce the boosted pressure of the boosted pressure air stream 32. It is to be pointed out that such nitrogen flow rates can be controlled by means of a valve, with appropriately sized equipment for the flow path, such as piping and heat exchangers. When the nitrogen is pumped, the pump flow and head characteristics control the nitrogen flow rates. Further, the liquid nitrogen stream 133 could be pumped so long it was not pumped beyond a supercritical pressure which is about 34 bar absolute.
The lower limit of 0.3 can be best explained with reference to
Referring to
A nitrogen vapor stream 140 composed of the nitrogen-rich vapor column overhead of the lower pressure column 60 is preferably divided into first and second nitrogen vapor streams 142 and 144. First nitrogen vapor stream 142 is introduced into the subcooling unit 76 for the subcooling duty required by such unit and then is fully warmed within the lower pressure heat exchanger 22. Second nitrogen vapor stream 144 is introduced into the higher pressure heat exchanger 28, fully warmed and discharged as a waste nitrogen stream 146. The flow rate of the first and second nitrogen streams 142 and 144 should be selected in a known manner to optimally balance the temperature profiles of the higher and lower pressure heat exchangers 28 and 22. This is done with the goal of avoiding tight temperature approaches in heat exchangers 28 and 22, and to minimize the heat transfer surface required. The first nitrogen stream 142 after having been fully warmed can be divided into a regeneration stream 148 that is used to regenerate adsorbents within pre-purification unit 18 with the remainder discharged as a waste nitrogen stream 150. It is to be noted that the second nitrogen stream 144 within the higher pressure heat exchanger will have no effect on the nitrogen to oxygen ratios set forth above.
As illustrated, the resulting nitrogen product stream 132, if desired at higher pressure can be in part compressed by a compressor 152 to produce a high pressure nitrogen stream 154. The remaining part of the nitrogen product stream 132 can therefore be taken as a lower pressure nitrogen stream 156.
The following table is a simulated example of the operation of air separation plant 1 in accordance with the present invention.
402
523
324
905
1Stream 142 after having been fully heated within lower pressure heat exchanger 22
2Stream 40 after booster compressor 42 and before entering lower pressure heat exchanger 22
3Stream 40 after having been partially cooled within lower pressure heat exchanger 22
4Stream 32 after aftercooler 34 and before entering higher pressure heat exchanger 28
5Stream 90 after having been subcooled within subcooling unit 76
While the present invention has been described with reference to a preferred embodiment, as will occur to those skilled in the art, numerous changes, additions and omissions can be made without departing from the spirit and scope of the invention as set forth in the appended claims.
